Crystallographic Investigation of n-Aminopyridinium Perhalometallates Appendix B: Detailed Crystallographic and Structural Data Crystallographic Data for Bis(2-aminopyridinium) tetrachlorozincate(II) Table 1. Crystal data and structure refinement for 2ampZnCl. Identification code 2ampZnCl Empirical formula C10 H14 Cl4 N4 Zn Formula weight 1589.32 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group C 2/c Unit cell dimensions a = 8.3104(6) ? ?= 90?. b = 14.1150(17) ? ?= 93.641(6)?. c = 13.8427(10) ? ? = 90?. Volume 1620.5(3) ?3 Z 1 Density (calculated) 1.629 Mg/m3 Absorption coefficient 2.166 mm-1 F(000) 800 Crystal size 0.6 x 0.4 x 0.1 mm3 Theta range for data collection 3.99 to 26.99?. Index ranges -9<=h<=10, -18<=k<=17, -16<=l<=17 Reflections collected 6308 Independent reflections 1772 [R(int) = 0.0219] Completeness to theta = 25.00? 99.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 1772 / 0 / 88 Goodness-of-fit on F2 1.050 Final R indices [I>2sigma(I)] R1 = 0.0213, wR2 = 0.0522 R indices (all data) R1 = 0.0290, wR2 = 0.0559 Extinction coefficient 0.0153(6) Largest diff. peak and hole0.295 and -0.236 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 2ampZnCl. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b1 Crystallographic Investigation of n-Aminopyridinium Perhalometallates x y z U(eq) ________________________________________________________________________________ C(1) 4124(2) 1933(1) 558(1) 46(1) C(2) 3293(2) 583(1) -377(2) 59(1) C(3) 4153(3) 854(2) -1117(2) 64(1) C(4) 5048(2) 1691(2) -1022(2) 62(1) C(5) 5043(2) 2223(1) -208(1) 53(1) Cl(1) 2111(1) 1318(1) 3026(1) 61(1) Cl(2) 999(1) -533(1) 1344(1) 68(1) N(1) 4023(2) 2426(1) 1365(1) 60(1) N(2) 3298(2) 1115(1) 439(1) 51(1) Zn(1) 0 394(1) 2500 45(1) Table 3. Bond lengths [?] and angles [?] for 2ampZnCl. _____________________________________________________ C(1)-N(1) 1.322(2) C(1)-N(2) 1.348(2) C(1)-C(5) 1.407(2) C(2)-C(3) 1.342(3) C(2)-N(2) 1.355(3) C(2)-H(2) 0.9300 C(3)-C(4) 1.398(3) C(3)-H(3) 0.9300 C(4)-C(5) 1.354(3) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 Cl(1)-Zn(1) 2.2688(5) Cl(2)-Zn(1) 2.2658(5) N(1)-H(1A) 0.8601 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8601 Zn(1)-Cl(2)#1 2.2658(5) Zn(1)-Cl(1)#1 2.2688(5) N(1)-C(1)-N(2) 119.67(16) N(1)-C(1)-C(5) 123.39(18) N(2)-C(1)-C(5) 116.94(17) Este? Lawrence, Masters Dissertation 2011 b2 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(3)-C(2)-N(2) 120.34(19) C(3)-C(2)-H(2) 119.8 N(2)-C(2)-H(2) 119.8 C(2)-C(3)-C(4) 118.3(2) C(2)-C(3)-H(3) 120.8 C(4)-C(3)-H(3) 120.8 C(5)-C(4)-C(3) 121.18(19) C(5)-C(4)-H(4) 119.4 C(3)-C(4)-H(4) 119.4 C(4)-C(5)-C(1) 119.78(18) C(4)-C(5)-H(5) 120.1 C(1)-C(5)-H(5) 120.1 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.1 H(1A)-N(1)-H(1B) 120.0 C(1)-N(2)-C(2) 123.45(16) C(1)-N(2)-H(2A) 118.3 C(2)-N(2)-H(2A) 118.3 Cl(2)#1-Zn(1)-Cl(2) 109.41(3) Cl(2)#1-Zn(1)-Cl(1) 114.57(2) Cl(2)-Zn(1)-Cl(1) 104.39(2) Cl(2)#1-Zn(1)-Cl(1)#1 104.39(2) Cl(2)-Zn(1)-Cl(1)#1 114.57(2) Cl(1)-Zn(1)-Cl(1)#1 109.81(3) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 2ampZnCl. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 35(1) 52(1) 51(1) 10(1) 2(1) 6(1) C(2) 52(1) 49(1) 75(1) 4(1) 2(1) -1(1) C(3) 66(1) 64(1) 61(1) -2(1) 8(1) -1(1) C(4) 57(1) 73(1) 57(1) 10(1) 15(1) -3(1) Este? Lawrence, Masters Dissertation 2011 b3 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(5) 46(1) 56(1) 59(1) 11(1) 7(1) -7(1) Cl(1) 59(1) 54(1) 69(1) -2(1) 6(1) -14(1) Cl(2) 66(1) 61(1) 79(1) -24(1) 32(1) -8(1) N(1) 59(1) 65(1) 57(1) 4(1) 11(1) -2(1) N(2) 42(1) 52(1) 62(1) 14(1) 12(1) 1(1) Zn(1) 44(1) 41(1) 52(1) 0 14(1) 0 Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 2ampZnCl. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 2690 28 -423 71 H(3) 4155 493 -1679 76 H(4) 5658 1886 -1526 74 H(5) 5645 2778 -156 64 H(1A) 3434 2223 1810 72 H(1B) 4547 2949 1444 72 H(2A) 2744 921 904 62 Table 6. Torsion angles [?] for 2ampZnCl. ________________________________________________________________ N(2)-C(2)-C(3)-C(4) 0.1(3) C(2)-C(3)-C(4)-C(5) -0.5(3) C(3)-C(4)-C(5)-C(1) 0.0(3) N(1)-C(1)-C(5)-C(4) -178.18(18) N(2)-C(1)-C(5)-C(4) 0.9(3) N(1)-C(1)-N(2)-C(2) 177.78(17) C(5)-C(1)-N(2)-C(2) -1.3(3) C(3)-C(2)-N(2)-C(1) 0.8(3) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2 Table 7. Hydrogen bonds for 2ampZnCl [? and ?]. ____________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b4 Crystallographic Investigation of n-Aminopyridinium Perhalometallates D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Cl(2) 0.86 2.43 3.276 166.9 N(1)-H(1B)...Cl(2)#2 0.86 2.47 3.316 169.4 N(2)-H(2A)...Cl(2) 0.86 2.61 3.305 139.3 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2 #2 x+1/2,y+1/2,z Este? Lawrence, Masters Dissertation 2011 b5 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(2-aminopyridinium) tetrabromozincate(II) Table 1. Crystal data and structure refinement for 2ampZnBr. Identification code 2ampZnBr Empirical formula C10 H14 Br4 N4 Zn Formula weight 517.21 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group C 2/c Unit cell dimensions a = 15.3064(11) ? ?= 90?. b = 7.7064(6) ? ?= 92.313(6)?. c = 14.7911(10) ? ? = 90?. Volume 1743.3(2) ?3 Z 4 Density (calculated) 1.971 Mg/m3 Absorption coefficient 10.551 mm-1 F(000) 968 Crystal size 0.4 x 0.2 x 0.2 mm3 Theta range for data collection 3.91 to 27.00?. Index ranges -18<=h<=19, -9<=k<=9, -15<=l<=18 Reflections collected 6551 Independent reflections 1895 [R(int) = 0.0249] Completeness to theta = 27.00? 99.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 1895 / 0 / 88 Goodness-of-fit on F2 1.027 Final R indices [I>2sigma(I)] R1 = 0.0237, wR2 = 0.0593 R indices (all data) R1 = 0.0324, wR2 = 0.0612 Extinction coefficient 0.00278(18) Largest diff. peak and hole0.837 and -0.699 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 2ampZnBr. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b6 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 1897(2) 1149(4) -975(2) 31(1) C(2) 733(2) 1816(4) 1(2) 41(1) C(3) 1142(2) 1001(4) 701(2) 41(1) C(4) 1948(2) 211(4) 570(2) 38(1) C(5) 2319(2) 277(4) -249(2) 35(1) Zn(1) 0 4480(1) 2500 27(1) Br(1) -1016(1) 2927(1) 1571(1) 47(1) Br(2) 877(1) 6496(1) 1635(1) 39(1) N(1) 2224(2) 1316(4) -1784(2) 46(1) N(2) 1115(2) 1867(3) -816(2) 37(1) Table 3. Bond lengths [?] and angles [?] for 2ampZnBr. _____________________________________________________ C(1)-N(1) 1.323(4) C(1)-N(2) 1.347(4) C(1)-C(5) 1.402(4) C(2)-C(3) 1.343(4) C(2)-N(2) 1.365(4) C(2)-H(2) 0.9300 C(3)-C(4) 1.396(4) C(3)-H(3) 0.9300 C(4)-C(5) 1.360(4) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 Zn(1)-Br(1) 2.3600(4) Zn(1)-Br(1)#1 2.3600(4) Zn(1)-Br(2) 2.4477(4) Zn(1)-Br(2)#1 2.4477(4) N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(1)-C(1)-N(2) 119.3(3) N(1)-C(1)-C(5) 124.0(3) N(2)-C(1)-C(5) 116.7(3) C(3)-C(2)-N(2) 119.6(3) C(3)-C(2)-H(2) 120.2 Este? Lawrence, Masters Dissertation 2011 b7 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(2)-C(2)-H(2) 120.2 C(2)-C(3)-C(4) 118.9(3) C(2)-C(3)-H(3) 120.5 C(4)-C(3)-H(3) 120.5 C(5)-C(4)-C(3) 120.7(3) C(5)-C(4)-H(4) 119.7 C(3)-C(4)-H(4) 119.7 C(4)-C(5)-C(1) 120.2(3) C(4)-C(5)-H(5) 119.9 C(1)-C(5)-H(5) 119.9 Br(1)-Zn(1)-Br(1)#1 119.03(3) Br(1)-Zn(1)-Br(2) 112.314(12) Br(1)#1-Zn(1)-Br(2) 105.327(11) Br(1)-Zn(1)-Br(2)#1 105.327(11) Br(1)#1-Zn(1)-Br(2)#1 112.314(12) Br(2)-Zn(1)-Br(2)#1 101.21(2) C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(1)-N(2)-C(2) 123.8(3) C(1)-N(2)-H(2A) 118.1 C(2)-N(2)-H(2A) 118.1 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 2ampZnBr. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 25(1) 28(2) 41(2) -6(1) -2(1) -5(1) C(2) 27(2) 43(2) 52(2) -3(2) 4(1) 2(1) C(3) 40(2) 41(2) 43(2) 3(2) 7(1) -4(2) C(4) 37(2) 30(2) 45(2) 9(1) -5(1) -4(1) C(5) 25(2) 27(2) 53(2) -4(1) -2(1) 1(1) Zn(1) 21(1) 25(1) 35(1) 0 2(1) 0 Este? Lawrence, Masters Dissertation 2011 b8 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Br(1) 28(1) 60(1) 52(1) -23(1) 0(1) -7(1) Br(2) 29(1) 37(1) 51(1) 13(1) 10(1) -1(1) N(1) 37(2) 59(2) 41(2) 0(1) 3(1) 4(1) N(2) 30(1) 41(2) 40(1) 2(1) -4(1) 6(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 2ampZnBr. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 194 2342 74 49 H(3) 892 963 1263 50 H(4) 2234 -367 1048 45 H(5) 2855 -258 -328 42 H(1A) 1939 1878 -2202 55 H(1B) 2723 863 -1891 55 H(2A) 840 2387 -1257 44 Table 6. Torsion angles [?] for 2ampZnBr. ________________________________________________________________ N(2)-C(2)-C(3)-C(4) -0.5(5) C(2)-C(3)-C(4)-C(5) 0.6(5) C(3)-C(4)-C(5)-C(1) 0.2(4) N(1)-C(1)-C(5)-C(4) 178.0(3) N(2)-C(1)-C(5)-C(4) -1.2(4) N(1)-C(1)-N(2)-C(2) -177.8(3) C(5)-C(1)-N(2)-C(2) 1.4(4) C(3)-C(2)-N(2)-C(1) -0.5(4) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2 Table 7. Hydrogen bonds for 2ampZnBr [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b9 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(1)-H(1A)...Br(2)#2 0.86 2.64 3.490(3) 172.4 N(1)-H(1B)...Br(2)#3 0.86 2.82 3.625(3) 155.6 N(2)-H(2A)...Br(2)#4 0.86 2.80 3.471(2) 136.1 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2 #2 x,-y+1,z-1/2 #3 -x+1/2,-y+1/2,-z #4 -x,-y+1,-z Este? Lawrence, Masters Dissertation 2011 b10 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(2-aminopyridinium) tetraiodozincate(II) Table 1. Crystal data and structure refinement for 2ampZnI. Identification code 2ampZnI Empirical formula C10 H14 I4 N4 Zn Formula weight 655.08 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group C 2/c Unit cell dimensions a = 35.2785(8) ? ?= 90?. b = 7.6246(2) ? ?= 108.5920(10)?. c = 22.6941(5) ? ? = 90?. Volume 5785.8(2) ?3 Z 20 Density (calculated) 3.760 Mg/m3 Absorption coefficient 12.745 mm-1 F(000) 5720 Crystal size 0.49 x 0.44 x 0.44 mm3 Theta range for data collection 1.22 to 27.00?. Index ranges -43<=h<=44, -9<=k<=9, -28<=l<=28 Reflections collected 31254 Independent reflections 6315 [R(int) = 0.1510] Completeness to theta = 27.00? 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 6315 / 0 / 259 Goodness-of-fit on F2 1.097 Final R indices [I>2sigma(I)] R1 = 0.0582, wR2 = 0.1516 R indices (all data) R1 = 0.0621, wR2 = 0.1566 Extinction coefficient 0.00032(4) Largest diff. peak and hole4.497 and -2.237 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 2ampZnI. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b11 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 2897(2) 11222(11) 5903(4) 36(2) C(2) 2632(3) 10695(11) 6727(4) 40(2) C(3) 2932(3) 11538(13) 7140(4) 51(2) C(4) 3225(3) 12265(12) 6937(4) 47(2) C(5) 3214(2) 12123(11) 6348(5) 40(2) C(6) 3809(2) 8601(10) 6997(4) 33(2) C(7) 3903(3) 9246(13) 8060(4) 46(2) C(8) 3574(3) 8331(13) 8054(4) 44(2) C(9) 3356(3) 7499(12) 7502(4) 41(2) C(10) 3469(2) 7633(10) 6986(4) 34(2) C(11) -381(2) 1007(11) 5540(4) 37(2) C(12) 316(3) 1074(15) 6087(5) 51(2) C(13) 408(4) 1922(15) 5668(6) 58(3) C(14) 106(4) 2487(12) 5166(5) 57(3) C(15) -306(4) 2036(13) 5080(4) 56(3) N(1) 2865(3) 11104(13) 5317(5) 55(2) N(2) 2619(2) 10539(9) 6123(3) 36(2) N(3) 3926(2) 8772(12) 6511(4) 48(2) N(4) 4016(2) 9343(10) 7541(4) 41(2) N(5) -745(3) 462(15) 5512(6) 69(3) N(6) -58(2) 603(10) 6044(3) 36(2) Zn(1) 1672(1) 6770(1) 5625(1) 26(1) Zn(2) 0 7401(2) 7500 26(1) I(1) 1826(1) 8852(1) 4791(1) 33(1) I(2) 2348(1) 5489(1) 6306(1) 34(1) I(3) 1178(1) 4356(1) 5044(1) 36(1) I(4) 1348(1) 8731(1) 6271(1) 40(1) I(5) -40(1) 5485(1) 6538(1) 39(1) I(6) 652(1) 9253(1) 7812(1) 47(1) Table 3. Bond lengths [?] and angles [?] for 2ampZnI. _____________________________________________________ C(1)-N(1) 1.303(13) C(1)-N(2) 1.338(11) C(1)-C(5) 1.423(12) C(2)-C(3) 1.333(15) C(2)-N(2) 1.362(12) Este? Lawrence, Masters Dissertation 2011 b12 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2)-H(2) 0.9300 C(3)-C(4) 1.377(16) C(3)-H(3) 0.9300 C(4)-C(5) 1.329(14) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(3) 1.301(12) C(6)-N(4) 1.341(11) C(6)-C(10) 1.404(11) C(7)-C(8) 1.352(15) C(7)-N(4) 1.361(14) C(7)-H(7) 0.9300 C(8)-C(9) 1.395(13) C(8)-H(8) 0.9300 C(9)-C(10) 1.355(13) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 C(11)-N(5) 1.332(12) C(11)-N(6) 1.368(10) C(11)-C(15) 1.396(15) C(12)-C(13) 1.275(16) C(12)-N(6) 1.340(12) C(12)-H(12) 0.9300 C(13)-C(14) 1.360(18) C(13)-H(13) 0.9300 C(14)-C(15) 1.443(17) C(14)-H(14) 0.9300 C(15)-H(15) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 N(5)-H(5A) 0.8600 N(5)-H(5B) 0.8600 N(6)-H(6) 0.8600 Este? Lawrence, Masters Dissertation 2011 b13 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Zn(1)-I(2) 2.5845(9) Zn(1)-I(3) 2.5886(10) Zn(1)-I(4) 2.6003(10) Zn(1)-I(1) 2.6549(10) Zn(2)-I(5) 2.5923(9) Zn(2)-I(5)#1 2.5923(9) Zn(2)-I(6) 2.5990(8) Zn(2)-I(6)#1 2.5990(8) N(1)-C(1)-N(2) 121.3(9) N(1)-C(1)-C(5) 123.3(9) N(2)-C(1)-C(5) 115.3(8) C(3)-C(2)-N(2) 121.0(9) C(3)-C(2)-H(2) 119.5 N(2)-C(2)-H(2) 119.5 C(2)-C(3)-C(4) 118.0(9) C(2)-C(3)-H(3) 121.0 C(4)-C(3)-H(3) 121.0 C(5)-C(4)-C(3) 121.4(9) C(5)-C(4)-H(4) 119.3 C(3)-C(4)-H(4) 119.3 C(4)-C(5)-C(1) 121.0(8) C(4)-C(5)-H(5) 119.5 C(1)-C(5)-H(5) 119.5 N(3)-C(6)-N(4) 120.8(8) N(3)-C(6)-C(10) 122.5(8) N(4)-C(6)-C(10) 116.7(8) C(8)-C(7)-N(4) 120.4(8) C(8)-C(7)-H(7) 119.8 N(4)-C(7)-H(7) 119.8 C(7)-C(8)-C(9) 118.0(9) C(7)-C(8)-H(8) 121.0 C(9)-C(8)-H(8) 121.0 C(10)-C(9)-C(8) 120.8(8) C(10)-C(9)-H(9) 119.6 C(8)-C(9)-H(9) 119.6 C(9)-C(10)-C(6) 120.6(8) Este? Lawrence, Masters Dissertation 2011 b14 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(9)-C(10)-H(10) 119.7 C(6)-C(10)-H(10) 119.7 N(5)-C(11)-N(6) 120.2(9) N(5)-C(11)-C(15) 123.3(9) N(6)-C(11)-C(15) 116.5(8) C(13)-C(12)-N(6) 124.0(11) C(13)-C(12)-H(12) 118.0 N(6)-C(12)-H(12) 118.0 C(12)-C(13)-C(14) 117.9(11) C(12)-C(13)-H(13) 121.0 C(14)-C(13)-H(13) 121.0 C(13)-C(14)-C(15) 121.6(9) C(13)-C(14)-H(14) 119.2 C(15)-C(14)-H(14) 119.2 C(11)-C(15)-C(14) 117.1(8) C(11)-C(15)-H(15) 121.4 C(14)-C(15)-H(15) 121.4 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(1)-N(2)-C(2) 123.2(8) C(1)-N(2)-H(2A) 118.4 C(2)-N(2)-H(2A) 118.4 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(6)-N(4)-C(7) 123.4(8) C(6)-N(4)-H(4A) 118.3 C(7)-N(4)-H(4A) 118.3 C(11)-N(5)-H(5A) 120.0 C(11)-N(5)-H(5B) 120.0 H(5A)-N(5)-H(5B) 120.0 C(12)-N(6)-C(11) 122.6(8) C(12)-N(6)-H(6) 118.7 C(11)-N(6)-H(6) 118.7 I(2)-Zn(1)-I(3) 112.30(4) I(2)-Zn(1)-I(4) 111.53(3) Este? Lawrence, Masters Dissertation 2011 b15 Crystallographic Investigation of n-Aminopyridinium Perhalometallates I(3)-Zn(1)-I(4) 110.52(3) I(2)-Zn(1)-I(1) 107.06(3) I(3)-Zn(1)-I(1) 108.64(3) I(4)-Zn(1)-I(1) 106.52(3) I(5)-Zn(2)-I(5)#1 111.38(5) I(5)-Zn(2)-I(6) 109.96(2) I(5)#1-Zn(2)-I(6) 105.732(19) I(5)-Zn(2)-I(6)#1 105.732(19) I(5)#1-Zn(2)-I(6)#1 109.96(2) I(6)-Zn(2)-I(6)#1 114.18(5) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+3/2 Table 4. Anisotropic displacement parameters (?2x 103)for 2ampZnI. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 35(4) 31(4) 38(4) 5(3) 8(3) 6(3) C(2) 48(5) 34(4) 42(5) 5(3) 20(4) 5(4) C(3) 70(6) 37(5) 33(4) 3(4) -3(4) 14(4) C(4) 48(5) 32(4) 41(5) -2(4) -13(4) 11(4) C(5) 27(4) 24(4) 65(6) 5(4) 7(4) 3(3) C(6) 34(4) 23(3) 39(4) 2(3) 7(3) 4(3) C(7) 48(5) 39(5) 37(5) -4(4) -6(4) 4(4) C(8) 47(5) 47(5) 37(4) 7(4) 11(4) 13(4) C(9) 39(4) 33(4) 49(5) 3(4) 10(4) -1(3) C(10) 31(4) 27(4) 36(4) -3(3) 1(3) -5(3) C(11) 28(4) 38(4) 36(4) -4(3) -1(3) 9(3) C(12) 33(4) 62(6) 57(6) -14(5) 12(4) -1(4) C(13) 68(7) 56(6) 59(6) -13(5) 37(6) -11(5) C(14) 109(9) 25(4) 61(6) -3(4) 61(7) -5(5) C(15) 88(8) 42(5) 22(4) -1(4) -4(4) 38(5) N(1) 55(5) 57(5) 56(5) -10(4) 20(4) -5(4) N(2) 35(3) 35(4) 35(4) -5(3) 5(3) -4(3) N(3) 41(4) 52(5) 50(5) 3(4) 14(3) -3(3) Este? Lawrence, Masters Dissertation 2011 b16 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(4) 29(3) 38(4) 42(4) -2(3) -6(3) -4(3) N(5) 29(4) 86(8) 86(8) -8(6) 11(4) -4(4) N(6) 39(4) 40(4) 27(3) 4(3) 9(3) 4(3) Zn(1) 22(1) 27(1) 27(1) 2(1) 4(1) 1(1) Zn(2) 28(1) 27(1) 21(1) 0 3(1) 0 I(1) 31(1) 35(1) 29(1) 5(1) 4(1) -9(1) I(2) 26(1) 39(1) 34(1) 3(1) 3(1) 10(1) I(3) 35(1) 36(1) 37(1) -4(1) 11(1) -13(1) I(4) 43(1) 41(1) 32(1) -2(1) 7(1) 17(1) I(5) 45(1) 42(1) 26(1) -9(1) 4(1) 7(1) I(6) 37(1) 48(1) 51(1) 2(1) 5(1) -18(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 2ampZnI. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 2429 10206 6853 48 H(3) 2942 11633 7554 61 H(4) 3435 12869 7217 56 H(5) 3418 12620 6225 48 H(7) 4054 9814 8422 55 H(8) 3495 8257 8407 53 H(9) 3131 6845 7488 50 H(10) 3319 7078 6621 41 H(12) 521 762 6445 61 H(13) 674 2147 5705 69 H(14) 165 3181 4870 68 H(15) -512 2416 4735 67 H(1A) 2663 10579 5063 66 H(1B) 3047 11551 5184 66 H(2A) 2423 9974 5871 44 H(3A) 4137 9367 6535 57 H(3B) 3791 8290 6165 57 H(4A) 4231 9910 7562 49 H(5A) -777 -144 5812 83 Este? Lawrence, Masters Dissertation 2011 b17 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(5B) -947 718 5195 83 H(6) -96 25 6346 43 Table 6. Torsion angles [?] for 2ampZnI. ________________________________________________________________ N(2)-C(2)-C(3)-C(4) 0.8(14) C(2)-C(3)-C(4)-C(5) -0.6(14) C(3)-C(4)-C(5)-C(1) 0.5(13) N(1)-C(1)-C(5)-C(4) 177.3(9) N(2)-C(1)-C(5)-C(4) -0.5(12) N(4)-C(7)-C(8)-C(9) 0.0(14) C(7)-C(8)-C(9)-C(10) -1.1(13) C(8)-C(9)-C(10)-C(6) 0.5(13) N(3)-C(6)-C(10)-C(9) -179.4(8) N(4)-C(6)-C(10)-C(9) 1.1(12) N(6)-C(12)-C(13)-C(14) 4.7(17) C(12)-C(13)-C(14)-C(15) -4.7(15) N(5)-C(11)-C(15)-C(14) -178.4(9) N(6)-C(11)-C(15)-C(14) 3.4(12) C(13)-C(14)-C(15)-C(11) 0.6(14) N(1)-C(1)-N(2)-C(2) -177.2(9) C(5)-C(1)-N(2)-C(2) 0.6(12) C(3)-C(2)-N(2)-C(1) -0.8(13) N(3)-C(6)-N(4)-C(7) 178.3(8) C(10)-C(6)-N(4)-C(7) -2.3(12) C(8)-C(7)-N(4)-C(6) 1.8(14) C(13)-C(12)-N(6)-C(11) -0.4(16) N(5)-C(11)-N(6)-C(12) 178.0(10) C(15)-C(11)-N(6)-C(12) -3.7(12) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+3/2 Table 7. Hydrogen bonds for 2ampZnI [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b18 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(1)-H(1A)...I(1) 0.86 3.11 3.876(10) 149.5 N(1)-H(1A)...I(2)#2 0.86 3.20 3.721(9) 121.4 N(1)-H(1B)...I(3)#2 0.86 3.02 3.735(9) 141.7 N(2)-H(2A)...I(1) 0.86 2.81 3.637(7) 162.6 N(3)-H(3A)...I(5)#3 0.86 3.02 3.856(8) 164.1 N(3)-H(3B)...I(1)#2 0.86 3.02 3.843(9) 161.8 N(3)-H(3B)...I(3)#2 0.86 3.31 3.714(9) 111.7 N(4)-H(4A)...I(5)#4 0.86 2.97 3.657(7) 138.6 N(5)-H(5A)...I(6)#5 0.86 3.05 3.826(13) 151.6 N(5)-H(5B)...I(1)#6 0.86 3.13 3.691(9) 125.2 N(5)-H(5B)...I(4)#6 0.86 3.20 3.975(12) 151.0 N(6)-H(6)...I(6)#5 0.86 3.20 3.960(7) 148.4 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+3/2 #2 -x+1/2,-y+3/2,-z+1 #3 x+1/2,y+1/2,z #4 -x+1/2,y+1/2,-z+3/2 #5 -x,y-1,-z+3/2 #6 -x,-y+1,-z+1 Este? Lawrence, Masters Dissertation 2011 b19 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(2-aminopyridinium) tetraiodocadmate(II) Table 1. Crystal data and structure refinement for 2ampCdI. Identification code 2ampCdI Empirical formula C10 H14 Cd I4 N4 Formula weight 752.20 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Triclinic Space group P -1 Unit cell dimensions a = 8.2597(3) ? ?= 81.9790(10)?. b = 8.7807(3) ? ?= 82.1140(10)?. c = 15.5171(5) ? ? = 63.1230(10)?. Volume 990.50(6) ?3 Z 4 Density (calculated) 5.044 Mg/m3 Absorption coefficient 14.628 mm-1 F(000) 1328 Crystal size 0.42 x 0.40 x 0.28 mm3 Theta range for data collection 1.33 to 27.00?. Index ranges -10<=h<=10, -11<=k<=11, -19<=l<=17 Reflections collected 9045 Independent reflections 4261 [R(int) = 0.1019] Completeness to theta = 27.00? 98.3 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4261 / 0 / 172 Goodness-of-fit on F2 1.079 Final R indices [I>2sigma(I)] R1 = 0.0466, wR2 = 0.1195 R indices (all data) R1 = 0.0520, wR2 = 0.1255 Largest diff. peak and hole2.357 and -1.727 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 2ampCdI. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ C(1) -5080(12) 9124(10) 1348(5) 45(2) Este? Lawrence, Masters Dissertation 2011 b20 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) -3338(16) 10659(13) 876(8) 62(3) C(3) -2096(13) 9362(15) 373(8) 63(3) C(4) -2375(12) 7918(13) 387(7) 57(2) C(5) -3870(11) 7793(10) 861(6) 46(2) C(6) 3830(10) 6549(9) 4125(5) 35(2) C(7) 1497(16) 6785(16) 5241(9) 82(4) C(8) 1542(18) 8120(16) 5534(7) 83(5) C(9) 2743(17) 8689(12) 5130(7) 68(3) C(10) 3875(13) 7948(11) 4419(7) 50(2) Cd(1) 688(1) 4831(1) 2320(1) 31(1) I(1) 2806(1) 5542(1) 954(1) 43(1) I(2) -1552(1) 7624(1) 3225(1) 45(1) I(3) -1106(1) 3090(1) 1890(1) 40(1) I(4) 3296(1) 2363(1) 3439(1) 38(1) N(1) -6558(12) 9062(11) 1812(6) 60(2) N(2) -4740(11) 10464(10) 1342(6) 53(2) N(3) 4895(11) 5802(10) 3452(5) 54(2) N(4) 2660(11) 5991(10) 4535(6) 51(2) Table 3. Bond lengths [?] and angles [?] for 2ampCdI. _____________________________________________________ C(1)-N(2) 1.326(11) C(1)-N(1) 1.349(12) C(1)-C(5) 1.386(11) C(2)-N(2) 1.345(14) C(2)-C(3) 1.390(17) C(2)-H(2) 0.9300 C(3)-C(4) 1.384(15) C(3)-H(3) 0.9300 C(4)-C(5) 1.389(14) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(3) 1.308(10) C(6)-N(4) 1.324(11) C(6)-C(10) 1.386(11) C(7)-C(8) 1.33(2) C(7)-N(4) 1.388(14) Este? Lawrence, Masters Dissertation 2011 b21 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(7)-H(7) 0.9300 C(8)-C(9) 1.348(19) C(8)-H(8) 0.9300 C(9)-C(10) 1.373(14) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 Cd(1)-I(1) 2.7470(7) Cd(1)-I(2) 2.7481(6) Cd(1)-I(3) 2.7534(7) Cd(1)-I(4) 2.8473(7) N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 N(2)-C(1)-N(1) 121.0(8) N(2)-C(1)-C(5) 117.8(8) N(1)-C(1)-C(5) 121.2(8) N(2)-C(2)-C(3) 119.2(9) N(2)-C(2)-H(2) 120.4 C(3)-C(2)-H(2) 120.4 C(4)-C(3)-C(2) 117.3(10) C(4)-C(3)-H(3) 121.3 C(2)-C(3)-H(3) 121.3 C(3)-C(4)-C(5) 121.4(8) C(3)-C(4)-H(4) 119.3 C(5)-C(4)-H(4) 119.3 C(1)-C(5)-C(4) 119.2(8) C(1)-C(5)-H(5) 120.4 C(4)-C(5)-H(5) 120.4 N(3)-C(6)-N(4) 120.3(8) N(3)-C(6)-C(10) 121.3(8) N(4)-C(6)-C(10) 118.4(8) C(8)-C(7)-N(4) 120.9(11) C(8)-C(7)-H(7) 119.5 Este? Lawrence, Masters Dissertation 2011 b22 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(4)-C(7)-H(7) 119.5 C(7)-C(8)-C(9) 118.6(9) C(7)-C(8)-H(8) 120.7 C(9)-C(8)-H(8) 120.7 C(8)-C(9)-C(10) 121.4(10) C(8)-C(9)-H(9) 119.3 C(10)-C(9)-H(9) 119.3 C(9)-C(10)-C(6) 119.5(9) C(9)-C(10)-H(10) 120.2 C(6)-C(10)-H(10) 120.2 I(1)-Cd(1)-I(2) 113.34(2) I(1)-Cd(1)-I(3) 114.12(2) I(2)-Cd(1)-I(3) 112.98(2) I(1)-Cd(1)-I(4) 103.22(2) I(2)-Cd(1)-I(4) 108.77(2) I(3)-Cd(1)-I(4) 103.24(2) C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(1)-N(2)-C(2) 125.0(8) C(1)-N(2)-H(2A) 117.5 C(2)-N(2)-H(2A) 117.5 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(6)-N(4)-C(7) 121.1(9) C(6)-N(4)-H(4A) 119.4 C(7)-N(4)-H(4A) 119.4 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 2ampCdI. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 55(5) 35(4) 38(4) -5(3) -6(3) -13(3) Este? Lawrence, Masters Dissertation 2011 b23 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 70(6) 48(5) 76(7) 9(5) -29(5) -31(5) C(3) 40(5) 77(7) 68(7) -8(5) -7(4) -23(5) C(4) 37(4) 56(5) 70(6) -32(5) -2(4) -7(4) C(5) 42(4) 33(4) 58(5) -15(3) -9(4) -8(3) C(6) 38(4) 25(3) 37(4) -3(3) -9(3) -7(3) C(7) 56(6) 71(7) 72(8) 19(6) 26(6) -3(5) C(8) 80(8) 61(7) 39(5) -1(5) 10(5) 25(6) C(9) 93(8) 38(4) 53(6) -19(4) -21(6) -3(5) C(10) 51(5) 35(4) 67(6) -11(4) -1(4) -20(4) Cd(1) 32(1) 28(1) 30(1) -8(1) 2(1) -10(1) I(1) 42(1) 47(1) 40(1) -4(1) 7(1) -23(1) I(2) 44(1) 32(1) 49(1) -19(1) -1(1) -6(1) I(3) 45(1) 44(1) 38(1) -13(1) -1(1) -23(1) I(4) 43(1) 29(1) 37(1) -4(1) -8(1) -9(1) N(1) 63(5) 49(4) 54(5) -11(3) 14(4) -17(4) N(2) 54(4) 41(4) 60(5) -18(3) -5(4) -13(3) N(3) 58(5) 46(4) 54(4) -23(3) 13(4) -19(3) N(4) 56(4) 41(4) 63(5) -6(3) -5(4) -26(3) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 2ampCdI. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) -3201 11650 891 74 H(3) -1116 9460 40 75 H(4) -1543 7012 73 68 H(5) -4056 6827 851 55 H(7) 674 6380 5513 98 H(8) 762 8648 6008 100 H(9) 2805 9604 5338 81 H(10) 4667 8382 4136 60 H(1A) -7297 9900 2110 72 H(1B) -6761 8185 1810 72 H(2A) -5472 11270 1661 64 H(3A) 4836 4945 3275 65 Este? Lawrence, Masters Dissertation 2011 b24 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(3B) 5653 6169 3187 65 H(4A) 2620 5121 4362 62 Table 6. Torsion angles [?] for 2ampCdI. ________________________________________________________________ N(2)-C(2)-C(3)-C(4) -0.5(16) C(2)-C(3)-C(4)-C(5) 2.2(16) N(2)-C(1)-C(5)-C(4) -0.4(13) N(1)-C(1)-C(5)-C(4) 179.4(9) C(3)-C(4)-C(5)-C(1) -1.8(15) N(4)-C(7)-C(8)-C(9) 0.1(18) C(7)-C(8)-C(9)-C(10) 1.5(17) C(8)-C(9)-C(10)-C(6) -2.2(16) N(3)-C(6)-C(10)-C(9) -179.6(9) N(4)-C(6)-C(10)-C(9) 1.3(13) N(1)-C(1)-N(2)-C(2) -177.6(10) C(5)-C(1)-N(2)-C(2) 2.3(14) C(3)-C(2)-N(2)-C(1) -1.8(16) N(3)-C(6)-N(4)-C(7) -178.8(10) C(10)-C(6)-N(4)-C(7) 0.3(13) C(8)-C(7)-N(4)-C(6) -1.0(17) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 2ampCdI[? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...I(3)#1 0.86 3.15 3.823(8) 136.9 N(1)-H(1B)...I(1)#2 0.86 3.00 3.796(9) 154.4 N(2)-H(2A)...I(4)#1 0.86 2.94 3.690(8) 146.6 N(3)-H(3A)...I(4) 0.86 3.03 3.807(8) 151.4 N(3)-H(3B)...I(2)#3 0.86 3.11 3.886(9) 150.7 N(4)-H(4A)...I(4) 0.86 2.78 3.615(8) 163.0 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x-1,y+1,z #2 x-1,y,z #3 x+1,y,z Este? Lawrence, Masters Dissertation 2011 b25 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(2-aminopyridinium) tetrachloromercurate(II) Table 1. Crystal data and structure refinement for 2ampHgCl. Identification code 2ampHgCl Empirical formula C10 H14 Cl4 Hg N4 Formula weight 474.59 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group C 2/c Unit cell dimensions a = 15.0298(8) ? ?= 90?. b = 7.4925(4) ? ?= 92.229(5)?. c = 14.7577(9) ? ? = 90?. Volume 1660.62(16) ?3 Z 4 Density (calculated) 1.898 Mg/m3 Absorption coefficient 9.884 mm-1 F(000) 880 Crystal size 0.4 x 0.4 x 0.3 mm3 Theta range for data collection 3.80 to 26.99?. Index ranges -14<=h<=19, -9<=k<=9, -18<=l<=18 Reflections collected 6193 Independent reflections 1813 [R(int) = 0.0241] Completeness to theta = 26.99? 99.7 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 1813 / 0 / 87 Goodness-of-fit on F2 1.061 Final R indices [I>2sigma(I)] R1 = 0.0177, wR2 = 0.0424 R indices (all data) R1 = 0.0193, wR2 = 0.0427 Largest diff. peak and hole0.524 and -0.609 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 2ampHgCl. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Cl(1) 5948(1) -1586(1) 1720(1) 48(1) Este? Lawrence, Masters Dissertation 2011 b26 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Cl(2) 3940(1) 1943(1) 1405(1) 53(1) C(1) 6914(2) 3898(4) -1070(2) 36(1) C(2) 5724(2) 3129(4) -133(3) 45(1) C(3) 6104(2) 3962(4) 585(3) 47(1) C(4) 6925(2) 4813(4) 486(2) 40(1) C(5) 7327(2) 4782(4) -325(2) 35(1) Hg(1) 5000 880(1) 2500 36(1) N(1) 7284(2) 3804(4) -1871(2) 51(1) N(2) 6122(2) 3113(3) -936(2) 43(1) Table 3. Bond lengths [?] and angles [?] for 2ampHgCl. _____________________________________________________ Cl(1)-Hg(1) 2.6260(8) Cl(2)-Hg(1) 2.3631(8) C(1)-N(1) 1.327(4) C(1)-N(2) 1.350(4) C(1)-C(5) 1.406(4) C(2)-C(3) 1.339(5) C(2)-N(2) 1.348(5) C(2)-H(2) 0.9300 C(3)-C(4) 1.401(5) C(3)-H(3) 0.9300 C(4)-C(5) 1.362(5) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 Hg(1)-Cl(2)#1 2.3631(8) Hg(1)-Cl(1)#1 2.6260(8) N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(1)-C(1)-N(2) 120.7(3) N(1)-C(1)-C(5) 122.2(3) N(2)-C(1)-C(5) 117.1(3) C(3)-C(2)-N(2) 120.6(3) C(3)-C(2)-H(2) 119.7 N(2)-C(2)-H(2) 119.7 Este? Lawrence, Masters Dissertation 2011 b27 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2)-C(3)-C(4) 118.7(3) C(2)-C(3)-H(3) 120.6 C(4)-C(3)-H(3) 120.6 C(5)-C(4)-C(3) 120.4(3) C(5)-C(4)-H(4) 119.8 C(3)-C(4)-H(4) 119.8 C(4)-C(5)-C(1) 119.9(3) C(4)-C(5)-H(5) 120.1 C(1)-C(5)-H(5) 120.1 Cl(2)#1-Hg(1)-Cl(2) 140.59(5) Cl(2)#1-Hg(1)-Cl(1) 100.03(3) Cl(2)-Hg(1)-Cl(1) 107.48(3) Cl(2)#1-Hg(1)-Cl(1)#1 107.48(3) Cl(2)-Hg(1)-Cl(1)#1 100.03(3) Cl(1)-Hg(1)-Cl(1)#1 90.58(4) C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(2)-N(2)-C(1) 123.3(3) C(2)-N(2)-H(2A) 118.4 C(1)-N(2)-H(2A) 118.4 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 2ampHgCl. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ Cl(1) 43(1) 45(1) 55(1) -15(1) 1(1) 10(1) Cl(2) 39(1) 59(1) 60(1) 20(1) -9(1) 4(1) C(1) 36(2) 30(1) 40(2) 1(1) -7(1) 5(1) C(2) 35(2) 40(2) 61(2) 3(2) -3(1) -3(1) C(3) 48(2) 47(2) 47(2) 3(2) 8(2) 9(2) C(4) 43(2) 32(2) 45(2) -7(1) -8(1) 7(1) C(5) 29(1) 26(1) 50(2) 1(1) -5(1) 1(1) Este? Lawrence, Masters Dissertation 2011 b28 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Hg(1) 30(1) 36(1) 43(1) 0 -4(1) 0 N(1) 58(2) 57(2) 39(2) -4(1) 0(1) -1(1) N(2) 42(1) 36(1) 48(2) -5(1) -13(1) -3(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 2ampHgCl. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 5180 2555 -77 55 H(3) 5829 3976 1138 57 H(4) 7197 5403 977 48 H(5) 7873 5344 -387 42 H(1A) 7019 3239 -2310 62 H(1B) 7790 4308 -1949 62 H(2A) 5857 2576 -1386 51 Table 6. Torsion angles [?] for 2ampHgCl. ________________________________________________________________ N(2)-C(2)-C(3)-C(4) -0.2(5) C(2)-C(3)-C(4)-C(5) -0.3(5) C(3)-C(4)-C(5)-C(1) 0.3(5) N(1)-C(1)-C(5)-C(4) -178.9(3) N(2)-C(1)-C(5)-C(4) 0.2(4) C(3)-C(2)-N(2)-C(1) 0.7(5) N(1)-C(1)-N(2)-C(2) 178.4(3) C(5)-C(1)-N(2)-C(2) -0.7(4) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,y,-z+1/2 Table 7. Hydrogen bonds for 2ampHgCl [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Cl(1)#2 0.86 2.45 3.286(3) 164.9 Este? Lawrence, Masters Dissertation 2011 b29 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(1)-H(1B)...Cl(1)#3 0.86 2.56 3.377(4) 158.0 N(2)-H(2A)...Cl(1)#4 0.86 2.84 3.470(3) 131.8 N(2)-H(2A)...Cl(1)#2 0.86 2.90 3.642(3) 145.6 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,y,-z+1/2 #2 x,-y,z-1/2 #3 -x+3/2,-y+1/2,-z #4 -x+1,-y,-z Este? Lawrence, Masters Dissertation 2011 b30 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(2-aminopyridinium) tetrabromomercurate(II) Table 1. Crystal data and structure refinement for 2ampHgBr. Identification code 2ampHgBr Empirical formula C10 H14 Br4 Hg N4 Formula weight 538.45 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = 6.9651(5) ? ?= 90.000(5)?. b = 17.7646(13) ? ?= 97.856(4)?. c = 14.3009(10) ? ? = 90.000(4)?. Volume 1752.9(2) ?3 Z 4 Density (calculated) 2.040 Mg/m3 Absorption coefficient 13.616 mm-1 F(000) 964 Crystal size 0.56 x 0.40 x 0.26 mm3 Theta range for data collection 1.84 to 27.00?. Index ranges -7<=h<=8, -22<=k<=22, -18<=l<=18 Reflections collected 14967 Independent reflections 3820 [R(int) = 0.2769] Completeness to theta = 27.00? 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3820 / 0 / 173 Goodness-of-fit on F2 0.929 Final R indices [I>2sigma(I)] R1 = 0.0735, wR2 = 0.1684 R indices (all data) R1 = 0.1173, wR2 = 0.1947 Extinction coefficient 0.0046(5) Largest diff. peak and hole2.746 and -2.269 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 2ampHgBr. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b31 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 9070(20) 3117(9) 4045(10) 52(4) C(2) 11940(30) 3833(11) 4018(14) 76(6) C(3) 12320(20) 3420(11) 3255(12) 63(4) C(4) 11120(30) 2874(11) 2894(11) 66(5) C(5) 9420(20) 2701(9) 3285(10) 56(4) C(6) -1560(20) 4148(9) 1383(11) 57(4) C(7) 1260(30) 4835(11) 1358(13) 74(5) C(8) 1830(30) 4433(11) 681(13) 74(5) C(9) 640(30) 3825(10) 319(12) 66(5) C(10) -1040(30) 3689(9) 691(12) 62(4) N(1) 7410(20) 2989(9) 4467(11) 77(4) N(2) 10275(19) 3671(7) 4387(8) 52(3) N(3) -3190(20) 4063(10) 1759(12) 90(5) N(4) -380(20) 4716(8) 1679(9) 61(4) Br(1) 5267(3) 6293(1) 1375(1) 63(1) Hg(1) 4944(1) 6206(1) 3159(1) 49(1) Br(2) 1218(2) 6039(1) 3378(1) 59(1) Br(3) 5898(2) 7438(1) 4047(1) 56(1) Br(4) 6605(3) 4982(1) 3836(1) 65(1) Table 3. Bond lengths [?] and angles [?] for 2ampHgBr. _____________________________________________________ C(1)-N(2) 1.343(19) C(1)-C(5) 1.364(19) C(1)-N(1) 1.394(19) C(2)-C(3) 1.37(3) C(2)-N(2) 1.37(2) C(2)-H(2) 0.9300 C(3)-C(4) 1.34(2) C(3)-H(3) 0.9300 C(4)-C(5) 1.41(2) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(3) 1.33(2) C(6)-N(4) 1.33(2) C(6)-C(10) 1.37(2) C(7)-N(4) 1.31(2) Este? Lawrence, Masters Dissertation 2011 b32 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(7)-C(8) 1.31(2) C(7)-H(7) 0.9300 C(8)-C(9) 1.42(2) C(8)-H(8) 0.9300 C(9)-C(10) 1.37(3) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 Br(1)-Hg(1) 2.5962(15) Hg(1)-Br(3) 2.5732(16) Hg(1)-Br(4) 2.5874(17) Hg(1)-Br(2) 2.6726(16) N(2)-C(1)-C(5) 121.0(14) N(2)-C(1)-N(1) 118.5(14) C(5)-C(1)-N(1) 120.5(16) C(3)-C(2)-N(2) 117.3(18) C(3)-C(2)-H(2) 121.3 N(2)-C(2)-H(2) 121.3 C(4)-C(3)-C(2) 121.3(16) C(4)-C(3)-H(3) 119.3 C(2)-C(3)-H(3) 119.3 C(3)-C(4)-C(5) 121.2(15) C(3)-C(4)-H(4) 119.4 C(5)-C(4)-H(4) 119.4 C(1)-C(5)-C(4) 116.8(15) C(1)-C(5)-H(5) 121.6 C(4)-C(5)-H(5) 121.6 N(3)-C(6)-N(4) 118.7(16) N(3)-C(6)-C(10) 123.5(16) N(4)-C(6)-C(10) 117.8(16) N(4)-C(7)-C(8) 122.8(18) Este? Lawrence, Masters Dissertation 2011 b33 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(4)-C(7)-H(7) 118.6 C(8)-C(7)-H(7) 118.6 C(7)-C(8)-C(9) 117.6(18) C(7)-C(8)-H(8) 121.2 C(9)-C(8)-H(8) 121.2 C(10)-C(9)-C(8) 118.8(16) C(10)-C(9)-H(9) 120.6 C(8)-C(9)-H(9) 120.6 C(9)-C(10)-C(6) 120.1(15) C(9)-C(10)-H(10) 120.0 C(6)-C(10)-H(10) 120.0 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(1)-N(2)-C(2) 122.4(14) C(1)-N(2)-H(2A) 118.8 C(2)-N(2)-H(2A) 118.8 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(7)-N(4)-C(6) 122.8(16) C(7)-N(4)-H(4A) 118.6 C(6)-N(4)-H(4A) 118.6 Br(3)-Hg(1)-Br(4) 117.28(6) Br(3)-Hg(1)-Br(1) 112.52(6) Br(4)-Hg(1)-Br(1) 108.90(6) Br(3)-Hg(1)-Br(2) 103.03(5) Br(4)-Hg(1)-Br(2) 104.77(6) Br(1)-Hg(1)-Br(2) 109.73(5) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 2ampHgBr. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b34 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 57(9) 57(10) 45(7) 12(8) 22(7) 14(8) C(2) 68(12) 85(15) 77(11) 36(11) 19(10) -10(9) C(3) 60(10) 69(13) 64(10) 16(10) 22(9) 6(9) C(4) 82(12) 74(13) 48(8) 0(9) 33(9) 8(10) C(5) 72(10) 38(9) 56(9) -12(7) 6(8) 16(7) C(6) 58(10) 52(10) 57(9) -2(8) -11(8) 2(8) C(7) 65(12) 85(14) 66(10) -5(11) -7(9) -16(10) C(8) 53(10) 104(16) 60(10) 3(11) -5(8) 22(10) C(9) 63(11) 81(13) 55(9) -10(9) 15(8) 19(9) C(10) 63(10) 49(10) 69(10) -12(9) -8(9) -3(8) N(1) 71(9) 80(11) 88(10) 3(9) 41(8) 8(8) N(2) 71(9) 47(8) 40(6) -1(6) 12(6) -7(6) N(3) 62(10) 102(13) 109(13) -16(11) 25(10) -13(9) N(4) 72(9) 52(9) 60(7) -24(7) 7(7) -9(7) Br(1) 70(1) 80(1) 43(1) -3(1) 20(1) -8(1) Hg(1) 55(1) 48(1) 47(1) -4(1) 14(1) 0(1) Br(2) 49(1) 77(1) 53(1) -7(1) 19(1) -9(1) Br(3) 64(1) 47(1) 60(1) -9(1) 24(1) -7(1) Br(4) 65(1) 53(1) 80(1) 11(1) 17(1) 9(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 2ampHgBr. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 12784 4209 4274 91 H(3) 13428 3521 2983 76 H(4) 11414 2603 2376 79 H(5) 8581 2321 3037 67 H(7) 2054 5222 1623 88 H(8) 2980 4543 445 88 H(9) 988 3524 -163 79 H(10) -1821 3284 473 74 H(1A) 7178 3262 4937 93 H(1B) 6614 2637 4259 93 H(2A) 9993 3934 4855 63 Este? Lawrence, Masters Dissertation 2011 b35 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(3A) -3468 4371 2185 108 H(3B) -3969 3699 1577 108 H(4A) -718 5018 2099 74 Table 6. Torsion angles [?] for 2ampHgBr. ________________________________________________________________ N(2)-C(2)-C(3)-C(4) -1(3) C(2)-C(3)-C(4)-C(5) 0(3) N(2)-C(1)-C(5)-C(4) 1(2) N(1)-C(1)-C(5)-C(4) 179.3(15) C(3)-C(4)-C(5)-C(1) 0(2) N(4)-C(7)-C(8)-C(9) -3(3) C(7)-C(8)-C(9)-C(10) 0(3) C(8)-C(9)-C(10)-C(6) 2(3) N(3)-C(6)-C(10)-C(9) 178.1(18) N(4)-C(6)-C(10)-C(9) -1(2) C(5)-C(1)-N(2)-C(2) -2(2) N(1)-C(1)-N(2)-C(2) 179.6(15) C(3)-C(2)-N(2)-C(1) 2(2) C(8)-C(7)-N(4)-C(6) 4(3) N(3)-C(6)-N(4)-C(7) 179.0(17) C(10)-C(6)-N(4)-C(7) -2(3) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 2ampHgBr [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Br(2)#1 0.86 2.80 3.547(17) 145.6 N(1)-H(1A)...Br(3)#1 0.86 3.02 3.424(13) 111.3 N(1)-H(1B)...Br(1)#2 0.86 2.81 3.659(16) 167.7 N(2)-H(2A)...Br(2)#1 0.86 2.77 3.531(12) 148.1 N(3)-H(3A)...Br(4)#3 0.86 2.59 3.409(18) 158.8 N(3)-H(3B)...Br(3)#4 0.86 2.70 3.552(17) 170.8 N(4)-H(4A)...Br(2) 0.86 2.79 3.453(12) 135.2 ____________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b36 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+1,-z+1 #2 -x+1,y-1/2,-z+1/2 #3 x-1,y,z #4 -x,y-1/2,-z+1/2 Este? Lawrence, Masters Dissertation 2011 b37 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(2-aminopyridinium) tetraiodomercuate(II) Table 1. Crystal data and structure refinement for 2ampHgI. Identification code 2ampHgI Empirical formula C10 H14 Hg I4 N4 Formula weight 840.39 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.1780(4) ? ?= 82.124(2)?. b = 8.7740(4) ? ?= 82.261(2)?. c = 15.4043(7) ? ? = 63.168(2)?. Volume 973.69(8) ?3 Z 4 Density (calculated) 5.733 Mg/m3 Absorption coefficient 28.445 mm-1 F(000) 1456 Crystal size 0.72 x 0.55 x 0.47 mm3 Theta range for data collection 1.34 to 27.00?. Index ranges -10<=h<=10, -11<=k<=11, -19<=l<=19 Reflections collected 17620 Independent reflections 4260 [R(int) = 0.2016] Completeness to theta = 27.00? 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4260 / 0 / 172 Goodness-of-fit on F2 1.051 Final R indices [I>2sigma(I)] R1 = 0.0763, wR2 = 0.1965 R indices (all data) R1 = 0.0807, wR2 = 0.2046 Largest diff. peak and hole6.434 and -5.970 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 2ampHgI. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ C(1) 4912(19) 9129(16) 1354(9) 34(3) Este? Lawrence, Masters Dissertation 2011 b38 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 6690(30) 10620(20) 868(13) 55(4) C(3) 7910(20) 9340(30) 404(12) 52(4) C(4) 7640(19) 7900(20) 394(10) 43(3) C(5) 6170(20) 7761(18) 893(10) 40(3) C(6) 3819(18) 6546(17) 4126(8) 31(2) C(7) 1500(30) 6680(20) 5233(12) 58(5) C(8) 1490(30) 8070(30) 5542(11) 70(7) C(9) 2680(30) 8680(20) 5118(12) 55(4) C(10) 3810(20) 7990(19) 4411(10) 41(3) Hg 666(1) 4858(1) 2298(1) 29(1) I(1) 2870(1) 5511(1) 941(1) 34(1) I(2) -1524(1) 7647(1) 3212(1) 38(1) I(3) -1096(1) 3054(1) 1887(1) 32(1) I(4) 3349(1) 2331(1) 3445(1) 31(1) N(1) 3440(20) 9010(20) 1847(9) 55(4) N(2) 5240(20) 10491(16) 1327(9) 46(3) N(3) 4914(18) 5777(17) 3440(9) 42(3) N(4) 2677(17) 5956(18) 4541(9) 45(3) Table 3. Bond lengths [?] and angles [?] for 2ampHgI. _____________________________________________________ C(1)-N(2) 1.334(19) C(1)-N(1) 1.37(2) C(1)-C(5) 1.388(19) C(2)-N(2) 1.34(2) C(2)-C(3) 1.33(3) C(2)-H(2) 0.9300 C(3)-C(4) 1.38(2) C(3)-H(3) 0.9300 C(4)-C(5) 1.38(2) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(4) 1.317(18) C(6)-N(3) 1.330(18) C(6)-C(10) 1.394(19) C(7)-N(4) 1.35(2) C(7)-C(8) 1.37(3) Este? Lawrence, Masters Dissertation 2011 b39 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(7)-H(7) 0.9300 C(8)-C(9) 1.37(3) C(8)-H(8) 0.9300 C(9)-C(10) 1.35(2) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 Hg-I(2) 2.7356(9) Hg-I(1) 2.7447(9) Hg-I(3) 2.7497(9) Hg-I(4) 2.9031(9) N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 N(2)-C(1)-N(1) 122.7(14) N(2)-C(1)-C(5) 117.6(14) N(1)-C(1)-C(5) 119.6(14) N(2)-C(2)-C(3) 120.4(16) N(2)-C(2)-H(2) 119.8 C(3)-C(2)-H(2) 119.8 C(2)-C(3)-C(4) 118.9(16) C(2)-C(3)-H(3) 120.5 C(4)-C(3)-H(3) 120.5 C(5)-C(4)-C(3) 120.0(14) C(5)-C(4)-H(4) 120.0 C(3)-C(4)-H(4) 120.0 C(4)-C(5)-C(1) 119.2(14) C(4)-C(5)-H(5) 120.4 C(1)-C(5)-H(5) 120.4 N(4)-C(6)-N(3) 119.5(13) N(4)-C(6)-C(10) 118.6(14) N(3)-C(6)-C(10) 121.9(13) N(4)-C(7)-C(8) 119.5(17) N(4)-C(7)-H(7) 120.2 Este? Lawrence, Masters Dissertation 2011 b40 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(8)-C(7)-H(7) 120.2 C(9)-C(8)-C(7) 117.4(16) C(9)-C(8)-H(8) 121.3 C(7)-C(8)-H(8) 121.3 C(10)-C(9)-C(8) 122.7(18) C(10)-C(9)-H(9) 118.6 C(8)-C(9)-H(9) 118.6 C(9)-C(10)-C(6) 118.3(15) C(9)-C(10)-H(10) 120.8 C(6)-C(10)-H(10) 120.8 I(2)-Hg-I(1) 113.45(3) I(2)-Hg-I(3) 114.61(3) I(1)-Hg-I(3) 114.93(3) I(2)-Hg-I(4) 108.34(3) I(1)-Hg-I(4) 102.01(3) I(3)-Hg-I(4) 101.69(3) C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(1)-N(2)-C(2) 123.7(15) C(1)-N(2)-H(2A) 118.2 C(2)-N(2)-H(2A) 118.2 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(6)-N(4)-C(7) 123.3(15) C(6)-N(4)-H(4A) 118.3 C(7)-N(4)-H(4A) 118.3 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 2ampHgI. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 36(7) 22(6) 37(7) 2(5) -12(5) -5(5) Este? Lawrence, Masters Dissertation 2011 b41 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 54(10) 45(9) 76(12) 15(8) -27(9) -30(8) C(3) 39(8) 62(11) 56(10) -11(8) -9(7) -21(8) C(4) 25(6) 43(8) 53(9) -16(6) -10(6) -4(6) C(5) 41(7) 24(6) 49(8) -15(6) -19(6) -3(6) C(6) 36(6) 31(6) 28(6) 3(5) -10(5) -18(5) C(7) 55(10) 41(9) 56(10) 12(7) 12(8) -11(8) C(8) 64(12) 59(12) 35(8) 5(7) 8(7) 14(9) C(9) 63(11) 36(8) 59(10) -16(7) -19(8) -8(8) C(10) 40(7) 36(7) 53(8) -12(6) -1(6) -22(6) Hg 27(1) 28(1) 30(1) -7(1) 3(1) -11(1) I(1) 31(1) 39(1) 36(1) -2(1) 4(1) -21(1) I(2) 37(1) 29(1) 41(1) -15(1) -5(1) -4(1) I(3) 32(1) 37(1) 33(1) -10(1) -4(1) -19(1) I(4) 35(1) 24(1) 32(1) -1(1) -11(1) -9(1) N(1) 54(8) 42(8) 48(8) -6(6) 7(6) -5(6) N(2) 50(8) 30(6) 53(8) -12(5) -10(6) -10(6) N(3) 40(6) 32(6) 50(7) -11(5) 4(5) -13(5) N(4) 33(6) 44(7) 64(8) -2(6) -15(6) -20(6) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 2ampHgI. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 6850 11602 872 66 H(3) 8934 9419 92 62 H(4) 8445 7024 50 51 H(5) 6030 6761 921 48 H(7) 695 6231 5497 69 H(8) 696 8587 6021 84 H(9) 2714 9614 5327 67 H(10) 4575 8462 4120 49 H(1A) 2690 9828 2156 66 H(1B) 3274 8107 1848 66 H(2A) 4485 11334 1620 55 H(3A) 4873 4902 3270 51 Este? Lawrence, Masters Dissertation 2011 b42 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(3B) 5664 6156 3165 51 H(4A) 2683 5067 4362 54 Table 6. Torsion angles [?] for 2ampHgI. ________________________________________________________________ N(2)-C(2)-C(3)-C(4) 1(3) C(2)-C(3)-C(4)-C(5) -3(2) C(3)-C(4)-C(5)-C(1) 4(2) N(2)-C(1)-C(5)-C(4) -4(2) N(1)-C(1)-C(5)-C(4) 179.6(14) N(4)-C(7)-C(8)-C(9) 1(3) C(7)-C(8)-C(9)-C(10) 1(3) C(8)-C(9)-C(10)-C(6) -3(3) N(4)-C(6)-C(10)-C(9) 2(2) N(3)-C(6)-C(10)-C(9) -179.2(15) N(1)-C(1)-N(2)-C(2) 178.3(15) C(5)-C(1)-N(2)-C(2) 1(2) C(3)-C(2)-N(2)-C(1) 0(3) N(3)-C(6)-N(4)-C(7) -178.8(15) C(10)-C(6)-N(4)-C(7) 0(2) C(8)-C(7)-N(4)-C(6) -1(3) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 2ampHgI [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(3)-H(3A)...I(4) 0.86 3.00 3.777(13) 151.5 N(3)-H(3B)...I(2)#1 0.86 3.13 3.896(14) 149.6 N(4)-H(4A)...I(4) 0.86 2.76 3.593(14) 164.8 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x+1,y,z Este? Lawrence, Masters Dissertation 2011 b43 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(3-aminopyridinium) tetrachlorozincate(II) Table 1. Crystal data and structure refinement for 3ampZnCl. Identification code 3ampZnCl Empirical formula C10 H14 Cl4 N4 Zn Formula weight 339.37 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Triclinic Space group P -1 Unit cell dimensions a = 6.8921(5) ? ?