Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2001 Title: Influences of Secondary Metal-Ligand Subunits on Molybdenum Oxide Structures: The Hydrothermal Synthesis and Structures of [M(tpytrz)2Mo4O13] (M= Fe, Co, Ni, Zn; tpytrz= tripyridyltriazine), [Ni(tpytrz)Mo2O7] and [Zn2(tpytrz)Mo2O8] Authors: Randy S. Rarig Jr. and Jon Zubieta Journal: Journal of the Royal Chemical Society: Dalton Transactions CCDC 163168 is Cmpd 1: [Fe(tpytrz)2Mo4O13] CCDC 163169 is Cmpd 2: [Co(tpytrz)2Mo4O13] CCDC 163170 is Cmpd 3: [Ni(tpytrz)2Mo4O13] CCDC 163171 is Cmpd 4: [Zn(tpytrz)2Mo4O13] CCDC 163172 is Cmpd 5: [Ni(H2O)4(Htpytrz)2][Mo8O26]1.2H2O CCDC 163173 is Cmpd 6: [Ni(tpytrz)Mo2O7] CCDC 163174 is Cmpd 7: [Zn2(tpytrz)Mo2O8 Table 1. Crystal data and structure refinement for [FeMo4O13(tpytrz)2]. Identification code p-1 Empirical formula C18 H12 Fe0.50 Mo2 N6 O6.50 Formula weight 636.14 Temperature 90(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.0932(7) Å ?=79.873(2)°. b = 8.8946(8) Å ?= 84.699(2)°. c = 13.755(1) Å ? =80.517(2)°. Volume 959.3(1) Å3 Z 2 Density (calculated) 2.202 Mg/m3 Absorption coefficient 1.728 mm-1 F(000) 622 Crystal size 0.3 x0.2x 0.1 mm3 Theta range for data collection 2.35 to 28.28°. Index ranges -10<=h<=10, -9<=k<=11, -18<=l<=18 Reflections collected 6328 Independent reflections 4366 [R(int) = 0.0250] Completeness to theta = 28.28° 91.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4366 / 0 / 301 Goodness-of-fit on F2 1.058 Final R indices [I>2sigma(I)] R1 = 0.0505, wR2 = 0.1387 R indices (all data) R1 = 0.0626, wR2 = 0.1497 Largest diff. peak and hole 2.684 and -1.975 e.Å-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for p-1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________ x y z U(eq) ______________________________________________________________ Fe(1) 5000 0 0 15(1) Mo(1) 1539(1) 3186(1) -760(1) 14(1) Mo(2) 3071(1) 6227(1) 493(1) 12(1) O(1) 2765(4) 1383(4) -385(2) 18(1) O(2) -646(4) 2877(4) -678(2) 18(1) O(3) 2155(5) 3850(4) -1961(3) 23(1) O(4) 1894(4) 4514(4) 11(3) 16(1) O(5) 5000 5000 0 16(1) O(6) 3881(4) 7934(4) 409(2) 13(1) O(7) 3186(4) 5425(4) 1704(2) 19(1) C(1) 3148(6) 7102(5) -2038(4) 18(1) C(2) 