= 99.008(6)?. b = 8.4555(6) ? ?= 89.573(5)?. c = 13.8003(9) ? ? = 100.194(6)?. Volume 781.60(9) ?3 Z 4 Density (calculated) 2.884 Mg/m3 Absorption coefficient 4.450 mm-1 F(000) 680 Crystal size 0.2 x 0.2 x 0.2 mm3 Theta range for data collection 3.97 to 27.00?. Index ranges -7<=h<=8, -10<=k<=10, -17<=l<=17 Reflections collected 6269 Independent reflections 3381 [R(int) = 0.0187] Completeness to theta = 27.00? 99.3 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3381 / 0 / 172 Goodness-of-fit on F2 0.977 Final R indices [I>2sigma(I)] R1 = 0.0217, wR2 = 0.0444 R indices (all data) R1 = 0.0301, wR2 = 0.0455 Largest diff. peak and hole0.320 and -0.272 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 3ampZnCl. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ C(1) 23660(3) 2990(2) 4843(1) 32(1) Este? Lawrence, Masters Dissertation 2011 b44 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 24451(3) 2918(2) 5756(1) 34(1) C(3) 27026(3) 1643(2) 5028(2) 39(1) C(4) 26303(3) 1703(2) 4126(2) 39(1) C(5) 24665(3) 2364(2) 4021(1) 33(1) C(6) 24081(2) 2011(2) 1366(1) 22(1) C(7) 25378(2) 3085(2) 898(1) 23(1) C(8) 27659(3) 1284(2) 677(1) 28(1) C(9) 26435(3) 193(2) 1139(1) 29(1) C(10) 24660(2) 540(2) 1476(1) 26(1) Cl(1) 31293(1) 3406(1) 9372(1) 25(1) Cl(2) 30995(1) 5321(1) 7065(1) 32(1) Cl(3) 26577(1) 3441(1) 8126(1) 26(1) Cl(4) 29870(1) 783(1) 6948(1) 33(1) Zn(1) 29840(1) 3242(1) 7899(1) 23(1) N(1) 22045(2) 3650(2) 4777(1) 48(1) N(2) 26060(2) 2270(2) 5811(1) 38(1) N(3) 22331(2) 2368(2) 1704(1) 35(1) N(4) 27082(2) 2685(2) 577(1) 25(1) Table 3. Bond lengths [?] and angles [?] for 3ampZnCl. _____________________________________________________ C(1)-N(1) 1.340(2) C(1)-C(2) 1.391(2) C(1)-C(5) 1.407(2) C(2)-N(2) 1.329(2) C(2)-H(2) 0.9300 C(3)-N(2) 1.351(2) C(3)-C(4) 1.356(3) C(3)-H(3) 0.9300 C(4)-C(5) 1.363(2) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(3) 1.357(2) C(6)-C(7) 1.388(2) C(6)-C(10) 1.402(2) C(7)-N(4) 1.333(2) C(7)-H(7) 0.9300 Este? Lawrence, Masters Dissertation 2011 b45 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(8)-N(4) 1.341(2) C(8)-C(9) 1.368(2) C(8)-H(8) 0.9300 C(9)-C(10) 1.369(2) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 Cl(1)-Zn(1) 2.2473(5) Cl(2)-Zn(1) 2.2742(5) Cl(3)-Zn(1) 2.3001(5) Cl(4)-Zn(1) 2.2813(5) N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 N(1)-C(1)-C(2) 120.45(17) N(1)-C(1)-C(5) 123.30(17) C(2)-C(1)-C(5) 116.24(17) N(2)-C(2)-C(1) 119.78(17) N(2)-C(2)-H(2) 120.1 C(1)-C(2)-H(2) 120.1 N(2)-C(3)-C(4) 117.17(18) N(2)-C(3)-H(3) 121.4 C(4)-C(3)-H(3) 121.4 C(3)-C(4)-C(5) 120.96(18) C(3)-C(4)-H(4) 119.5 C(5)-C(4)-H(4) 119.5 C(4)-C(5)-C(1) 121.17(17) C(4)-C(5)-H(5) 119.4 C(1)-C(5)-H(5) 119.4 N(3)-C(6)-C(7) 121.61(15) N(3)-C(6)-C(10) 121.28(15) C(7)-C(6)-C(10) 117.11(15) N(4)-C(7)-C(6) 119.60(15) N(4)-C(7)-H(7) 120.2 Este? Lawrence, Masters Dissertation 2011 b46 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(6)-C(7)-H(7) 120.2 N(4)-C(8)-C(9) 118.40(16) N(4)-C(8)-H(8) 120.8 C(9)-C(8)-H(8) 120.8 C(8)-C(9)-C(10) 119.82(16) C(8)-C(9)-H(9) 120.1 C(10)-C(9)-H(9) 120.1 C(9)-C(10)-C(6) 120.98(15) C(9)-C(10)-H(10) 119.5 C(6)-C(10)-H(10) 119.5 Cl(1)-Zn(1)-Cl(2) 115.004(18) Cl(1)-Zn(1)-Cl(4) 111.586(18) Cl(2)-Zn(1)-Cl(4) 111.051(18) Cl(1)-Zn(1)-Cl(3) 108.686(17) Cl(2)-Zn(1)-Cl(3) 103.445(17) Cl(4)-Zn(1)-Cl(3) 106.364(18) C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(2)-N(2)-C(3) 124.68(16) C(2)-N(2)-H(2A) 117.7 C(3)-N(2)-H(2A) 117.7 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(7)-N(4)-C(8) 124.07(15) C(7)-N(4)-H(4A) 118.0 C(8)-N(4)-H(4A) 118.0 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 3ampZnCl. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 29(1) 33(1) 31(1) 5(1) -1(1) 1(1) Este? Lawrence, Masters Dissertation 2011 b47 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 37(1) 40(1) 23(1) 5(1) 1(1) -3(1) C(3) 33(1) 38(1) 48(1) 16(1) 2(1) -1(1) C(4) 37(1) 39(1) 41(1) 7(1) 10(1) 4(1) C(5) 38(1) 36(1) 22(1) 4(1) 0(1) 3(1) C(6) 23(1) 23(1) 20(1) 3(1) -2(1) 5(1) C(7) 28(1) 19(1) 25(1) 5(1) -1(1) 6(1) C(8) 27(1) 29(1) 29(1) 0(1) 0(1) 9(1) C(9) 38(1) 23(1) 30(1) 4(1) -1(1) 13(1) C(10) 33(1) 20(1) 25(1) 6(1) 1(1) 2(1) Cl(1) 27(1) 25(1) 26(1) 6(1) 2(1) 8(1) Cl(2) 38(1) 30(1) 31(1) 12(1) 11(1) 7(1) Cl(3) 25(1) 24(1) 30(1) 4(1) 6(1) 8(1) Cl(4) 38(1) 26(1) 35(1) -2(1) 7(1) 10(1) Zn(1) 26(1) 20(1) 23(1) 4(1) 5(1) 6(1) N(1) 46(1) 66(1) 35(1) 2(1) 1(1) 23(1) N(2) 37(1) 45(1) 32(1) 16(1) -5(1) -1(1) N(3) 30(1) 35(1) 48(1) 19(1) 11(1) 15(1) N(4) 25(1) 24(1) 25(1) 5(1) 3(1) 1(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 3ampZnCl. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 23856 3322 6327 41 H(3) 28140 1191 5105 47 H(4) 26933 1286 3570 47 H(5) 24205 2402 3395 39 H(7) 25059 4077 810 28 H(8) 28862 1060 437 34 H(9) 26806 -782 1223 35 H(10) 23827 -211 1784 31 H(1A) 21491 4033 5301 58 H(1B) 21562 3691 4210 58 H(2A) 26520 2247 6385 46 H(3A) 22002 3277 1632 42 Este? Lawrence, Masters Dissertation 2011 b48 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(3B) 21550 1684 1992 42 H(4A) 27859 3368 288 30 Table 6. Torsion angles [?] for 3ampZnCl. ________________________________________________________________ N(1)-C(1)-C(2)-N(2) -179.56(17) C(5)-C(1)-C(2)-N(2) -0.6(2) N(2)-C(3)-C(4)-C(5) -0.2(3) C(3)-C(4)-C(5)-C(1) -0.7(3) N(1)-C(1)-C(5)-C(4) -179.96(18) C(2)-C(1)-C(5)-C(4) 1.1(3) N(3)-C(6)-C(7)-N(4) -179.97(15) C(10)-C(6)-C(7)-N(4) 0.2(2) N(4)-C(8)-C(9)-C(10) 0.7(2) C(8)-C(9)-C(10)-C(6) -0.7(3) N(3)-C(6)-C(10)-C(9) -179.58(15) C(7)-C(6)-C(10)-C(9) 0.2(2) C(1)-C(2)-N(2)-C(3) -0.4(3) C(4)-C(3)-N(2)-C(2) 0.8(3) C(6)-C(7)-N(4)-C(8) -0.2(2) C(9)-C(8)-N(4)-C(7) -0.2(2) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 3ampZnCl [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Cl(2)#3 0.86 2.55 3.379 161.4 N(2)-H(2A)...Cl(3) 0.86 2.45 3.197 145.0 N(4)-H(4A)...Cl(1)#1 0.86 2.65 3.286 131.4 N(4)-H(4A)...Cl(1)#2 0.86 2.67 3.343 135.9 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+6,-y+1,-z+1 #2 x, y, z-1 #3 x-1, y, z Este? Lawrence, Masters Dissertation 2011 b49 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(3-ammoniopyridinium) tetrabromozincate(II) monohydrate Table 1. Crystal data and structure refinement for 3ampZnBr?H2O. Identification code 3ampZnBr?H2O Empirical formula C5 H10 Br4 N2 O Zn Formula weight 448.44 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = 7.017(2) ? ?= 90?. b = 23.380(7) ? ?= 94.299(17)?. c = 7.766(2) ? ? = 90?. Volume 1270.5(6) ?3 Z 6 Density (calculated) 3.517 Mg/m3 Absorption coefficient 21.688 mm-1 F(000) 1228 Crystal size 0.98 x 0.50 x 0.40 mm3 Theta range for data collection 1.74 to 27.00?. Index ranges -8<=h<=8, -29<=k<=29, -8<=l<=9 Reflections collected 12195 Independent reflections 2759 [R(int) = 0.5444] Completeness to theta = 27.00? 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2759 / 0 / 122 Goodness-of-fit on F2 1.073 Final R indices [I>2sigma(I)] R1 = 0.1048, wR2 = 0.2113 R indices (all data) R1 = 0.1298, wR2 = 0.2427 Extinction coefficient 0.028(3) Largest diff. peak and hole1.517 and -2.292 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 3ampZnBr?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b50 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) -6309(14) 6265(5) 5520(10) 33(2) C(2) -4663(14) 6222(5) 4663(12) 37(2) C(3) -4386(17) 7202(6) 4618(13) 48(3) C(4) -6046(18) 7267(6) 5453(17) 51(3) C(5) -7001(16) 6787(5) 5917(14) 43(3) N(1) -7248(13) 5728(4) 5988(11) 42(2) N(2) -3787(12) 6683(4) 4251(9) 39(2) O(1) -4175(13) 5045(4) 7114(12) 57(2) Zn(1) 340(2) 6208(1) 772(1) 36(1) Br(1) 3697(2) 6109(1) 328(1) 43(1) Br(2) -1301(2) 6170(1) -2048(1) 45(1) Br(4) -714(2) 5500(1) 2754(1) 46(1) Br(5) -261(2) 7111(1) 2098(1) 48(1) Table 3. Bond lengths [?] and angles [?] for 3ampZnBr?H2O. _____________________________________________________ C(1)-C(5) 1.357(15) C(1)-C(2) 1.379(12) C(1)-N(1) 1.475(13) C(2)-N(2) 1.294(14) C(2)-H(2) 0.9300 C(3)-N(2) 1.322(16) C(3)-C(4) 1.383(17) C(3)-H(3) 0.9300 C(4)-C(5) 1.369(17) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 N(1)-H(1A) 0.8900 N(1)-H(1B) 0.8900 N(1)-H(1C) 0.8900 N(2)-H(2A) 0.8600 O(1)-H(1D) 1.013(9) O(1)-H(1E) 0.954(9) Zn(1)-Br(2) 2.3981(16) Zn(1)-Br(5) 2.4015(18) Zn(1)-Br(4) 2.4146(16) Zn(1)-Br(1) 2.4163(16) Este? Lawrence, Masters Dissertation 2011 b51 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(5)-C(1)-C(2) 120.1(10) C(5)-C(1)-N(1) 122.3(8) C(2)-C(1)-N(1) 117.5(10) N(2)-C(2)-C(1) 119.3(10) N(2)-C(2)-H(2) 120.4 C(1)-C(2)-H(2) 120.4 N(2)-C(3)-C(4) 119.6(12) N(2)-C(3)-H(3) 120.2 C(4)-C(3)-H(3) 120.2 C(5)-C(4)-C(3) 118.7(12) C(5)-C(4)-H(4) 120.7 C(3)-C(4)-H(4) 120.7 C(1)-C(5)-C(4) 119.1(10) C(1)-C(5)-H(5) 120.4 C(4)-C(5)-H(5) 120.4 C(1)-N(1)-H(1A) 109.5 C(1)-N(1)-H(1B) 109.5 H(1A)-N(1)-H(1B) 109.5 C(1)-N(1)-H(1C) 109.5 H(1A)-N(1)-H(1C) 109.5 H(1B)-N(1)-H(1C) 109.5 C(2)-N(2)-C(3) 123.2(9) C(2)-N(2)-H(2A) 118.4 C(3)-N(2)-H(2A) 118.4 H(1D)-O(1)-H(1E) 115.7(9) Br(2)-Zn(1)-Br(5) 109.65(6) Br(2)-Zn(1)-Br(4) 114.08(6) Br(5)-Zn(1)-Br(4) 104.91(6) Br(2)-Zn(1)-Br(1) 105.84(5) Br(5)-Zn(1)-Br(1) 110.44(6) Br(4)-Zn(1)-Br(1) 111.97(6) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 3ampZnBr?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b52 Crystallographic Investigation of n-Aminopyridinium Perhalometallates U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 40(5) 50(6) 11(3) 3(4) 5(3) -4(5) C(2) 34(4) 56(7) 21(4) -3(4) 7(4) 4(5) C(3) 53(6) 65(9) 26(4) -2(5) 5(4) -13(6) C(4) 63(7) 41(7) 51(6) 3(5) 18(6) 0(6) C(5) 41(5) 47(7) 44(5) 3(5) 17(4) 7(5) N(1) 46(5) 42(6) 37(4) 6(4) 9(4) -3(4) N(2) 42(4) 54(6) 20(3) -5(4) 7(3) -6(4) O(1) 63(5) 52(6) 55(5) 6(4) -10(4) -5(5) Zn(1) 40(1) 48(1) 19(1) 3(1) 9(1) -2(1) Br(1) 39(1) 62(1) 29(1) 4(1) 9(1) 2(1) Br(2) 44(1) 69(1) 24(1) 2(1) 3(1) -7(1) Br(4) 50(1) 53(1) 36(1) 13(1) 15(1) -2(1) Br(5) 54(1) 49(1) 43(1) -5(1) 25(1) -7(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 3ampZnBr?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) -4187 5865 4385 44 H(3) -3695 7522 4316 58 H(4) -6504 7629 5694 61 H(5) -8109 6818 6497 52 H(1A) -7993 5795 6844 62 H(1B) -6364 5471 6326 62 H(1C) -7955 5595 5075 62 H(2A) -2766 6651 3712 46 H(1D) -4030 4719 7973 2000(2000) H(1E) -3355 5365 7353 1400(1500) Table 6. Torsion angles [?] for 3ampZnBr?H2O. ________________________________________________________________ C(5)-C(1)-C(2)-N(2) 0.2(14) N(1)-C(1)-C(2)-N(2) -179.2(9) Este? Lawrence, Masters Dissertation 2011 b53 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(2)-C(3)-C(4)-C(5) 1.6(17) C(2)-C(1)-C(5)-C(4) 0.1(16) N(1)-C(1)-C(5)-C(4) 179.5(10) C(3)-C(4)-C(5)-C(1) -1.1(17) C(1)-C(2)-N(2)-C(3) 0.4(14) C(4)-C(3)-N(2)-C(2) -1.3(16) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 3ampZnBr?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Br(2)#1 0.89 2.68 3.483(9) 150.2 N(1)-H(1A)...Br(1)#1 0.89 2.96 3.502(9) 120.6 N(1)-H(1B)...O(1) 0.89 1.89 2.772(14) 169.1 N(1)-H(1C)...Br(4)#2 0.89 2.55 3.404(10) 160.0 N(2)-H(2A)...Br(5) 0.86 2.48 3.246(8) 148.9 O(1)-H(1D)...Br(1)#3 1.013(9) 2.3453(13) 3.353(9) 173.1(6) O(1)-H(1E)...Br(2)#4 0.954(9) 2.3946(13) 3.348(9) 179.9(7) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x-1,y,z+1 #2 x-1,y,z #3 -x,-y+1,-z+1 #4 x,y,z+1 Este? Lawrence, Masters Dissertation 2011 b54 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(3-ammoniopyridinium) tetraiodomercurate(II) monohydrate Table 1. Crystal data and structure refinement for 3ampHgI ?H2O. Identification code 3ampHgI ?H2O Empirical formula C4.97 H7.70 Hg0.98 I3.96 N1.86 O Formula weight 840.39 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group P 21/n Unit cell dimensions a = 8.3752(2) ? ?= 90?. b = 14.7432(3) ? ?= 93.663(2)?. c = 12.1260(3) ? ? = 90?. Volume 1494.23(6) ?3 Z 4 Density (calculated) 3.736 Mg/m3 Absorption coefficient 18.536 mm-1 F(000) 1456 Crystal size 0.5 x 0.5 x 0.2 mm3 Theta range for data collection 3.64 to 27.00?. Index ranges -10<=h<=10, -18<=k<=15, -15<=l<=15 Reflections collected 11030 Independent reflections 3261 [R(int) = 0.0380] Completeness to theta = 27.00? 99.7 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3261 / 0 / 142 Goodness-of-fit on F2 1.076 Final R indices [I>2sigma(I)] R1 = 0.0402, wR2 = 0.1191 R indices (all data) R1 = 0.0487, wR2 = 0.1300 Largest diff. peak and hole3.091 and -2.458 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 3ampHgI ?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ C(1) 7930(11) 9151(6) 2751(8) 27(3) Este? Lawrence, Masters Dissertation 2011 b55 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 6982(12) 8517(7) 3184(9) 30(4) C(3) 7099(11) 9323(6) 4886(8) 25(3) C(4) 8019(12) 9996(7) 4434(9) 29(3) C(5) 8447(11) 9915(6) 3366(9) 28(3) Hg(1) 6853(1) 7548(1) 8481(1) 29(1) I(1) 9651(1) 8539(1) 8966(1) 24(1) I(2) 5213(1) 7464(1) 10423(1) 27(1) I(3) 7572(1) 5869(1) 7581(1) 27(1) I(4) 4590(1) 8319(1) 6982(1) 32(1) N(1) 8348(11) 9050(6) 1622(7) 24(3) N(2) 6612(9) 8630(5) 4258(7) 20(3) O(1) 8429(10) 5282(7) 4559(9) 50(4) Table 3. Bond lengths [?] and angles [?] for 3ampHgI ?H2O. _____________________________________________________ C(1)-C(2) 1.354(14) C(1)-C(5) 1.403(14) C(1)-N(1) 1.443(12) C(2)-N(2) 1.368(14) C(2)-H(2) 0.9300 C(3)-N(2) 1.324(13) C(3)-C(4) 1.390(14) C(3)-H(3) 0.9300 C(4)-C(5) 1.371(14) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 Hg(1)-I(4) 2.7834(8) Hg(1)-I(3) 2.7868(7) Hg(1)-I(1) 2.7914(7) Hg(1)-I(2) 2.8043(8) N(1)-H(1A) 0.8900 N(1)-H(1B) 0.8900 N(1)-H(1C) 0.8900 N(2)-H(2A) 0.8600 O(1)-H(1D) 0.831(10) O(1)-H(1E) 0.814(11) Este? Lawrence, Masters Dissertation 2011 b56 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2)-C(1)-C(5) 121.2(9) C(2)-C(1)-N(1) 118.7(9) C(5)-C(1)-N(1) 120.1(9) C(1)-C(2)-N(2) 117.3(9) C(1)-C(2)-H(2) 121.4 N(2)-C(2)-H(2) 121.4 N(2)-C(3)-C(4) 118.9(9) N(2)-C(3)-H(3) 120.6 C(4)-C(3)-H(3) 120.6 C(5)-C(4)-C(3) 119.7(10) C(5)-C(4)-H(4) 120.2 C(3)-C(4)-H(4) 120.2 C(4)-C(5)-C(1) 118.8(9) C(4)-C(5)-H(5) 120.6 C(1)-C(5)-H(5) 120.6 I(4)-Hg(1)-I(3) 105.17(2) I(4)-Hg(1)-I(1) 116.85(2) I(3)-Hg(1)-I(1) 110.37(2) I(4)-Hg(1)-I(2) 102.52(2) I(3)-Hg(1)-I(2) 114.77(2) I(1)-Hg(1)-I(2) 107.22(2) C(1)-N(1)-H(1A) 109.5 C(1)-N(1)-H(1B) 109.5 H(1A)-N(1)-H(1B) 109.5 C(1)-N(1)-H(1C) 109.5 H(1A)-N(1)-H(1C) 109.5 H(1B)-N(1)-H(1C) 109.5 C(3)-N(2)-C(2) 124.2(8) C(3)-N(2)-H(2A) 117.9 C(2)-N(2)-H(2A) 117.9 H(1D)-O(1)-H(1E) 111.2(11) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 3ampHgI ?