2914(6) 8004(6) -2978(4) 17(1) C(3) 1792(6) 9377(5) -3029(3) 15(1) C(4) 984(6) 9803(5) -2151(3) 17(1) C(5) 1356(6) 8849(5) -1264(3) 17(1) C(6) 3502(6) 1676(6) 1687(3) 17(1) C(7) 2677(6) 1950(5) 2581(3) 17(1) C(8) 2830(6) 760(6) 3405(3) 15(1) C(9) 3843(6) -617(6) 3288(4) 20(1) C(10) 4556(6) -826(5) 2349(3) 16(1) C(11) 1925(6) 1033(6) 4361(3) 16(1) C(12) 1432(6) 414(5) 6008(3) 15(1) C(13) -102(6) 2512(5) 5173(3) 15(1) C(14) -1474(6) 3848(6) 5158(4) 18(1) C(15) -1906(6) 4800(6) 4267(3) 19(1) C(16) -3154(6) 6064(6) 4302(4) 19(1) C(17) -3593(6) 5469(6) 5974(4) 21(1) C(18) -2338(6) 4198(6) 6032(4) 19(1) N(1) 2386(5) 7497(5) -1198(3) 17(1) N(2) 4383(5) 310(5) 1549(3) 16(1) N(3) 2329(5) 59(5) 5186(3) 16(1) N(4) 198(5) 1611(5) 6047(3) 16(1) N(5) 716(5) 2276(5) 4303(3) 16(1) N(6) -4013(5) 6431(5) 5133(3) 21(1) ____________________________________________________________ Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for p-1. ______________________________________________________________ x y z U(eq) ______________________________________________________________ H(1) 3879 6173 -2001 21 H(2) 3488 7694 -3545 20 H(4) 215 10706 -2164 21 H(5) 862 9166 -681 20 H(6) 3441 2483 1155 21 H(7) 2033 2903 2636 20 H(9) 4047 -1395 3829 24 H(10) 5172 -1780 2268 19 H(15) -1370 4590 3667 22 H(16) -3415 6703 3708 23 H(17) -4189 5673 6560 25 H(18) -2081 3596 6638 22 Table 3. Bond lengths [Å] and angles [°] for p-1. _____________________________________________________ Fe(1)-O(1) 2.069(3) Fe(1)-O(1)#1 2.069(3) Fe(1)-O(6)#2 2.146(3) Fe(1)-O(6)#3 2.146(3) Fe(1)-N(2)#1 2.198(4) Fe(1)-N(2) 2.198(4) Mo(1)-O(3) 1.712(3) Mo(1)-O(1) 1.761(3) Mo(1)-O(4) 1.792(3) Mo(1)-O(2) 1.825(3) Mo(2)-O(7) 1.698(3) Mo(2)-O(6) 1.732(3) Mo(2)-O(5) 1.8949(4) Mo(2)-O(2)#4 2.004(3) Mo(2)-O(4) 2.149(3) Mo(2)-N(1) 2.469(4) O(2)-Mo(2)#4 2.004(3) O(5)-Mo(2)#3 1.8949(4) O(6)-Fe(1)#5 2.146(3) C(1)-N(1) 1.334(6) C(1)-C(2) 1.408(7) C(2)-C(3) 1.391(6) C(3)-C(4) 1.401(6) C(3)-C(12)#6 1.497(6) C(4)-C(5) 1.386(6) C(5)-N(1) 1.340(6) C(6)-N(2) 1.339(6) C(6)-C(7) 1.385(6) C(7)-C(8) 1.407(6) C(8)-C(9) 1.383(7) C(8)-C(11) 1.484(6) C(9)-C(10) 1.396(7) C(10)-N(2) 1.356(6) C(11)-N(3) 1.332(6) C(11)-N(5) 1.346(6) C(12)-N(4) 