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b57 Crystallographic Investigation of n-Aminopyridinium Perhalometallates U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 27(5) 29(5) 23(6) -2(4) 0(4) 9(4) C(2) 24(5) 32(6) 34(7) 2(4) -3(4) -1(4) C(3) 28(5) 24(5) 21(6) -2(4) 1(4) 0(4) C(4) 37(6) 22(5) 28(6) -2(4) 3(4) -1(4) C(5) 29(5) 20(5) 34(6) 1(4) 4(4) 3(4) Hg(1) 24(1) 27(1) 35(1) -3(1) -2(1) 0(1) I(1) 22(1) 20(1) 31(1) 0(1) 2(1) -3(1) I(2) 22(1) 28(1) 30(1) -4(1) -1(1) -2(1) I(3) 29(1) 21(1) 32(1) -2(1) 4(1) -1(1) I(4) 25(1) 29(1) 41(1) 10(1) -4(1) -1(1) N(1) 31(5) 21(5) 20(5) 1(3) 1(3) 2(3) N(2) 18(4) 19(4) 22(5) 7(3) 0(3) -3(3) O(1) 38(5) 51(6) 58(7) -9(4) -9(4) 1(4) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 3ampHgI ?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 6599 8024 2768 36 H(3) 6831 9360 5617 30 H(4) 8342 10499 4853 35 H(5) 9069 10357 3054 33 H(1A) 7962 8527 1353 36 H(1B) 9408 9054 1598 36 H(1C) 7932 9506 1218 36 H(2A) 6025 8225 4543 24 H(1D) 8771 5791 4398 74 H(1E) 7921 5304 5108 74 Table 6. Torsion angles [?] for 3ampHgI ?H2O. ________________________________________________________________ C(5)-C(1)-C(2)-N(2) -2.9(14) N(1)-C(1)-C(2)-N(2) 179.7(8) Este? Lawrence, Masters Dissertation 2011 b58 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(2)-C(3)-C(4)-C(5) -2.2(15) C(3)-C(4)-C(5)-C(1) 0.5(15) C(2)-C(1)-C(5)-C(4) 2.1(15) N(1)-C(1)-C(5)-C(4) 179.4(9) C(4)-C(3)-N(2)-C(2) 1.4(15) C(1)-C(2)-N(2)-C(3) 1.1(15) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 3ampHgI ?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...I(2)#1 0.89 2.95 3.740(9) 149.0 N(1)-H(1A)...I(4)#2 0.89 3.12 3.662(9) 121.6 N(1)-H(1B)...I(3)#2 0.89 2.84 3.654(9) 153.3 N(1)-H(1C)...O(1)#3 0.89 1.83 2.701(13) 164.5 N(2)-H(2A)...I(1)#4 0.86 2.91 3.602(8) 138.7 N(2)-H(2A)...I(4) 0.86 3.27 3.834(8) 126.0 O(1)-H(1D)...I(2)#2 0.831(10) 3.07 3.765(9) 142.6(7) O(1)-H(1D)...I(4)#2 0.831(10) 3.32 3.918(11) 131.1(7) O(1)-H(1E)...I(3) 0.814(11) 3.14 3.877(11) 151.3(6) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,z-1 #2 x+1/2,-y+3/2,z-1/2 #3 -x+3/2,y+1/2,-z+1/2 #4 x-1/2,-y+3/2,z-1/2 Este? Lawrence, Masters Dissertation 2011 b59 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetrachlorozincate(II) Table 1. Crystal data and structure refinement for 4ampZnCl. Identification code 4ampZnCl Empirical formula C10 H14 Cl4 N4 Zn Formula weight 339.37 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P 21 21 21 Unit cell dimensions a = 7.1525(3) ? ?= 90?. b = 14.9902(12) ? ?= 90?. c = 14.9993(2) ? ? = 90?. Volume 1608.19(15) ?3 Z 4 Density (calculated) 1.402 Mg/m3 Absorption coefficient 2.163 mm-1 F(000) 680 Crystal size 0.4 x 0.4 x 0.3 mm3 Theta range for data collection 3.84 to 28.00?. Index ranges -9<=h<=9, -17<=k<=19, -17<=l<=19 Reflections collected 13762 Independent reflections 3869 [R(int) = 0.0211] Completeness to theta = 28.00? 99.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3869 / 0 / 172 Goodness-of-fit on F2 1.348 Final R indices [I>2sigma(I)] R1 = 0.0962, wR2 = 0.2277 R indices (all data) R1 = 0.0987, wR2 = 0.2286 Absolute structure parameter 0.05(5) Largest diff. peak and hole0.992 and -1.087 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampZnCl. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b60 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 2830(20) 13084(9) 4244(9) 40(3) C(2) 2710(20) 14032(9) 4387(11) 43(3) C(3) 2380(20) 14330(10) 5258(9) 44(3) C(4) 2260(20) 12900(10) 5838(12) 48(4) C(5) 2410(20) 12527(9) 4918(10) 44(3) C(6) 4688(15) 11835(8) 9451(7) 24(2) C(7) 4707(16) 11923(8) 8474(7) 28(2) C(8) 4950(20) 12763(12) 8130(10) 49(4) C(9) 5210(20) 13397(9) 9560(13) 52(4) C(10) 4982(16) 12608(8) 9969(8) 28(2) Cl(5) 2904(5) 10526(2) 6327(2) 41(1) N(1) 3075(19) 12731(8) 3477(7) 46(3) N(2) 2113(19) 13776(9) 5932(9) 51(3) N(3) 4510(20) 11023(7) 9795(8) 46(3) N(4) 5238(16) 13503(8) 8721(9) 44(3) Cl(1) 3399(5) 9368(2) 8440(2) 41(1) Cl(3) -669(6) 10922(2) 8182(2) 45(1) Cl(4) -521(5) 8794(2) 7011(2) 41(1) Zn(1) 1261(2) 9962(1) 7490(1) 26(1) Table 3. Bond lengths [?] and angles [?] for 4ampZnCl. _____________________________________________________ C(1)-N(1) 1.278(16) C(1)-C(5) 1.345(19) C(1)-C(2) 1.441(19) C(2)-C(3) 1.40(2) C(2)-H(2A) 0.9300 C(3)-N(2) 1.32(2) C(3)-H(3) 0.9300 C(4)-N(2) 1.325(19) C(4)-C(5) 1.49(2) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(3) 1.329(15) C(6)-C(10) 1.411(16) C(6)-C(7) 1.471(14) C(7)-C(8) 1.37(2) Este? Lawrence, Masters Dissertation 2011 b61 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(7)-H(7) 0.9300 C(8)-N(4) 1.43(2) C(8)-H(8) 0.9300 C(9)-N(4) 1.27(2) C(9)-C(10) 1.343(18) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 Cl(5)-Zn(1) 2.267(3) N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 Cl(1)-Zn(1) 2.272(3) Cl(3)-Zn(1) 2.248(3) Cl(4)-Zn(1) 2.282(3) N(1)-C(1)-C(5) 116.8(13) N(1)-C(1)-C(2) 123.4(13) C(5)-C(1)-C(2) 119.1(13) C(3)-C(2)-C(1) 117.6(14) C(3)-C(2)-H(2A) 121.2 C(1)-C(2)-H(2A) 121.2 N(2)-C(3)-C(2) 122.5(14) N(2)-C(3)-H(3) 118.8 C(2)-C(3)-H(3) 118.7 N(2)-C(4)-C(5) 118.4(16) N(2)-C(4)-H(4) 120.8 C(5)-C(4)-H(4) 120.8 C(1)-C(5)-C(4) 118.5(13) C(1)-C(5)-H(5) 120.7 C(4)-C(5)-H(5) 120.7 N(3)-C(6)-C(10) 123.5(10) N(3)-C(6)-C(7) 118.0(11) C(10)-C(6)-C(7) 118.3(11) C(8)-C(7)-C(6) 117.3(11) Este? Lawrence, Masters Dissertation 2011 b62 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(8)-C(7)-H(7) 121.4 C(6)-C(7)-H(7) 121.4 C(7)-C(8)-N(4) 119.7(12) C(7)-C(8)-H(8) 120.2 N(4)-C(8)-H(8) 120.2 N(4)-C(9)-C(10) 124.4(15) N(4)-C(9)-H(9) 117.8 C(10)-C(9)-H(9) 117.8 C(9)-C(10)-C(6) 119.3(12) C(9)-C(10)-H(10) 120.3 C(6)-C(10)-H(10) 120.4 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(4)-N(2)-C(3) 122.0(14) C(4)-N(2)-H(2) 119.0 C(3)-N(2)-H(2) 119.0 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(9)-N(4)-C(8) 121.0(13) C(9)-N(4)-H(4A) 119.5 C(8)-N(4)-H(4A) 119.5 Cl(3)-Zn(1)-Cl(5) 115.79(13) Cl(3)-Zn(1)-Cl(1) 111.96(14) Cl(5)-Zn(1)-Cl(1) 106.29(14) Cl(3)-Zn(1)-Cl(4) 107.04(15) Cl(5)-Zn(1)-Cl(4) 109.48(13) Cl(1)-Zn(1)-Cl(4) 105.84(14) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 4ampZnCl. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b63 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 53(8) 36(6) 30(6) -1(5) 18(6) -5(6) C(2) 35(7) 33(6) 62(9) 6(6) -8(7) 0(5) C(3) 50(8) 47(8) 34(7) -14(6) -10(6) 14(7) C(4) 28(6) 41(7) 74(11) -18(7) -3(7) 0(6) C(5) 62(10) 33(6) 37(7) 7(5) -4(7) 16(7) C(6) 14(5) 39(6) 19(5) -1(4) 3(4) 3(4) C(7) 26(5) 46(6) 13(5) -9(4) -1(4) 12(5) C(8) 34(7) 80(11) 35(7) -1(7) -6(6) 22(7) C(9) 42(8) 25(6) 88(13) 10(7) 13(8) 1(6) C(10) 29(6) 30(6) 27(5) 6(4) -6(5) 1(5) Cl(5) 41(2) 40(2) 42(2) 19(1) 6(1) 0(1) N(1) 72(9) 40(6) 25(5) 5(5) -3(6) -3(6) N(2) 56(8) 52(7) 46(7) -25(6) -4(6) 8(6) N(3) 64(8) 31(6) 42(6) -2(5) -9(6) -6(6) N(4) 34(6) 39(6) 59(8) 10(6) 20(6) -3(5) Cl(1) 51(2) 32(2) 41(2) 6(1) -14(1) 1(1) Cl(3) 70(2) 36(2) 27(1) -2(1) 4(2) 20(2) Cl(4) 57(2) 41(2) 27(1) -9(1) 8(1) -27(2) Zn(1) 33(1) 21(1) 24(1) 0(1) -1(1) -2(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampZnCl. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2A) 2838 14432 3917 52 H(3) 2343 14940 5366 52 H(4) 2275 12527 6333 57 H(5) 2216 11922 4813 53 H(7) 4561 11429 8105 34 H(8) 4926 12853 7516 59 H(9) 5352 13901 9915 62 H(10) 5019 12571 10588 34 H(1A) 2969 12163 3412 55 H(1B) 3346 13061 3027 55 H(2) 1836 13991 6447 61 Este? Lawrence, Masters Dissertation 2011 b64 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(3A) 4570 10948 10363 55 H(3B) 4331 10572 9450 55 H(4A) 5435 14025 8503 53 Table 6. Torsion angles [?] for 4ampZnCl. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) 178.0(15) C(5)-C(1)-C(2)-C(3) 8(2) C(1)-C(2)-C(3)-N(2) -3(2) N(1)-C(1)-C(5)-C(4) 175.2(14) C(2)-C(1)-C(5)-C(4) -14(2) N(2)-C(4)-C(5)-C(1) 16(2) N(3)-C(6)-C(7)-C(8) -178.1(12) C(10)-C(6)-C(7)-C(8) -2.2(17) C(6)-C(7)-C(8)-N(4) 2.3(18) N(4)-C(9)-C(10)-C(6) -2(2) N(3)-C(6)-C(10)-C(9) 177.8(13) C(7)-C(6)-C(10)-C(9) 2.1(18) C(5)-C(4)-N(2)-C(3) -11(2) C(2)-C(3)-N(2)-C(4) 4(2) C(10)-C(9)-N(4)-C(8) 3(2) C(7)-C(8)-N(4)-C(9) -3(2) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 4ampZnCl [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Cl(1)#1 0.86 2.50 3.32 160.0 N(1)-H(1B)...Cl(3)#2 0.86 2.47 3.33 174.9 N(2)-H(2)...Cl(4)#3 0.86 2.51 3.29 150.5 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1/2, -y+2, z-1/2 #2 x+1/2, -y+5/2, -z+1 #3 -x, y+1/2, -z+3/2 Este? Lawrence, Masters Dissertation 2011 b65 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetrabromozincate(II) Table 1. Crystal data and structure refinement for 4ampZnBr. Identification code 4ampZnBr Empirical formula C10 H14 Br4 N4 Zn Formula weight 575.26 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P 21 21 21 Unit cell dimensions a = 7.3747(7) ? ?= 90?. b = 15.4569(13) ? ?= 90?. c = 15.4716(15) ? ? = 90?. Volume 1763.6(3) ?3 Z 4 Density (calculated) 2.167 Mg/m3 Absorption coefficient 10.447 mm-1 F(000) 1088 Crystal size 0.2 x 0.2 x 0.2 mm3 Theta range for data collection 3.82 to 27.00?. Index ranges -9<=h<=8, -19<=k<=19, -19<=l<=19 Reflections collected 14103 Independent reflections 3839 [R(int) = 0.0491] Completeness to theta = 25.00? 99.5 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3839 / 0 / 173 Goodness-of-fit on F2 0.889 Final R indices [I>2sigma(I)] R1 = 0.0264, wR2 = 0.0502 R indices (all data) R1 = 0.0533, wR2 = 0.0527 Absolute structure parameter 0.002(15) Extinction coefficient 0.0294(5) Largest diff. peak and hole0.418 and -0.352 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampZnBr. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) Este? Lawrence, Masters Dissertation 2011 b66 Crystallographic Investigation of n-Aminopyridinium Perhalometallates ________________________________________________________________________________ C(1) 10254(7) 8167(3) 598(3) 56(1) C(2) 9935(6) 7410(3) 139(4) 62(2) C(3) 9668(7) 6661(4) 572(5) 76(2) C(4) 10076(6) 7332(5) 1885(4) 81(2) C(5) 10341(7) 8126(4) 1516(3) 67(1) C(6) 7206(7) 8154(4) 4234(4) 65(2) C(7) 7496(6) 7619(4) 4949(4) 65(2) C(8) 7850(8) 7968(5) 5723(5) 91(2) C(9) 7692(7) 9364(5) 5121(5) 87(2) C(10) 7295(6) 9065(4) 4319(5) 72(2) N(1) 10496(6) 8892(3) 200(3) 85(1) N(2) 9750(6) 6632(3) 1432(4) 82(2) N(3) 6834(7) 7820(3) 3511(4) 93(2) N(4) 7955(6) 8836(6) 5798(4) 104(2) Zn(1) 6311(1) 5067(1) 2503(1) 46(1) Br(1) 4418(1) 4078(1) 3270(1) 69(1) Br(2) 8557(1) 5670(1) 3468(1) 68(1) Br(3) 4453(1) 6261(1) 2028(1) 63(1) Br(4) 7854(1) 4446(1) 1305(1) 71(1) Table 3. Bond lengths [?] and angles [?] for 4ampZnBr. _____________________________________________________ C(1)-N(1) 1.291(6) C(1)-C(2) 1.389(7) C(1)-C(5) 1.423(7) C(2)-C(3) 1.351(7) C(2)-H(2) 0.9300 C(3)-N(2) 1.333(7) C(3)-H(3) 0.9300 C(4)-N(2) 1.311(7) C(4)-C(5) 1.367(8) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(3) 1.261(6) C(6)-C(7) 1.398(8) C(6)-C(10) 1.415(7) Este? Lawrence, Masters Dissertation 2011 b67 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(7)-C(8) 1.339(8) C(7)-H(7) 0.9300 C(8)-N(4) 1.350(8) C(8)-H(8) 0.9300 C(9)-N(4) 1.342(8) C(9)-C(10) 1.356(9) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 Zn(1)-Br(4) 2.3768(7) Zn(1)-Br(1) 2.3854(7) Zn(1)-Br(3) 2.4138(7) Zn(1)-Br(2) 2.4167(7) N(1)-C(1)-C(2) 120.8(5) N(1)-C(1)-C(5) 120.5(5) C(2)-C(1)-C(5) 118.7(5) C(3)-C(2)-C(1) 119.6(6) C(3)-C(2)-H(2) 120.2 C(1)-C(2)-H(2) 120.2 N(2)-C(3)-C(2) 121.1(6) N(2)-C(3)-H(3) 119.4 C(2)-C(3)-H(3) 119.4 N(2)-C(4)-C(5) 122.9(6) N(2)-C(4)-H(4) 118.6 C(5)-C(4)-H(4) 118.5 C(4)-C(5)-C(1) 116.8(5) C(4)-C(5)-H(5) 121.6 C(1)-C(5)-H(5) 121.6 N(3)-C(6)-C(7) 119.5(6) N(3)-C(6)-C(10) 120.0(6) C(7)-C(6)-C(10) 120.5(6) Este? Lawrence, Masters Dissertation 2011 b68 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(8)-C(7)-C(6) 120.0(6) C(8)-C(7)-H(7) 120.0 C(6)-C(7)-H(7) 120.0 C(7)-C(8)-N(4) 119.2(7) C(7)-C(8)-H(8) 120.4 N(4)-C(8)-H(8) 120.4 N(4)-C(9)-C(10) 122.6(6) N(4)-C(9)-H(9) 118.7 C(10)-C(9)-H(9) 118.7 C(9)-C(10)-C(6) 115.7(6) C(9)-C(10)-H(10) 122.2 C(6)-C(10)-H(10) 122.1 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(4)-N(2)-C(3) 120.9(5) C(4)-N(2)-H(2A) 119.5 C(3)-N(2)-H(2A) 119.5 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(9)-N(4)-C(8) 122.0(6) C(9)-N(4)-H(4A) 119.0 C(8)-N(4)-H(4A) 119.0 Br(4)-Zn(1)-Br(1) 114.16(3) Br(4)-Zn(1)-Br(3) 110.05(3) Br(1)-Zn(1)-Br(3) 108.00(3) Br(4)-Zn(1)-Br(2) 108.01(3) Br(1)-Zn(1)-Br(2) 109.96(3) Br(3)-Zn(1)-Br(2) 106.39(2) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 4ampZnBr. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 Este? Lawrence, Masters Dissertation 2011 b69 Crystallographic Investigation of n-Aminopyridinium Perhalometallates ______________________________________________________________________________ C(1) 51(3) 48(3) 67(4) 7(3) 7(3) 8(2) C(2) 71(4) 54(4) 60(3) -5(3) 3(3) -4(3) C(3) 58(4) 81(5) 87(5) 1(4) -3(4) -3(3) C(4) 62(4) 119(6) 62(4) 19(4) 7(3) 8(4) C(5) 60(3) 82(4) 57(4) -10(3) 5(3) -1(3) C(6) 51(3) 94(5) 51(4) -23(4) 1(3) -3(3) C(7) 71(4) 66(4) 56(4) 3(3) -6(3) -2(3) C(8) 60(4) 69(5) 144(7) -35(5) 16(4) -4(3) C(9) 53(4) 93(5) 115(6) -50(5) -4(4) 1(3) C(10) 51(3) 52(4) 113(6) 6(4) 1(3) 0(3) N(1) 120(4) 67(3) 68(3) -7(3) 5(3) -8(3) N(2) 71(3) 68(4) 106(5) 19(3) 3(3) -4(3) N(3) 123(4) 67(3) 88(4) 1(3) 7(3) 4(3) N(4) 64(3) 185(7) 62(4) -26(4) -5(3) 9(4) Zn(1) 57(1) 40(1) 41(1) -1(1) -1(1) 1(1) Br(1) 99(1) 55(1) 52(1) 4(1) 11(1) -18(1) Br(2) 90(1) 48(1) 66(1) 1(1) -34(1) -5(1) Br(3) 79(1) 62(1) 49(1) 10(1) -1(1) 24(1) Br(4) 86(1) 62(1) 67(1) -21(1) 21(1) 3(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampZnBr. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 9905 7418 -462 74 H(3) 9424 6158 264 91 H(4) 10129 7287 2484 97 H(5) 10568 8615 1849 80 H(7) 7444 7021 4887 78 H(8) 8021 7615 6204 109 H(9) 7786 9958 5205 104 H(10) 7095 9435 3854 87 H(1A) 10461 8910 -355 102 H(1B) 10693 9357 491 102 Este? Lawrence, Masters Dissertation 2011 b70 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(2A) 9586 6148 1694 98 H(3A) 6761 7267 3461 111 H(3B) 6654 8146 3069 111 H(4A) 8198 9058 6294 124 Table 6. Torsion angles [?] for 4ampZnBr. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) -179.4(5) C(5)-C(1)-C(2)-C(3) 1.7(7) C(1)-C(2)-C(3)-N(2) -1.6(8) N(2)-C(4)-C(5)-C(1) -0.2(8) N(1)-C(1)-C(5)-C(4) -179.7(5) C(2)-C(1)-C(5)-C(4) -0.9(8) N(3)-C(6)-C(7)-C(8) -178.4(6) C(10)-C(6)-C(7)-C(8) 0.5(8) C(6)-C(7)-C(8)-N(4) -1.3(8) N(4)-C(9)-C(10)-C(6) -1.1(8) N(3)-C(6)-C(10)-C(9) 179.6(5) C(7)-C(6)-C(10)-C(9) 0.7(8) C(5)-C(4)-N(2)-C(3) 0.3(8) C(2)-C(3)-N(2)-C(4) 0.6(9) C(10)-C(9)-N(4)-C(8) 0.4(9) C(7)-C(8)-N(4)-C(9) 0.9(9) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 4ampZnBr [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Br(3)#1 0.86 2.71 3.540(5) 163.9 N(1)-H(1B)...Br(2)#2 0.86 2.65 3.505(4) 173.3 N(2)-H(2A)...Br(2) 0.86 2.94 3.592(6) 134.0 N(2)-H(2A)...Br(4) 0.86 2.99 3.662(5) 137.1 N(3)-H(3A)...Br(2) 0.86 2.80 3.559(5) 147.8 N(4)-H(4A)...Br(3)#3 0.86 2.80 3.544(6) 145.7 N(4)-H(4A)...Br(1)#3 0.86 3.09 3.693(7) 128.8 Este? Lawrence, Masters Dissertation 2011 b71 Crystallographic Investigation of n-Aminopyridinium Perhalometallates ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x+1/2,-y+3/2,-z #2 -x+2,y+1/2,-z+1/2 #3 x+1/2,-y+3/2,-z+1 Este? Lawrence, Masters Dissertation 2011 b72 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetraiodozincate(II) Table 1. Crystal data and structure refinement for 4ampZnI Identification code 4ampZnI Empirical formula C10 H14 I4 N4 Zn Formula weight 463.36 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P 21 21 21 Unit cell dimensions a = 7.5844(4) ? ?= 90?. b = 16.0413(7) ? ?= 90?. c = 16.041 ? ? = 90?. Volume 1951.64(13) ?3 Z 4 Density (calculated) 1.577 Mg/m3 Absorption coefficient 4.399 mm-1 F(000) 852 Crystal size 0.50 x 0.37 x 0.34 mm3 Theta range for data collection 1.80 to 26.97?. Index ranges -9<=h<=9, -20<=k<=20, -18<=l<=20 Reflections collected 10847 Independent reflections 4001 [R(int) = 0.1539] Completeness to theta = 26.97? 98.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4001 / 0 / 162 Goodness-of-fit on F2 1.159 Final R indices [I>2sigma(I)] R1 = 0.0502, wR2 = 0.1310 R indices (all data) R1 = 0.0527, wR2 = 0.1377 Absolute structure parameter 0.04(7) Largest diff. peak and hole1.300 and -2.223 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampZnI U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b73 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 5383(15) 1702(8) 698(8) 27(2) C(2) 5308(17) 1735(11) 1583(9) 36(3) C(3) 4831(15) 2492(10) 1936(8) 34(3) C(4) 4530(20) 3121(10) 644(11) 45(4) C(5) 4948(16) 2400(10) 234(11) 39(3) C(6) 2719(15) 1868(7) 5707(8) 25(2) C(7) 2860(14) 973(8) 5700(10) 32(3) C(8) 2589(17) 563(9) 4985(9) 34(3) C(9) 1980(18) 1799(10) 4259(8) 35(3) C(10) 2200(20) 2235(9) 4957(9) 38(3) N(1) 5844(15) 977(9) 339(8) 38(3) N(2) 4406(14) 3138(9) 1475(9) 42(3) N(3) 2994(15) 2308(9) 6398(8) 39(3) N(4) 2102(12) 941(9) 4302(7) 38(3) Zn(1) 3838(2) 5024(1) -2586(1) 21(1) I(1) 6218(1) 6012(1) -3256(1) 29(1) I(2) 1786(1) 4549(1) -3805(1) 27(1) I(3) 1986(1) 5901(1) -1546(1) 29(1) I(4) 5386(1) 3763(1) -1914(1) 32(1) Table 3. Bond lengths [?] and angles [?] for 4ampZnI _____________________________________________________ C(1)-N(1) 1.344(18) C(1)-C(5) 1.38(2) C(1)-C(2) 1.42(2) C(2)-C(3) 1.39(2) C(2)-H(2) 0.9300 C(3)-N(2) 1.31(2) C(3)-H(3) 0.9300 C(4)-N(2) 1.34(2) C(4)-C(5) 1.37(2) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-N(3) 1.330(17) C(6)-C(10) 1.396(19) C(6)-C(7) 1.440(16) C(7)-C(8) 1.34(2) Este? Lawrence, Masters Dissertation 2011 b74 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(7)-H(7) 0.9300 C(8)-N(4) 1.31(2) C(8)-H(8) 0.9300 C(9)-C(10) 1.33(2) C(9)-N(4) 1.38(2) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 Zn(1)-I(4) 2.5748(15) Zn(1)-I(3) 2.5951(15) Zn(1)-I(2) 2.6129(15) Zn(1)-I(1) 2.6321(15) N(1)-C(1)-C(5) 122.2(13) N(1)-C(1)-C(2) 118.1(14) C(5)-C(1)-C(2) 119.7(14) C(3)-C(2)-C(1) 116.8(14) C(3)-C(2)-H(2) 121.6 C(1)-C(2)-H(2) 121.6 N(2)-C(3)-C(2) 121.7(12) N(2)-C(3)-H(3) 119.2 C(2)-C(3)-H(3) 119.2 N(2)-C(4)-C(5) 120.9(16) N(2)-C(4)-H(4) 119.5 C(5)-C(4)-H(4) 119.5 C(4)-C(5)-C(1) 118.8(15) C(4)-C(5)-H(5) 120.6 C(1)-C(5)-H(5) 120.6 N(3)-C(6)-C(10) 122.6(11) N(3)-C(6)-C(7) 121.6(13) C(10)-C(6)-C(7) 115.7(12) C(8)-C(7)-C(6) 119.1(13) Este? Lawrence, Masters Dissertation 2011 b75 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(8)-C(7)-H(7) 120.5 C(6)-C(7)-H(7) 120.5 N(4)-C(8)-C(7) 122.4(13) N(4)-C(8)-H(8) 118.8 C(7)-C(8)-H(8) 118.8 C(10)-C(9)-N(4) 118.2(13) C(10)-C(9)-H(9) 120.9 N(4)-C(9)-H(9) 120.9 C(9)-C(10)-C(6) 122.7(13) C(9)-C(10)-H(10) 118.6 C(6)-C(10)-H(10) 118.6 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(3)-N(2)-C(4) 121.8(13) C(3)-N(2)-H(2A) 119.1 C(4)-N(2)-H(2A) 119.1 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(8)-N(4)-C(9) 121.5(12) C(8)-N(4)-H(4A) 119.2 C(9)-N(4)-H(4A) 119.2 I(4)-Zn(1)-I(3) 113.83(5) I(4)-Zn(1)-I(2) 110.86(6) I(3)-Zn(1)-I(2) 108.47(5) I(4)-Zn(1)-I(1) 109.32(5) I(3)-Zn(1)-I(1) 107.90(5) I(2)-Zn(1)-I(1) 106.13(5) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (?2x 103)for 4ampZnI The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b76 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 26(5) 26(6) 28(6) -1(5) 1(5) 2(5) C(2) 29(5) 47(8) 33(7) 11(6) 5(5) -2(6) C(3) 23(5) 56(9) 23(6) -6(6) -6(5) 5(5) C(4) 52(8) 27(7) 57(10) -8(7) 5(8) 13(7) C(5) 24(5) 41(8) 51(9) 6(7) -8(6) -3(5) C(6) 25(5) 18(5) 31(6) -5(5) 3(5) 0(4) C(7) 24(5) 18(6) 53(8) 0(5) 15(5) 9(4) C(8) 38(6) 25(6) 39(7) -5(5) 5(6) 0(5) C(9) 37(6) 43(8) 25(6) 8(6) -4(5) 6(6) C(10) 58(8) 27(6) 30(6) 1(5) 13(6) 12(6) N(2) 22(4) 44(7) 60(8) -34(7) 4(5) 4(5) N(4) 21(4) 61(8) 32(6) -24(6) 2(4) -16(5) Zn(1) 24(1) 17(1) 23(1) 0(1) -1(1) 0(1) I(1) 36(1) 26(1) 24(1) -3(1) 4(1) -13(1) I(2) 32(1) 19(1) 30(1) -2(1) -10(1) -2(1) I(3) 39(1) 23(1) 24(1) -1(1) 6(1) 6(1) I(4) 35(1) 27(1) 35(1) 8(1) -4(1) 7(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampZnI ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 5567 1272 1909 44 H(3) 4812 2543 2513 41 H(4) 4340 3607 341 54 H(5) 4937 2379 -345 46 H(7) 3134 684 6186 38 H(8) 2754 -11 4975 41 H(9) 1750 2066 3755 42 H(10) 1998 2806 4945 46 H(1A) 5876 936 -195 46 H(1B) 6107 554 644 46 H(2A) 4034 3585 1714 50 H(3A) 2851 2840 6394 46 H(3B) 3314 2061 6849 46 Este? Lawrence, Masters Dissertation 2011 b77 Crystallographic Investigation of n-Aminopyridinium Perhalometallates H(4A) 1851 648 3869 46 Table 6. Torsion angles [?] for 4ampZnI ________________________________________________________________ N(1)-C(1)-C(2)-C(3) 179.9(11) C(5)-C(1)-C(2)-C(3) -1.5(19) C(1)-C(2)-C(3)-N(2) 2.4(19) N(2)-C(4)-C(5)-C(1) -6(2) N(1)-C(1)-C(5)-C(4) -178.4(13) C(2)-C(1)-C(5)-C(4) 3(2) N(3)-C(6)-C(7)-C(8) -179.3(11) C(10)-C(6)-C(7)-C(8) 3.7(17) C(6)-C(7)-C(8)-N(4) -4.0(18) N(4)-C(9)-C(10)-C(6) 7(2) N(3)-C(6)-C(10)-C(9) 177.8(13) C(7)-C(6)-C(10)-C(9) -5(2) C(2)-C(3)-N(2)-C(4) -5(2) C(5)-C(4)-N(2)-C(3) 7(2) C(7)-C(8)-N(4)-C(9) 5.6(19) C(10)-C(9)-N(4)-C(8) -7(2) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 7. Hydrogen bonds for 4ampZnI [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...I(1)#1 0.86 2.95 3.689(13) 145.1 N(1)-H(1A)...I(2)#1 0.86 3.27 3.812(13) 123.8 N(1)-H(1B)...I(3)#2 0.86 2.83 3.685(14) 176.1 N(2)-H(2A)...I(3)#3 0.86 3.01 3.683(12) 136.6 N(2)-H(2A)...I(2)#3 0.86 3.17 3.844(14) 137.2 N(3)-H(3A)...I(2)#4 0.86 2.88 3.724(14) 169.1 N(3)-H(3B)...I(1)#5 0.86 2.84 3.683(13) 168.0 N(4)-H(4A)...I(1)#6 0.86 2.88 3.616(12) 144.8 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Este? Lawrence, Masters Dissertation 2011 b78 Crystallographic Investigation of n-Aminopyridinium Perhalometallates #1 -x+1,y-1/2,-z-1/2 #2 x+1/2,-y+1/2,-z #3 -x+1/2,-y+1,z+1/2 #4 x,y,z+1 #5 -x+1,y-1/2,-z+1/2 #6 x-1/2,-y+1/2,-z Este? Lawrence, Masters Dissertation 2011 b79 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Catena-(bis(4-aminopyridinium) bis(?2-chloro) dichlorocadmium(II) monohydrate) Table 1. Crystal data and structure refinement for 4ampCdCl?H2O. Identification code 4ampCdCl?H2O Empirical formula C10 H16 Cd2 Cl8 N4 O Formula weight 253.09 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = 7.496(5) ? ?= 90?. b = 24.413(5) ? ?= 101.93(4)?. c = 12.453(5) ? ? = 90?. Volume 2229.8(18) ?3 Z 4 Density (calculated) 0.754 Mg/m3 Absorption coefficient 1.244 mm-1 F(000) 474 Crystal size 1.00 x 1.00 x 1.00 mm3 Theta range for data collection 4.23 to 27.00?. Index ranges -9<=h<=7, -31<=k<=31, -15<=l<=15 Reflections collected 15532 Independent reflections 4852 [R(int) = 0.3919] Completeness to theta = 27.00? 99.5 % Max. and min. transmission 0.3693 and 0.3693 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4852 / 0 / 221 Goodness-of-fit on F2 1.881 Final R indices [I>2sigma(I)] R1 = 0.1997, wR2 = 0.4957 R indices (all data) R1 = 0.2077, wR2 = 0.5042 Extinction coefficient 0.009(3) Largest diff. peak and hole5.159 and -4.067 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampCdCl?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) Este? Lawrence, Masters Dissertation 2011 b80 Crystallographic Investigation of n-Aminopyridinium Perhalometallates ________________________________________________________________________________ C(1) -4790(40) 6486(9) 3360(20) 65(6) C(2) -5180(30) 6078(11) 4007(16) 65(6) C(3) -5670(30) 5579(10) 3682(18) 69(6) C(4) -5120(40) 5806(17) 1960(20) 91(10) C(5) -4840(40) 6366(12) 2266(18) 73(7) C(6) 120(30) 3996(10) 7576(14) 56(5) C(7) 430(30) 4369(9) 6805(19) 62(5) C(8) 480(40) 4181(10) 5820(20) 75(7) C(9) -70(60) 3314(12) 6190(30) 108(12) C(10) -230(50) 3463(14) 7370(30) 91(9) Cl(1) -1864(6) 5703(2) 6837(3) 40(1) Cl(2) 3869(6) 6740(2) 8940(4) 49(1) Cl(3) 8935(6) 6668(2) 9090(3) 47(1) Cl(4) 3125(5) 5810(2) 6637(3) 38(1) Cl(5) 5980(20) 5485(5) 8901(10) 149(5) Cl(6) 1934(7) 5368(2) 9320(4) 54(1) Cl(7) 70(30) 6871(6) 6550(13) 172(6) Cl(8) 6016(7) 7147(2) 6500(4) 54(1) O(1) 2100(20) 7689(9) 5938(16) 88(6) N(1) -4440(30) 6981(8) 3702(17) 73(6) N(2) -5590(30) 5468(8) 2590(20) 78(6) N(3) 160(30) 4145(9) 8647(15) 74(5) N(4) 169(1) 3663(1) 5502(1) 84(7) Cd(1) 1079(1) 6168(1) 7968(1) 39(1) Cd(2) 5990(1) 6308(1) 7766(1) 38(1) Table 3. Bond lengths [?] and angles [?] for 4ampCdCl?H2O. _____________________________________________________ C(1)-N(1) 1.29(3) C(1)-C(2) 1.34(3) C(1)-C(5) 1.39(3) C(2)-C(3) 1.31(4) C(2)-H(2) 0.9300 C(3)-N(2) 1.40(3) C(3)-H(3) 0.9300 C(4)-N(2) 1.24(4) Este? Lawrence, Masters Dissertation 2011 b81 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(4)-C(5) 1.43(5) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 C(6)-C(10) 1.34(4) C(6)-N(3) 1.38(2) C(6)-C(7) 1.38(3) C(7)-C(8) 1.32(3) C(7)-H(7) 0.9300 C(8)-N(4) 1.33(2) C(8)-H(8) 0.9300 C(9)-N(4) 1.25(4) C(9)-C(10) 1.54(5) C(9)-H(9) 0.9300 C(10)-H(10) 0.9300 Cl(1)-Cd(1) 2.619(4) Cl(1)-Cd(2)#1 2.622(4) Cl(2)-Cd(2) 2.597(4) Cl(2)-Cd(1) 2.597(4) Cl(3)-Cd(2) 2.619(5) Cl(3)-Cd(1)#2 2.637(4) Cl(4)-Cd(2) 2.611(4) Cl(4)-Cd(1) 2.630(3) Cl(5)-Cd(2) 2.458(11) Cl(6)-Cd(1) 2.572(5) Cl(7)-Cd(1) 2.467(19) Cl(7)-H(1D) 1.8094 Cl(8)-Cd(2) 2.588(4) O(1)-H(1C) 0.9048 O(1)-H(1D) 0.9033 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 N(3)-H(3A) 0.8600 N(3)-H(3B) 0.8600 N(4)-H(4A) 0.8600 Cd(1)-Cl(3)#1 2.637(4) Cd(2)-Cl(1)#2 2.622(4) Este? Lawrence, Masters Dissertation 2011 b82 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(1)-C(1)-C(2) 124(2) N(1)-C(1)-C(5) 119(2) C(2)-C(1)-C(5) 118(2) C(3)-C(2)-C(1) 126(2) C(3)-C(2)-H(2) 117.1 C(1)-C(2)-H(2) 117.1 C(2)-C(3)-N(2) 114.5(18) C(2)-C(3)-H(3) 122.8 N(2)-C(3)-H(3) 122.7 N(2)-C(4)-C(5) 121(2) N(2)-C(4)-H(4) 119.6 C(5)-C(4)-H(4) 119.6 C(1)-C(5)-C(4) 116(2) C(1)-C(5)-H(5) 122.1 C(4)-C(5)-H(5) 122.1 C(10)-C(6)-N(3) 114(2) C(10)-C(6)-C(7) 124(2) N(3)-C(6)-C(7) 122(2) C(8)-C(7)-C(6) 118(2) C(8)-C(7)-H(7) 121.3 C(6)-C(7)-H(7) 121.2 C(7)-C(8)-N(4) 125(2) C(7)-C(8)-H(8) 117.6 N(4)-C(8)-H(8) 117.7 N(4)-C(9)-C(10) 123(2) N(4)-C(9)-H(9) 118.5 C(10)-C(9)-H(9) 118.5 C(6)-C(10)-C(9) 111(2) C(6)-C(10)-H(10) 124.4 C(9)-C(10)-H(10) 124.4 Cd(1)-Cl(1)-Cd(2)#1 92.52(12) Cd(2)-Cl(2)-Cd(1) 92.67(12) Cd(2)-Cl(3)-Cd(1)#2 92.16(12) Cd(2)-Cl(4)-Cd(1) 91.60(12) Cd(1)-Cl(7)-H(1D) 127.1 H(1C)-O(1)-H(1D) 99.7 Este? Lawrence, Masters Dissertation 2011 b83 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(4)-N(2)-C(3) 124(2) C(4)-N(2)-H(2A) 117.9 C(3)-N(2)-H(2A) 117.9 C(6)-N(3)-H(3A) 120.0 C(6)-N(3)-H(3B) 120.0 H(3A)-N(3)-H(3B) 120.0 C(9)-N(4)-C(8) 118.9(14) C(9)-N(4)-H(4A) 120.5 C(8)-N(4)-H(4A) 120.6 Cl(7)-Cd(1)-Cl(6) 174.4(3) Cl(7)-Cd(1)-Cl(2) 93.3(4) Cl(6)-Cd(1)-Cl(2) 92.04(17) Cl(7)-Cd(1)-Cl(1) 79.5(4) Cl(6)-Cd(1)-Cl(1) 95.21(15) Cl(2)-Cd(1)-Cl(1) 172.69(16) Cl(7)-Cd(1)-Cl(4) 85.0(4) Cl(6)-Cd(1)-Cl(4) 93.50(14) Cl(2)-Cd(1)-Cl(4) 87.38(12) Cl(1)-Cd(1)-Cl(4) 93.06(12) Cl(7)-Cd(1)-Cl(3)#1 85.8(4) Cl(6)-Cd(1)-Cl(3)#1 95.79(16) Cl(2)-Cd(1)-Cl(3)#1 91.40(13) Cl(1)-Cd(1)-Cl(3)#1 86.99(12) Cl(4)-Cd(1)-Cl(3)#1 170.67(15) Cl(5)-Cd(2)-Cl(8) 177.5(3) Cl(5)-Cd(2)-Cl(2) 86.2(3) Cl(8)-Cd(2)-Cl(2) 95.92(15) Cl(5)-Cd(2)-Cl(4) 80.1(4) Cl(8)-Cd(2)-Cl(4) 98.61(16) Cl(2)-Cd(2)-Cl(4) 87.78(13) Cl(5)-Cd(2)-Cl(3) 90.9(4) Cl(8)-Cd(2)-Cl(3) 90.36(17) Cl(2)-Cd(2)-Cl(3) 92.49(13) Cl(4)-Cd(2)-Cl(3) 170.95(15) Este? Lawrence, Masters Dissertation 2011 b84 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Cl(5)-Cd(2)-Cl(1)#2 82.5(3) Cl(8)-Cd(2)-Cl(1)#2 95.45(13) Cl(2)-Cd(2)-Cl(1)#2 168.62(15) Cl(4)-Cd(2)-Cl(1)#2 90.66(12) Cl(3)-Cd(2)-Cl(1)#2 87.29(13) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x-1,y,z #2 x+1,y,z Table 4. Anisotropic displacement parameters (?2x 103)for 4ampCdCl?