1.339(6) C(12)-N(3) 1.343(6) C(12)-C(3)#7 1.497(6) C(13)-N(4) 1.340(6) C(13)-N(5) 1.346(6) C(13)-C(14) 1.485(7) C(14)-C(18) 1.391(7) C(14)-C(15) 1.399(7) C(15)-C(16) 1.387(7) C(16)-N(6) 1.344(6) C(17)-N(6) 1.348(7) C(17)-C(18) 1.386(7) O(1)-Fe(1)-O(1)#1 180.00(11) O(1)-Fe(1)-O(6)#2 94.03(13) O(1)#1-Fe(1)-O(6)#2 85.97(13) O(1)-Fe(1)-O(6)#3 85.97(13) O(1)#1-Fe(1)-O(6)#3 94.03(13) O(6)#2-Fe(1)-O(6)#3 180.00(8) O(1)-Fe(1)-N(2)#1 90.41(14) O(1)#1-Fe(1)-N(2)#1 89.59(14) O(6)#2-Fe(1)-N(2)#1 94.72(13) O(6)#3-Fe(1)-N(2)#1 85.28(13) O(1)-Fe(1)-N(2) 89.59(14) O(1)#1-Fe(1)-N(2) 90.41(14) O(6)#2-Fe(1)-N(2) 85.28(13) O(6)#3-Fe(1)-N(2) 94.72(13) N(2)#1-Fe(1)-N(2) 180.0(2) O(3)-Mo(1)-O(1) 108.32(17) O(3)-Mo(1)-O(4) 109.33(17) O(1)-Mo(1)-O(4) 108.99(15) O(3)-Mo(1)-O(2) 109.77(17) O(1)-Mo(1)-O(2) 107.47(16) O(4)-Mo(1)-O(2) 112.84(15) O(7)-Mo(2)-O(6) 103.95(16) O(7)-Mo(2)-O(5) 97.25(12) O(6)-Mo(2)-O(5) 98.76(10) O(7)-Mo(2)-O(2)#4 93.04(15) O(6)-Mo(2)-O(2)#4 96.98(14) O(5)-Mo(2)-O(2)#4 158.51(10) O(7)-Mo(2)-O(4) 98.38(15) O(6)-Mo(2)-O(4) 157.55(14) O(5)-Mo(2)-O(4) 80.44(9) O(2)#4-Mo(2)-O(4) 79.43(13) O(7)-Mo(2)-N(1) 170.23(15) O(6)-Mo(2)-N(1) 78.88(14) O(5)-Mo(2)-N(1) 91.49(10) O(2)#4-Mo(2)-N(1) 77.29(13) O(4)-Mo(2)-N(1) 78.72(13) Mo(1)-O(1)-Fe(1) 152.6(2) Mo(1)-O(2)-Mo(2)#4 147.4(2) Mo(1)-O(4)-Mo(2) 157.8(2) Mo(2)-O(5)-Mo(2)#3 180.0 Mo(2)-O(6)-Fe(1)#5 168.53(18) N(1)-C(1)-C(2) 124.1(4) C(3)-C(2)-C(1) 117.6(4) C(2)-C(3)-C(4) 118.8(4) C(2)-C(3)-C(12)#6 122.0(4) C(4)-C(3)-C(12)#6 119.1(4) C(5)-C(4)-C(3) 118.6(4) N(1)-C(5)-C(4) 123.7(4) N(2)-C(6)-C(7) 123.5(4) C(6)-C(7)-C(8) 118.7(4) C(9)-C(8)-C(7) 118.1(4) C(9)-C(8)-C(11) 122.7(4) C(7)-C(8)-C(11) 119.2(4) C(8)-C(9)-C(10) 119.3(5) N(2)-C(10)-C(9) 122.5(4) N(3)-C(11)-N(5) 125.5(4) N(3)-C(11)-C(8) 119.5(4) N(5)-C(11)-C(8) 115.0(4) N(4)-C(12)-N(3) 125.7(4) N(4)-C(12)-C(3)#7 116.1(4) N(3)-C(12)-C(3)#7 118.2(4) N(4)-C(13)-N(5) 125.0(4) N(4)-C(13)-C(14) 117.6(4) N(5)-C(13)-C(14) 117.4(4) C(18)-C(14)-C(15) 118.5(4) C(18)-C(14)-C(13) 120.7(4) C(15)-C(14)-C(13) 120.8(4) C(16)-C(15)-C(14) 118.2(5) N(6)-C(16)-C(15) 124.7(5) N(6)-C(17)-C(18) 124.8(5) C(17)-C(18)-C(14) 118.3(5) C(1)-N(1)-C(5) 117.2(4) C(1)-N(1)-Mo(2) 126.0(3) C(5)-N(1)-Mo(2) 115.8(3) C(6)-N(2)-C(10) 117.5(4) C(6)-N(2)-Fe(1) 115.8(3) C(10)-N(2)-Fe(1) 125.6(3) C(11)-N(3)-C(12) 114.5(4) C(12)-N(4)-C(13) 114.7(4) C(11)-N(5)-C(13) 114.6(4) C(16)-N(6)-C(17) 115.5(4) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y,-z #2 x,y-1,z #3 -x+1,-y+1,-z #4 -x,-y+1,-z #5 x,y+1,z #6 x,y+1,z-1 #7 x,y-1,z+1 Table 4. Anisotropic displacement parameters (Å2x 103) for p-1. The anisotropic displacement factor exponent takes the form: -2?2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________ Fe(1) 15(1) 16(1) 13(1) -1(1) 0(1) 0(1) Mo(1) 13(1) 15(1) 13(1) 0(1) 0(1) -2(1) Mo(2) 10(1) 13(1) 11(1) 0(1) 1(1) -1(1) O(1) 16(2) 17(2) 20(2) -1(1) -3(1) 0(1) O(2) 15(2) 19(2) 17(2) -2(1) 0(1) 2(1) O(3) 29(2) 25(2) 13(2) 3(1) 3(2) -7(2) O(4) 15(2) 14(2) 22(2) -1(1) -8(1) -7(1) O(5) 13(2) 18(2) 18(2) -4(2) -2(2) 0(2) O(6) 12(2) 16(2) 10(1) 1(1) -1(1) -2(1) O(7) 22(2) 18(2) 13(2) 3(1) -2(1) 1(1) C(1) 18(2) 16(2) 16(2) -1(2) 1(2) 4(2) C(2) 15(2) 17(2) 17(2) -3(2) 5(2) 1(2) C(3) 16(2) 14(2) 13(2) 2(2) 3(2) -3(2) C(4) 20(2) 14(2) 15(2) -2(2) 1(2) 2(2) C(5) 21(2) 15(2) 12(2) 0(2) 1(2) -1(2) C(6) 22(2) 17(2) 10(2) 4(2) -1(2) -1(2) C(7) 17(2) 15(2) 16(2) -1(2) 1(2) 1(2) C(8) 11(2) 20(2) 13(2) 0(2) 0(2) -4(2) C(9) 19(2) 23(3) 15(2) 2(2) 2(2) -3(2) C(10) 21(2) 14(2) 12(2) -2(2) 0(2) -2(2) C(11) 14(2) 21(2) 13(2) -2(2) 1(2) -5(2) C(12) 16(2) 15(2) 13(2) 1(2) 0(2) -6(2) C(13) 14(2) 16(2) 12(2) 2(2) 3(2) -2(2) C(14) 15(2) 20(2) 17(2) -2(2) -1(2) 1(2) C(15) 20(2) 25(3) 11(2) -5(2) -2(2) -4(2) C(16) 20(2) 18(2) 17(2) 3(2) -1(2) 0(2) C(17) 21(3) 25(3) 15(2) -2(2) 2(2) -2(2) C(18) 18(2) 20(2) 18(2) -2(2) -1(2) -2(2) N(1) 15(2) 17(2) 16(2) 2(2) -2(2) -4(2) N(2) 16(2) 15(2) 17(2) -1(2) 1(2) -2(2) N(3) 20(2) 15(2) 11(2) 3(2) 1(2) -2(2) N(4) 17(2) 23(2) 9(2) -1(2) 1(2) -3(2) N(5) 15(2) 17(2) 14(2) 0(2) 1(2) -1(2) N(6) 18(2) 23(2) 20(2) -3(2) -2(2) 1(2) ______________________________________________________________ #END Table 1. Crystal data and structure refinement for [CoMo4O13(tpytrz)2]. . Identification code p-1 Empirical formula C18 H12 Co0.50 Mo2 N6 O6.50 Formula weight 637.68 Temperature 90(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.068(1) Å ?