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 98(16) 41(10) 75(14) 8(9) 60(13) 25(10) C(2) 89(16) 88(17) 24(8) 13(8) 28(9) 10(12) C(3) 78(14) 72(15) 52(12) 15(10) 3(11) -26(11) C(4) 82(16) 160(30) 42(12) -11(15) 40(12) -33(18) C(5) 93(18) 90(20) 36(10) 20(10) 17(11) -12(13) C(6) 73(13) 76(13) 22(8) -8(7) 17(8) 14(10) C(7) 83(14) 47(11) 59(12) 2(8) 24(11) 4(9) C(8) 104(18) 59(14) 80(16) -13(11) 64(15) -19(12) C(9) 200(40) 51(15) 80(20) -40(15) 40(20) -25(19) C(10) 100(20) 90(20) 72(18) 24(14) -4(15) -15(15) Cl(1) 52(2) 37(2) 39(2) -13(1) 26(2) -3(2) Cl(2) 55(2) 53(2) 48(2) -25(2) 31(2) -13(2) Cl(3) 52(2) 63(3) 33(2) -19(2) 22(2) -6(2) Cl(4) 40(2) 49(2) 30(2) -7(1) 20(1) 0(1) Cl(5) 241(14) 93(8) 129(9) 15(6) 76(9) 11(8) Cl(6) 73(3) 54(3) 37(2) 11(2) 19(2) 0(2) Cl(7) 262(17) 133(11) 150(11) -40(8) 110(12) -69(10) Cl(8) 73(3) 50(3) 46(2) 11(2) 33(2) 12(2) O(1) 60(9) 126(17) 87(13) 51(11) 36(9) -12(9) N(1) 109(16) 53(11) 66(12) -2(8) 36(11) 31(10) N(2) 94(14) 37(9) 110(17) -27(10) 36(13) -17(8) N(3) 120(16) 66(13) 45(10) -5(8) 37(10) -3(11) N(4) 140(20) 54(12) 71(14) -24(10) 59(14) -1(11) Este? Lawrence, Masters Dissertation 2011 b85 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Cd(1) 50(1) 40(1) 32(1) -1(1) 23(1) -2(1) Cd(2) 47(1) 36(1) 38(1) -2(1) 24(1) 1(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampCdCl?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) -5087 6157 4746 78 H(3) -6034 5321 4141 83 H(4) -4951 5691 1275 109 H(5) -4691 6636 1763 88 H(7) 590 4739 6973 74 H(8) 759 4428 5310 90 H(9) -156 2947 5988 130 H(10) -523 3216 7875 109 H(1A) -4454 7066 4371 88 H(1B) -4206 7227 3258 88 H(2A) -5888 5144 2346 94 H(3A) -24 3903 9114 89 H(3B) 371 4479 8849 89 H(4A) 132 3570 4832 101 H(1C) 3218 7533 6100 126 H(1D) 1432 7415 6145 126 Table 6. Torsion angles [?] for 4ampCdCl?H2O. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) 175(3) C(5)-C(1)-C(2)-C(3) -3(4) C(1)-C(2)-C(3)-N(2) 6(4) N(1)-C(1)-C(5)-C(4) 177(3) C(2)-C(1)-C(5)-C(4) -6(4) N(2)-C(4)-C(5)-C(1) 11(4) C(10)-C(6)-C(7)-C(8) -4(4) N(3)-C(6)-C(7)-C(8) 175(2) C(6)-C(7)-C(8)-N(4) 4(4) Este? Lawrence, Masters Dissertation 2011 b86 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(3)-C(6)-C(10)-C(9) -174(3) C(7)-C(6)-C(10)-C(9) 5(4) N(4)-C(9)-C(10)-C(6) -7(5) C(5)-C(4)-N(2)-C(3) -8(5) C(2)-C(3)-N(2)-C(4) -1(4) C(10)-C(9)-N(4)-C(8) 7(5) C(7)-C(8)-N(4)-C(9) -5(4) Cd(2)-Cl(2)-Cd(1)-Cl(7) -90.6(4) Cd(2)-Cl(2)-Cd(1)-Cl(6) 87.66(17) Cd(2)-Cl(2)-Cd(1)-Cl(1) -99.3(8) Cd(2)-Cl(2)-Cd(1)-Cl(4) -5.75(15) Cd(2)-Cl(2)-Cd(1)-Cl(3)#1 -176.49(16) Cd(2)#1-Cl(1)-Cd(1)-Cl(7) -78.6(4) Cd(2)#1-Cl(1)-Cd(1)-Cl(6) 103.22(15) Cd(2)#1-Cl(1)-Cd(1)-Cl(2) -69.8(9) Cd(2)#1-Cl(1)-Cd(1)-Cl(4) -162.98(12) Cd(2)#1-Cl(1)-Cd(1)-Cl(3)#1 7.67(14) Cd(2)-Cl(4)-Cd(1)-Cl(7) 99.2(4) Cd(2)-Cl(4)-Cd(1)-Cl(6) -86.18(15) Cd(2)-Cl(4)-Cd(1)-Cl(2) 5.71(15) Cd(2)-Cl(4)-Cd(1)-Cl(1) 178.41(12) Cd(2)-Cl(4)-Cd(1)-Cl(3)#1 88.3(8) Cd(1)-Cl(2)-Cd(2)-Cl(5) -74.5(4) Cd(1)-Cl(2)-Cd(2)-Cl(8) 104.22(18) Cd(1)-Cl(2)-Cd(2)-Cl(4) 5.79(15) Cd(1)-Cl(2)-Cd(2)-Cl(3) -165.16(16) Cd(1)-Cl(2)-Cd(2)-Cl(1)#2 -76.5(7) Cd(1)-Cl(4)-Cd(2)-Cl(5) 80.8(3) Cd(1)-Cl(4)-Cd(2)-Cl(8) -101.37(13) Cd(1)-Cl(4)-Cd(2)-Cl(2) -5.71(14) Cd(1)-Cl(4)-Cd(2)-Cl(3) 86.2(7) Cd(1)-Cl(4)-Cd(2)-Cl(1)#2 163.02(12) Cd(1)#2-Cl(3)-Cd(2)-Cl(5) 90.1(3) Cd(1)#2-Cl(3)-Cd(2)-Cl(8) -87.77(15) Cd(1)#2-Cl(3)-Cd(2)-Cl(2) 176.28(15) Cd(1)#2-Cl(3)-Cd(2)-Cl(4) 84.8(7) Cd(1)#2-Cl(3)-Cd(2)-Cl(1)#2 7.67(14) Este? Lawrence, Masters Dissertation 2011 b87 Crystallographic Investigation of n-Aminopyridinium Perhalometallates ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x-1,y,z #2 x+1,y,z Table 7. Hydrogen bonds for 4ampCdCl?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Cl(8)#1 0.86 2.61 3.45(2) 167.6 N(1)-H(1B)...Cl(8)#3 0.86 2.70 3.54(2) 166.3 N(2)-H(2A)...Cl(5)#4 0.86 2.18 2.96(2) 150.6 N(2)-H(2A)...Cl(1)#5 0.86 2.98 3.59(2) 129.7 N(3)-H(3A)...Cl(3)#6 0.86 2.62 3.40(2) 151.4 N(3)-H(3B)...Cl(6) 0.86 2.48 3.31(2) 161.9 N(4)-H(4A)...Cl(7)#4 0.86 2.01 2.841(13) 162.7 O(1)-H(1C)...Cl(8) 0.90 2.26 3.163(19) 179.6 O(1)-H(1D)...Cl(7) 0.90 1.81 2.71(2) 179.3 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x-1,y,z #2 x+1,y,z #3 x-1,-y+3/2,z-1/2 #4 -x,-y+1,-z+1 #5 -x-1,-y+1,-z+1 #6 -x+1,-y+1,-z+2 Este? Lawrence, Masters Dissertation 2011 b88 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetrabromocadmate(II) monohydrate Table 1. Crystal data and structure refinement for 4ampCdBr?H2O. Identification code 4ampCdBr?H2O Empirical formula C10 H16 Br4 Cd N4 O Formula weight 640.31 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P b c m Unit cell dimensions a = 6.8746(12) ? ?= 90?. b = 14.082(2) ? ?= 90?. c = 18.842(3) ? ? = 90?. Volume 1824.1(5) ?3 Z 4 Density (calculated) 2.332 Mg/m3 Absorption coefficient 9.959 mm-1 F(000) 1200 Crystal size 0.3 x 0.2 x 0.2 mm3 Theta range for data collection 2.16 to 27.00?. Index ranges -8<=h<=8, -17<=k<=17, -24<=l<=24 Reflections collected 21740 Independent reflections 2049 [R(int) = 0.0945] Completeness to theta = 25.00? 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2049 / 3 / 102 Goodness-of-fit on F2 1.068 Final R indices [I>2sigma(I)] R1 = 0.0296, wR2 = 0.0650 R indices (all data) R1 = 0.0372, wR2 = 0.0687 Extinction coefficient 0.0109(4) Largest diff. peak and hole0.836 and -0.527 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampCdBr?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b89 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 8586(5) 8723(3) 170(2) 38(1) C(2) 6867(6) 9026(3) -177(2) 51(1) C(3) 6932(8) 9366(4) -835(3) 63(1) C(4) 10256(8) 9101(3) -896(2) 57(1) C(5) 10308(6) 8765(3) -224(2) 45(1) N(1) 8551(5) 8422(3) 842(2) 50(1) N(2) 8599(7) 9414(3) -1193(2) 61(1) O(1) 9128(8) 372(3) 7500 55(1) Br(1) 8578(1) 7404(1) 2500 40(1) Br(2) 3947(1) 5417(1) 2500 45(1) Br(3) 3581(1) 7997(1) 1342(1) 48(1) Cd(1) 4828(1) 7208(1) 2500 38(1) Table 3. Bond lengths [?] and angles [?] for 4ampCdBr?H2O. _____________________________________________________ C(1)-N(1) 1.335(5) C(1)-C(5) 1.399(6) C(1)-C(2) 1.416(6) C(2)-C(3) 1.331(7) C(2)-H(2) 0.9300 C(3)-N(2) 1.331(7) C(3)-H(3) 0.9300 C(4)-N(2) 1.343(7) C(4)-C(5) 1.352(6) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 O(1)-H(1D) 0.843(19) O(1)-H(1E) 0.838(19) Br(1)-Cd(1) 2.5926(8) Br(2)-Cd(1) 2.5934(8) Br(3)-Cd(1) 2.5944(6) Cd(1)-Br(3)#1 2.5944(6) N(1)-C(1)-C(5) 122.2(4) Este? Lawrence, Masters Dissertation 2011 b90 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(1)-C(1)-C(2) 121.2(4) C(5)-C(1)-C(2) 116.6(4) C(3)-C(2)-C(1) 120.7(5) C(3)-C(2)-H(2) 119.6 C(1)-C(2)-H(2) 119.6 C(2)-C(3)-N(2) 121.2(5) C(2)-C(3)-H(3) 119.4 N(2)-C(3)-H(3) 119.4 N(2)-C(4)-C(5) 121.7(4) N(2)-C(4)-H(4) 119.1 C(5)-C(4)-H(4) 119.1 C(4)-C(5)-C(1) 119.4(4) C(4)-C(5)-H(5) 120.3 C(1)-C(5)-H(5) 120.3 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(3)-N(2)-C(4) 120.2(4) C(3)-N(2)-H(2A) 119.9 C(4)-N(2)-H(2A) 119.9 H(1D)-O(1)-H(1E) 126(5) Br(1)-Cd(1)-Br(2) 109.61(2) Br(1)-Cd(1)-Br(3)#1 106.436(15) Br(2)-Cd(1)-Br(3)#1 109.845(17) Br(1)-Cd(1)-Br(3) 106.436(15) Br(2)-Cd(1)-Br(3) 109.845(16) Br(3)#1-Cd(1)-Br(3) 114.49(3) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 4ampCdBr?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 41(2) 36(2) 36(2) 0(2) -2(2) -4(2) Este? Lawrence, Masters Dissertation 2011 b91 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 48(2) 55(3) 49(2) 3(2) -6(2) -2(2) C(3) 76(3) 66(3) 48(3) 3(2) -19(2) -2(3) C(4) 78(3) 45(2) 49(2) -5(2) 26(2) -8(2) C(5) 47(2) 42(2) 47(2) -1(2) 7(2) 1(2) N(1) 50(2) 63(2) 37(2) 13(2) 2(2) 0(2) N(2) 107(4) 49(2) 28(2) -2(2) -3(2) -4(2) O(1) 68(3) 56(3) 42(2) 0 0 1(2) Br(1) 35(1) 48(1) 36(1) 0 0 -4(1) Br(2) 47(1) 42(1) 46(1) 0 0 -5(1) Br(3) 38(1) 64(1) 42(1) 15(1) -5(1) -1(1) Cd(1) 38(1) 43(1) 32(1) 0 0 -1(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampCdBr?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 5680 8986 58 61 H(3) 5791 9573 -1050 76 H(4) 11399 9116 -1160 69 H(5) 11476 8565 -26 55 H(1A) 9610 8246 1046 60 H(1B) 7469 8404 1071 60 H(2A) 8615 9645 -1615 74 H(1D) 10350(30) 410(50) 7500 67 H(1E) 8340(70) 830(30) 7500 67 Table 6. Torsion angles [?] for 4ampCdBr?H2O. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) 176.9(4) C(5)-C(1)-C(2)-C(3) -2.5(7) C(1)-C(2)-C(3)-N(2) 1.4(8) N(2)-C(4)-C(5)-C(1) 1.3(7) N(1)-C(1)-C(5)-C(4) -178.2(4) C(2)-C(1)-C(5)-C(4) 1.2(6) C(2)-C(3)-N(2)-C(4) 1.2(8) Este? Lawrence, Masters Dissertation 2011 b92 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(5)-C(4)-N(2)-C(3) -2.6(7) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 7. Hydrogen bonds for 4ampCdBr?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Br(3)#2 0.86 2.81 3.634(4) 161.4 N(1)-H(1B)...Br(3) 0.86 2.78 3.594(4) 158.4 N(2)-H(2A)...O(1)#3 0.86 1.99 2.832(5) 166.8 O(1)-H(1D)...Br(2)#4 0.843(19) 2.74(3) 3.494(5) 151(6) O(1)-H(1E)...Br(3)#5 0.838(19) 3.042(14) 3.675(4) 134.1(3) O(1)-H(1E)...Br(3)#6 0.838(19) 3.042(14) 3.675(4) 134.1(3) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 #2 x+1,y,z #3 x,y+1,z-1 #4 x+1,-y+1/2,-z+1 #5 -x+1,-y+1,-z+1 #6 -x+1,-y+1,z+1/2 Este? Lawrence, Masters Dissertation 2011 b93 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetraiodocadmate(II) monohydrate Table 1. Crystal data and structure refinement for 4ampCdI?H2O. Identification code 4ampCdI?H2O Empirical formula C10 H16 Cd I4 N4 O Formula weight 828.27 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P b c m Unit cell dimensions a = 7.3983(3) ? ?= 90?. b = 14.7586(7) ? ?= 90?. c = 18.7562(10) ? ? = 90?. Volume 2047.96(17) ?3 Z 4 Density (calculated) 2.686 Mg/m3 Absorption coefficient 7.097 mm-1 F(000) 1488 Crystal size 0.3 x 0.2 x 0.2 mm3 Theta range for data collection 3.77 to 27.00?. Index ranges -9<=h<=9, -18<=k<=18, -19<=l<=23 Reflections collected 15153 Independent reflections 2305 [R(int) = 0.0279] Completeness to theta = 27.00? 99.7 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2305 / 3 / 98 Goodness-of-fit on F2 1.062 Final R indices [I>2sigma(I)] R1 = 0.0231, wR2 = 0.0560 R indices (all data) R1 = 0.0296, wR2 = 0.0584 Extinction coefficient 0.00845(19) Largest diff. peak and hole0.949 and -0.902 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampCdI?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b94 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 8535(5) 8751(2) 126(2) 40(1) C(2) 6942(6) 9105(3) -188(3) 54(1) C(3) 7054(8) 9525(3) -826(3) 62(1) C(4) 10141(7) 9245(3) -900(2) 57(1) C(5) 10139(6) 8824(3) -255(2) 45(1) N(1) 8485(5) 8365(3) 767(2) 61(1) N(2) 8635(6) 9594(2) -1171(2) 63(1) O(1) 9002(6) 570(3) 7500 55(1) I(1) 8544(1) 7251(1) 2500 39(1) I(2) 3860(1) 5191(1) 2500 44(1) I(3) 3547(1) 7828(1) 1253(1) 46(1) Cd(1) 4818(1) 7019(1) 2500 38(1) Table 3. Bond lengths [?] and angles [?] for 4ampCdI?H2O. _____________________________________________________ C(1)-N(1) 1.332(5) C(1)-C(5) 1.389(5) C(1)-C(2) 1.417(6) C(2)-C(3) 1.351(6) C(2)-H(2) 0.9300 C(3)-N(2) 1.340(7) C(3)-H(3) 0.9300 C(4)-N(2) 1.329(6) C(4)-C(5) 1.360(6) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 O(1)-H(1D) 0.893(4) O(1)-H(1C) 0.828(4) I(1)-Cd(1) 2.7774(5) I(2)-Cd(1) 2.7902(5) I(3)-Cd(1) 2.7886(3) Cd(1)-I(3)#1 2.7886(3) N(1)-C(1)-C(5) 121.4(4) Este? Lawrence, Masters Dissertation 2011 b95 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(1)-C(1)-C(2) 120.7(4) C(5)-C(1)-C(2) 117.9(4) C(3)-C(2)-C(1) 119.1(4) C(3)-C(2)-H(2) 120.5 C(1)-C(2)-H(2) 120.5 N(2)-C(3)-C(2) 121.1(4) N(2)-C(3)-H(3) 119.5 C(2)-C(3)-H(3) 119.5 N(2)-C(4)-C(5) 121.1(4) N(2)-C(4)-H(4) 119.4 C(5)-C(4)-H(4) 119.4 C(4)-C(5)-C(1) 119.6(4) C(4)-C(5)-H(5) 120.2 C(1)-C(5)-H(5) 120.2 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(4)-N(2)-C(3) 121.2(4) C(4)-N(2)-H(2A) 119.4 C(3)-N(2)-H(2A) 119.4 H(1D)-O(1)-H(1C) 139.2(5) I(1)-Cd(1)-I(3) 106.385(11) I(1)-Cd(1)-I(3)#1 106.385(11) I(3)-Cd(1)-I(3)#1 113.984(18) I(1)-Cd(1)-I(2) 111.784(16) I(3)-Cd(1)-I(2) 109.151(11) I(3)#1-Cd(1)-I(2) 109.151(11) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 4ampCdI?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 45(2) 35(2) 40(2) 0(2) -3(2) -3(2) Este? Lawrence, Masters Dissertation 2011 b96 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 42(2) 55(2) 64(3) 6(2) -8(2) 0(2) C(3) 74(3) 55(3) 56(3) 2(2) -20(2) 3(2) C(4) 72(3) 46(2) 52(2) -8(2) 15(2) -3(2) C(5) 46(2) 42(2) 48(2) -5(2) 4(2) 1(2) N(1) 61(2) 69(2) 54(2) 18(2) 5(2) 4(2) N(2) 113(4) 45(2) 30(2) 4(2) -4(2) -3(2) O(1) 62(3) 55(2) 46(2) 0 0 -4(2) I(1) 34(1) 42(1) 42(1) 0 0 -3(1) I(2) 44(1) 37(1) 51(1) 0 0 -5(1) I(3) 40(1) 53(1) 44(1) 10(1) -6(1) -2(1) Cd(1) 37(1) 39(1) 38(1) 0 0 -1(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampCdI?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 5834 9048 42 64 H(3) 6018 9770 -1030 74 H(4) 11214 9290 -1155 68 H(5) 11205 8587 -69 54 H(1A) 9459 8154 954 73 H(1B) 7478 8326 994 73 H(2A) 8675 9869 -1575 75 H(1D) 7916 306 7500 65 H(1C) 10084 426 7500 65 Table 6. Torsion angles [?] for 4ampCdI?H2O. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) 177.3(4) C(5)-C(1)-C(2)-C(3) -2.4(6) C(1)-C(2)-C(3)-N(2) 1.4(7) N(2)-C(4)-C(5)-C(1) 0.4(6) N(1)-C(1)-C(5)-C(4) -178.3(4) C(2)-C(1)-C(5)-C(4) 1.5(6) C(5)-C(4)-N(2)-C(3) -1.6(7) Este? Lawrence, Masters Dissertation 2011 b97 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2)-C(3)-N(2)-C(4) 0.6(7) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 7. Hydrogen bonds for 4ampCdI?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...I(3)#2 0.86 3.11 3.935(4) 160.7 N(1)-H(1B)...I(3) 0.86 3.04 3.848(4) 157.5 N(2)-H(2A)...O(1)#3 0.86 2.04 2.892(4) 174.5 O(1)-H(1D)...I(2)#4 0.893(4) 3.09 3.967(4) 167.9(3) O(1)-H(1C)...I(2)#5 0.828(4) 2.94 3.765(4) 176.9(3) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 #2 x+1,y,z #3 x,y+1,z-1 #4 x,-y+1/2,z+1/2 #5 x+1,-y+1/2,z+1/2 Este? Lawrence, Masters Dissertation 2011 b98 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetrachloromercurate(II) monohydrate Table 1. Crystal data and structure refinement for 4ampHgCl?H2O. Identification code 4ampHgCl?H2O Empirical formula C10 H16 Cl4 Hg N4 O Formula weight 550.53 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P b c m Unit cell dimensions a = 6.5735(5) ? ?= 90?. b = 13.6799(10) ? ?= 90?. c = 18.7593(14) ? ? = 90?. Volume 1686.9(2) ?3 Z 4 Density (calculated) 2.168 Mg/m3 Absorption coefficient 9.757 mm-1 F(000) 1040 Crystal size 0.3 x 0.2 x 0.2 mm3 Theta range for data collection 3.79 to 27.00?. Index ranges -8<=h<=8, -17<=k<=17, -20<=l<=23 Reflections collected 12670 Independent reflections 1895 [R(int) = 0.0489] Completeness to theta = 25.00? 99.5 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 1895 / 0 / 99 Goodness-of-fit on F2 0.842 Final R indices [I>2sigma(I)] R1 = 0.0219, wR2 = 0.0350 R indices (all data) R1 = 0.0440, wR2 = 0.0369 Largest diff. peak and hole0.876 and -0.798 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampHgCl?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ C(1) 6426(6) 3717(2) 4802(2) 36(1) Este? Lawrence, Masters Dissertation 2011 b99 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 4631(6) 3736(2) 5202(2) 47(1) C(3) 4699(7) 4020(2) 5894(2) 56(1) C(4) 8161(7) 4256(3) 5836(2) 62(1) C(5) 8210(6) 3969(3) 5152(2) 47(1) Cl(1) 6412(2) 2523(1) 2500 46(1) Cl(2) 10995(2) 568(1) 2500 55(1) Cl(3) 11406(1) 3109(1) 1382(1) 56(1) Hg(1) 10181(1) 2340(1) 2500 50(1) N(1) 6433(5) 3466(2) 4122(2) 51(1) N(2) 6426(6) 4292(2) 6197(2) 61(1) O(1) 4261(7) 4728(3) 2500 67(1) Table 3. Bond lengths [?] and angles [?] for 4ampHgCl?H2O. _____________________________________________________ C(1)-N(1) 1.322(4) C(1)-C(5) 1.387(5) C(1)-C(2) 1.398(5) C(2)-C(3) 1.356(5) C(2)-H(2) 0.9300 C(3)-N(2) 1.323(5) C(3)-H(3) 0.9300 C(4)-N(2) 1.328(5) C(4)-C(5) 1.342(5) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 Cl(1)-Hg(1) 2.4903(12) Cl(2)-Hg(1) 2.4826(14) Cl(3)-Hg(1) 2.4796(9) Hg(1)-Cl(3)#1 2.4796(9) N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 O(1)-H(1C) 0.942(4) O(1)-H(1D) 0.747(5) N(1)-C(1)-C(5) 121.2(4) N(1)-C(1)-C(2) 121.7(3) Este? Lawrence, Masters Dissertation 2011 b100 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(5)-C(1)-C(2) 117.0(3) C(3)-C(2)-C(1) 119.4(4) C(3)-C(2)-H(2) 120.3 C(1)-C(2)-H(2) 120.3 N(2)-C(3)-C(2) 121.3(4) N(2)-C(3)-H(3) 119.3 C(2)-C(3)-H(3) 119.3 N(2)-C(4)-C(5) 121.3(4) N(2)-C(4)-H(4) 119.4 C(5)-C(4)-H(4) 119.4 C(4)-C(5)-C(1) 120.3(4) C(4)-C(5)-H(5) 119.8 C(1)-C(5)-H(5) 119.8 Cl(3)#1-Hg(1)-Cl(3) 115.44(5) Cl(3)#1-Hg(1)-Cl(2) 110.14(3) Cl(3)-Hg(1)-Cl(2) 110.14(3) Cl(3)#1-Hg(1)-Cl(1) 106.27(3) Cl(3)-Hg(1)-Cl(1) 106.27(3) Cl(2)-Hg(1)-Cl(1) 108.21(4) C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(3)-N(2)-C(4) 120.5(3) C(3)-N(2)-H(2A) 119.7 C(4)-N(2)-H(2A) 119.7 H(1C)-O(1)-H(1D) 119.0(5) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 4ampHgCl?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 43(2) 30(2) 34(2) 1(2) -1(2) 1(2) C(2) 45(2) 45(2) 50(2) -1(2) 2(2) 1(2) Este? Lawrence, Masters Dissertation 2011 b101 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(3) 71(3) 43(2) 54(3) 6(2) 25(2) 10(2) C(4) 61(3) 64(3) 60(3) 1(2) -20(2) 0(2) C(5) 46(2) 56(3) 39(2) -6(2) -4(2) 2(2) Cl(1) 44(1) 60(1) 35(1) 0 0 5(1) Cl(2) 61(1) 54(1) 50(1) 0 0 5(1) Cl(3) 46(1) 79(1) 44(1) 17(1) 5(1) 0(1) Hg(1) 54(1) 62(1) 35(1) 0 0 4(1) N(1) 55(2) 63(2) 35(2) -8(2) 1(2) 0(2) N(2) 96(3) 59(2) 28(2) -1(2) -7(2) 5(2) O(1) 108(4) 60(3) 34(2) 0 0 16(3) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampHgCl?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 3402 3554 4995 56 H(3) 3507 4025 6161 67 H(4) 9366 4433 6061 74 H(5) 9445 3938 4911 56 H(1A) 7558 3457 3888 61 H(1B) 5313 3312 3913 61 H(2A) 6425 4493 6632 73 H(1C) 4871 4105 2500 200(40) H(1D) 4926 5171 2500 250(70) Table 6. Torsion angles [?] for 4ampHgCl?H2O. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) -178.5(3) C(5)-C(1)-C(2)-C(3) 1.9(5) C(1)-C(2)-C(3)-N(2) 0.8(5) N(2)-C(4)-C(5)-C(1) 1.1(6) N(1)-C(1)-C(5)-C(4) 177.6(3) C(2)-C(1)-C(5)-C(4) -2.8(5) C(2)-C(3)-N(2)-C(4) -2.6(5) C(5)-C(4)-N(2)-C(3) 1.7(6) Este? Lawrence, Masters Dissertation 2011 b102 Crystallographic Investigation of n-Aminopyridinium Perhalometallates ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 7. Hydrogen bonds for 4ampHgCl?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Cl(3)#1 0.86 2.62 3.437(3) 158.5 N(1)-H(1B)...Cl(3)#2 0.86 2.64 3.472(3) 162.4 N(2)-H(2A)...O(1)#3 0.86 2.00 2.824(4) 160.6 O(1)-H(1C)...Cl(1) 0.942(4) 2.3891(12) 3.331(4) 179.9(3) O(1)-H(1D)...Cl(2)#4 0.747(5) 2.7358(13) 3.324(5) 137.3(3) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 #2 x-1,y,-z+1/2 #3 -x+1,-y+1,-z+1 #4 -x+2,y+1/2,z Este? Lawrence, Masters Dissertation 2011 b103 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetrabromomercurate(II) monohydrate Table 1. Crystal data and structure refinement for 4ampHgBr?H2O. Identification code 4ampHgBr?H2O Empirical formula C10 H16 Br4 Hg N4 O Formula weight 728.50 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P b c m Unit cell dimensions a = 6.8625(3) ? ?= 90?. b = 14.0041(6) ? ?= 90?. c = 18.8161(9) ? ? = 90?. Volume 1808.29(14) ?3 Z 4 Density (calculated) 2.676 Mg/m3 Absorption coefficient 17.350 mm-1 F(000) 1328 Crystal size 0.3 x 0.3 x 0.1 mm3 Theta range for data collection 2.16 to 27.00?. Index ranges -8<=h<=8, -17<=k<=17, -24<=l<=18 Reflections collected 12149 Independent reflections 2031 [R(int) = 0.0837] Completeness to theta = 27.00? 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2031 / 3 / 101 Goodness-of-fit on F2 1.104 Final R indices [I>2sigma(I)] R1 = 0.0330, wR2 = 0.0630 R indices (all data) R1 = 0.0522, wR2 = 0.0676 Largest diff. peak and hole1.746 and -1.376 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampHgBr?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ C(1) 8573(8) 8727(4) 174(3) 34(1) Este? Lawrence, Masters Dissertation 2011 b104 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 6855(9) 9022(5) -169(3) 50(2) C(3) 6935(12) 9355(5) -837(4) 61(2) C(4) 10245(11) 9103(5) -892(3) 56(2) C(5) 10295(9) 8761(5) -220(3) 44(2) N(1) 8531(8) 8425(4) 840(2) 53(2) N(2) 8601(11) 9410(4) -1188(3) 60(2) O(1) 9031(11) 389(5) 7500 57(2) Br(1) 8624(1) 7397(1) 2500 41(1) Br(2) 3901(1) 5372(1) 2500 47(1) Br(3) 3576(1) 7982(1) 1338(1) 49(1) Hg(1) 4860(1) 7168(1) 2500 43(1) Table 3. Bond lengths [?] and angles [?] for 4ampHgBr?H2O. _____________________________________________________ C(1)-N(1) 1.323(7) C(1)-C(5) 1.396(8) C(1)-C(2) 1.406(8) C(2)-C(3) 1.342(9) C(2)-H(2) 0.9300 C(3)-N(2) 1.323(9) C(3)-H(3) 0.9300 C(4)-N(2) 1.331(9) C(4)-C(5) 1.352(9) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 O(1)-H(1D) 0.84(2) O(1)-H(1E) 0.85(2) Br(1)-Hg(1) 2.6027(9) Br(2)-Hg(1) 2.5996(11) Br(3)-Hg(1) 2.6193(6) Hg(1)-Br(3)#1 2.6193(6) N(1)-C(1)-C(5) 122.2(5) N(1)-C(1)-C(2) 120.7(5) Este? Lawrence, Masters Dissertation 2011 b105 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(5)-C(1)-C(2) 117.1(5) C(3)-C(2)-C(1) 119.8(6) C(3)-C(2)-H(2) 120.1 C(1)-C(2)-H(2) 120.1 N(2)-C(3)-C(2) 121.6(7) N(2)-C(3)-H(3) 119.2 C(2)-C(3)-H(3) 119.2 N(2)-C(4)-C(5) 121.9(6) N(2)-C(4)-H(4) 119.1 C(5)-C(4)-H(4) 119.1 C(4)-C(5)-C(1) 119.2(6) C(4)-C(5)-H(5) 120.4 C(1)-C(5)-H(5) 120.4 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(3)-N(2)-C(4) 120.3(6) C(3)-N(2)-H(2A) 119.9 C(4)-N(2)-H(2A) 119.9 H(1D)-O(1)-H(1E) 124(6) Br(2)-Hg(1)-Br(1) 111.76(3) Br(2)-Hg(1)-Br(3)#1 109.64(2) Br(1)-Hg(1)-Br(3)#1 106.265(19) Br(2)-Hg(1)-Br(3) 109.64(2) Br(1)-Hg(1)-Br(3) 106.265(19) Br(3)#1-Hg(1)-Br(3) 113.23(3) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 4ampHgBr?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 37(3) 27(3) 37(3) -3(2) -2(2) -1(2) C(2) 39(3) 62(5) 48(3) 3(4) -6(3) -4(3) Este? Lawrence, Masters Dissertation 2011 b106 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(3) 69(5) 66(5) 48(4) 3(4) -20(4) -1(4) C(4) 71(5) 49(5) 49(3) -9(3) 24(4) -8(4) C(5) 42(3) 44(4) 48(3) -5(3) 9(3) -2(3) N(1) 45(3) 76(5) 36(3) 12(3) 2(2) 4(3) N(2) 102(6) 50(4) 29(3) 3(2) -2(3) -6(4) O(1) 68(5) 60(5) 42(3) 0 0 5(4) Br(1) 35(1) 52(1) 36(1) 0 0 -4(1) Br(2) 46(1) 46(1) 48(1) 0 0 -6(1) Br(3) 37(1) 67(1) 43(1) 14(1) -5(1) -1(1) Hg(1) 42(1) 51(1) 37(1) 0 0 -2(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampHgBr?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 5666 8987 67 59 H(3) 5792 9552 -1058 73 H(4) 11393 9124 -1154 67 H(5) 11462 8552 -23 53 H(1A) 9588 8241 1044 63 H(1B) 7447 8412 1069 63 H(2A) 8620 9646 -1610 72 H(1D) 10250(30) 400(60) 7500 68 H(1E) 8330(100) 890(40) 7500 68 Table 6. Torsion angles [?] for 4ampHgBr?H2O. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) 177.9(6) C(5)-C(1)-C(2)-C(3) -2.6(10) C(1)-C(2)-C(3)-N(2) 0.3(12) N(2)-C(4)-C(5)-C(1) 0.2(10) N(1)-C(1)-C(5)-C(4) -178.1(6) C(2)-C(1)-C(5)-C(4) 2.3(9) C(2)-C(3)-N(2)-C(4) 2.3(11) C(5)-C(4)-N(2)-C(3) -2.5(11) Este? Lawrence, Masters Dissertation 2011 b107 Crystallographic Investigation of n-Aminopyridinium Perhalometallates ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 7. Hydrogen bonds for 4ampHgBr?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...Br(3)#2 0.86 2.81 3.639(5) 161.1 N(1)-H(1B)...Br(3) 0.86 2.77 3.581(5) 157.8 N(2)-H(2A)...O(1)#3 0.86 1.99 2.838(7) 168.2 O(1)-H(1D)...Br(2)#4 0.84(2) 2.73(4) 3.508(8) 156(8) O(1)-H(1E)...Br(3)#5 0.85(2) 2.996(14) 3.632(6) 132.9(7) O(1)-H(1E)...Br(3)#6 0.85(2) 2.996(14) 3.632(6) 132.9(7) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 #2 x+1,y,z #3 x,y+1,z-1 #4 x+1,-y+1/2,z+1/2 #5 -x+1,-y+1,-z+1 #6 -x+1,-y+1,z+1/2 Este? Lawrence, Masters Dissertation 2011 b108 Crystallographic Investigation of n-Aminopyridinium Perhalometallates Crystallographic Data for Bis(4-aminopyridinium) tetraiodomercurate(II) monohydrate Table 1. Crystal data and structure refinement for 4ampHgI?H2O. Identification code 4ampHgI?H2O Empirical formula C10 H16 Hg I4 N4 O Formula weight 916.46 Temperature 293(2) K Wavelength 0.71073 ? Crystal system Orthorhombic Space group P b c m Unit cell dimensions a = 7.2736(4) ? ?= 90?. b = 14.4831(7) ? ?= 90?. c = 18.5793(8) ? ? = 90?. Volume 1957.22(17) ?3 Z 4 Density (calculated) 3.110 Mg/m3 Absorption coefficient 14.174 mm-1 F(000) 1616 Crystal size 0.49 x 0.40 x 0.24 mm3 Theta range for data collection 2.19 to 27.00?. Index ranges -8<=h<=9, -18<=k<=15, -23<=l<=23 Reflections collected 13205 Independent reflections 2211 [R(int) = 0.0485] Completeness to theta = 27.00? 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2211 / 3 / 102 Goodness-of-fit on F2 1.108 Final R indices [I>2sigma(I)] R1 = 0.0224, wR2 = 0.0475 R indices (all data) R1 = 0.0262, wR2 = 0.0487 Extinction coefficient 0.00128(5) Largest diff. peak and hole1.547 and -0.912 e.?-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (?2x 103) for 4ampHgI?H2O. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ Este? Lawrence, Masters Dissertation 2011 b109 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(1) 8534(7) 8751(3) 129(2) 21(1) C(2) 6934(8) 9114(3) -184(3) 28(1) C(3) 7034(9) 9546(4) -821(3) 34(1) C(4) 10171(9) 9261(4) -903(3) 33(1) C(5) 10176(7) 8827(3) -260(2) 24(1) N(1) 8488(7) 8347(3) 778(2) 32(1) N(2) 8627(7) 9629(3) -1170(2) 34(1) O(1) 8910(8) 607(4) 7500 30(1) I(1) 8641(1) 7217(1) 2500 21(1) I(2) 3826(1) 5111(1) 2500 23(1) I(3) 3572(1) 7794(1) 1250(1) 24(1) Hg(1) 4879(1) 6945(1) 2500 24(1) Table 3. Bond lengths [?] and angles [?] for 4ampHgI?H2O. _____________________________________________________ C(1)-N(1) 1.339(6) C(1)-C(5) 1.401(7) C(1)-C(2) 1.403(7) C(2)-C(3) 1.342(7) C(2)-H(2) 0.9300 C(3)-N(2) 1.333(8) C(3)-H(3) 0.9300 C(4)-N(2) 1.338(8) C(4)-C(5) 1.349(7) C(4)-H(4) 0.9300 C(5)-H(5) 0.9300 N(1)-H(1A) 0.8600 N(1)-H(1B) 0.8600 N(2)-H(2A) 0.8600 O(1)-H(1D) 0.823(19) O(1)-H(1C) 0.83(2) I(1)-Hg(1) 2.7642(6) I(2)-Hg(1) 2.7650(5) I(3)-Hg(1) 2.7940(3) Hg(1)-I(3)#1 2.7940(3) N(1)-C(1)-C(5) 121.3(5) Este? Lawrence, Masters Dissertation 2011 b110 Crystallographic Investigation of n-Aminopyridinium Perhalometallates N(1)-C(1)-C(2) 121.1(5) C(5)-C(1)-C(2) 117.6(4) C(3)-C(2)-C(1) 119.7(5) C(3)-C(2)-H(2) 120.1 C(1)-C(2)-H(2) 120.1 N(2)-C(3)-C(2) 121.2(5) N(2)-C(3)-H(3) 119.4 C(2)-C(3)-H(3) 119.4 N(2)-C(4)-C(5) 121.0(5) N(2)-C(4)-H(4) 119.5 C(5)-C(4)-H(4) 119.5 C(4)-C(5)-C(1) 119.5(5) C(4)-C(5)-H(5) 120.3 C(1)-C(5)-H(5) 120.3 C(1)-N(1)-H(1A) 120.0 C(1)-N(1)-H(1B) 120.0 H(1A)-N(1)-H(1B) 120.0 C(3)-N(2)-C(4) 120.9(5) C(3)-N(2)-H(2A) 119.5 C(4)-N(2)-H(2A) 119.6 H(1D)-O(1)-H(1C) 148(7) I(1)-Hg(1)-I(2) 114.256(16) I(1)-Hg(1)-I(3) 105.927(10) I(2)-Hg(1)-I(3) 109.177(11) I(1)-Hg(1)-I(3)#1 105.927(10) I(2)-Hg(1)-I(3)#1 109.177(11) I(3)-Hg(1)-I(3)#1 112.396(17) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 4. Anisotropic displacement parameters (?2x 103)for 4ampHgI?H2O. The anisotropic displacement factor exponent takes the form: -2pi2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ C(1) 26(3) 17(2) 20(2) -1(2) -1(2) 2(2) Este? Lawrence, Masters Dissertation 2011 b111 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(2) 25(3) 25(3) 35(3) 5(2) -3(2) -1(2) C(3) 43(3) 27(3) 31(3) 0(2) -14(2) 2(3) C(4) 47(4) 25(3) 27(2) -7(2) 13(2) -3(3) C(5) 29(3) 21(2) 22(2) 0(2) 2(2) 2(2) N(1) 30(3) 35(3) 30(2) 9(2) 2(2) 2(2) N(2) 59(3) 25(2) 17(2) 1(2) -1(2) -2(2) O(1) 34(3) 27(3) 30(2) 0 0 3(3) I(1) 22(1) 22(1) 21(1) 0 0 -2(1) I(2) 25(1) 20(1) 25(1) 0 0 -2(1) I(3) 23(1) 27(1) 23(1) 5(1) -3(1) -1(1) Hg(1) 26(1) 23(1) 23(1) 0 0 -1(1) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (?2x 103) for 4ampHgI?H2O. ________________________________________________________________________________ x y z U(eq) ________________________________________________________________________________ H(2) 5809 9056 50 34 H(3) 5972 9792 -1024 40 H(4) 11258 9305 -1164 40 H(5) 11260 8581 -77 29 H(1A) 9480 8128 963 38 H(1B) 7467 8307 1009 38 H(2A) 8664 9923 -1572 40 H(1D) 7780(30) 640(60) 7500 36 H(1C) 9840(60) 270(50) 7500 36 Table 6. Torsion angles [?] for 4ampHgI?H2O. ________________________________________________________________ N(1)-C(1)-C(2)-C(3) 177.5(5) C(5)-C(1)-C(2)-C(3) -2.5(7) C(1)-C(2)-C(3)-N(2) 0.8(8) N(2)-C(4)-C(5)-C(1) 0.8(8) N(1)-C(1)-C(5)-C(4) -178.2(5) C(2)-C(1)-C(5)-C(4) 1.7(7) C(2)-C(3)-N(2)-C(4) 1.8(8) Este? Lawrence, Masters Dissertation 2011 b112 Crystallographic Investigation of n-Aminopyridinium Perhalometallates C(5)-C(4)-N(2)-C(3) -2.6(8) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 Table 7. Hydrogen bonds for 4ampHgI?H2O [? and ?]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(1)-H(1A)...I(3)#2 0.86 3.06 3.884(5) 160.6 N(1)-H(1A)...I(1) 0.86 3.20 3.596(4) 110.4 N(1)-H(1B)...I(3) 0.86 2.96 3.769(5) 156.7 N(2)-H(2A)...O(1)#3 0.86 2.00 2.856(5) 176.6 O(1)-H(1D)...I(2)#4 0.823(19) 3.07(3) 3.841(6) 156(7) O(1)-H(1C)...I(2)#5 0.83(2) 2.95(3) 3.724(6) 155(7) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x,y,-z+1/2 #2 x+1,y,z #3 x,y+1,z-1 #4 x,-y+1/2,z+1/2 #5 x+1,-y+1/2,z+1/2 Este? Lawrence, Masters Dissertation 2011 b113