= 79.885(2)°. b = 8.881(1) Å ?= 84.593(2)°. c = 13.698(1) Å ? = 80.606(2)°. Volume 951.2(2) Å3 Z 2 Density (calculated) 2.226 Mg/m3 Absorption coefficient 1.797 mm-1 F(000) 623 Crystal size 0.6 x 0.4 x 0.2 mm3 Theta range for data collection 2.36 to 28.28°. Index ranges -7<=h<=10, -11<=k<=11, -17<=l<=15 Reflections collected 6149 Independent reflections 4216 [R(int) = 0.0391] Completeness to theta = 28.28° 89.1 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4216 / 0 / 302 Goodness-of-fit on F2 1.110 Final R indices [I>2sigma(I)] R1 = 0.0687, wR2 = 0.1884 R indices (all data) R1 = 0.0692, wR2 = 0.1886 Extinction coefficient 0.022(2) Largest diff. peak and hole 2.455 and -2.956 e.Å-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for p-1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ Co(1) 0 10000 5000 7(1) Mo(1) 3457(1) 6821(1) 5753(1) 8(1) Mo(2) 8070(1) 6237(1) 5488(1) 7(1) O(1) 2235(7) 8612(6) 5374(5) 11(1) O(2) 3122(7) 5488(7) 4965(4) 11(1) O(3) 2815(8) 6167(7) 6961(5) 17(1) O(4) 8174(8) 5452(7) 6713(5) 15(1) O(5) 10000 5000 5000 12(2) O(6) 8900(7) 7942(6) 5407(4) 10(1) O(8) 5646(7) 7138(6) 5674(4) 11(1) C(1) 1496(10) 8315(9) 3344(6) 11(2) C(2) 2302(10) 8044(9) 2434(6) 11(2) C(3) 2153(10) 9210(9) 1626(6) 12(2) C(4) 1163(11) 10617(9) 1742(6) 13(2) C(5) 464(11) 10821(9) 2692(6) 13(2) C(6) 3069(10) 8954(9) 659(6) 10(2) C(7) 5109(10) 7498(9) -158(6) 10(1) C(8) 3562(10) 9590(9) -994(6) 10(1) C(9) 6464(10) 6163(9) -150(6) 10(2) C(10) 6889(10) 5210(10) 743(6) 11(2) C(11) 8151(10) 3929(9) 707(6) 12(2) C(12) 8582(10) 4521(10) -970(6) 12(2) C(13) 7338(10) 5808(9) -1022(6) 13(2) C(14) 8169(10) 7087(9) 2943(6) 10(2) C(15) 7902(10) 8004(9) 2010(6) 10(1) C(16) 6793(10) 9382(9) 1959(6) 10(1) C(17) 5981(11) 9808(9) 2832(6) 12(2) C(18) 6339(10) 8851(9) 3729(6) 10(1) N(1) 620(9) 9681(8) 3490(5) 10(1) N(2) 2657(9) 9941(8) -168(5) 11(1) N(3) 4283(9) 7720(8) 715(5) 11(1) N(4) 4775(9) 8384(8) -1032(5) 11(1) N(5) 9003(9) 3570(8) -124(6) 14(1) N(6) 7399(8) 7498(8) 3793(5) 9(1) ________________________________________________________________________ Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for p-1. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ H(4) 1570 7505 3877 13 H(3) 2933 7087 2373 13 H(2) 973 11401 1200 16 H(1) -135 11781 2779 16 H(16) 6349 5420 1345 13 H(17) 8411 3287 1303 14 H(18) 9163 4303 -1560 14 H(14) 7096 6420 -1630 15 H(9) 8905 6160 2974 12 H(8) 8458 7694 1436 12 H(6) 5214 10715 2817 15 H(5) 5823 9157 4314 12 ________________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for p-1. _____________________________________________________ Co(1)-O(1)#1 2.064(6) Co(1)-O(1) 2.064(6) Co(1)-O(6)#2 2.126(6) Co(1)-O(6)#3 2.126(6) Co(1)-N(1) 2.139(7) Co(1)-N(1)#1 2.139(7) Mo(1)-O(3) 1.716(6) Mo(1)-O(1) 1.752(6) Mo(1)-O(2) 1.802(6) Mo(1)-O(8) 1.824(6) Mo(2)-O(4) 1.704(6) Mo(2)-O(6) 1.735(6) Mo(2)-O(5) 1.8927(6) Mo(2)-O(8) 1.999(6) Mo(2)-O(2)#4 2.141(6) Mo(2)-N(6) 2.462(7) O(2)-Mo(2)#4 2.141(6) O(5)-Mo(2)#5 1.8927(6) O(6)-Co(1)#6 2.126(5) C(1)-N(1) 1.338(10) C(1)-C(2) 1.390(11) C(2)-C(3) 1.376(11) C(3)-C(4) 1.394(11) C(3)-C(6) 1.490(11) C(4)-C(5) 1.398(12) C(5)-N(1) 1.353(10) C(6)-N(2) 1.338(10) C(6)-N(3) 1.342(10) C(7)-N(4) 1.336(10) C(7)-N(3) 1.342(10) C(7)-C(9) 1.475(11) C(8)-N(4) 1.332(10) C(8)-N(2) 1.344(11) C(8)-C(16)#7 1.492(10) C(9)-C(13) 1.388(12) C(9)-C(10) 1.396(10) C(10)-C(11) 1.402(11) C(11)-N(5) 1.334(11) C(12)-N(5) 1.345(11) C(12)-C(13) 1.389(11) C(14)-N(6) 1.347(10) C(14)-C(15) 1.404(10) C(15)-C(16) 1.388(11) C(16)-C(17) 1.390(11) C(16)-C(8)#7 1.492(10) C(17)-C(18) 1.391(10) C(18)-N(6) 1.351(10) O(1)#1-Co(1)-O(1) 180.0(3) O(1)#1-Co(1)-O(6)#2 85.5(2) O(1)-Co(1)-O(6)#2 94.5(2) O(1)#1-Co(1)-O(6)#3 94.5(2) O(1)-Co(1)-O(6)#3 85.5(2) O(6)#2-Co(1)-O(6)#3 180.000(1) O(1)#1-Co(1)-N(1) 91.3(2) O(1)-Co(1)-N(1) 88.7(2) O(6)#2-Co(1)-N(1) 85.6(2) O(6)#3-Co(1)-N(1) 94.4(2) O(1)#1-Co(1)-N(1)#1 88.7(2) O(1)-Co(1)-N(1)#1 91.3(2) O(6)#2-Co(1)-N(1)#1 94.4(2) O(6)#3-Co(1)-N(1)#1 85.6(2) N(1)-Co(1)-N(1)#1 180.000(2) O(3)-Mo(1)-O(1) 108.0(3) O(3)-Mo(1)-O(2) 110.0(3) O(1)-Mo(1)-O(2) 108.8(3) O(3)-Mo(1)-O(8) 110.1(3) O(1)-Mo(1)-O(8) 107.4(3) O(2)-Mo(1)-O(8) 112.5(3) O(4)-Mo(2)-O(6) 103.2(3) O(4)-Mo(2)-O(5) 97.4(2) O(6)-Mo(2)-O(5) 98.67(18) O(4)-Mo(2)-O(8) 92.7(3) O(6)-Mo(2)-O(8) 97.2(2) O(5)-Mo(2)-O(8) 158.63(18) O(4)-Mo(2)-O(2)#4 97.8(3) O(6)-Mo(2)-O(2)#4 158.8(2) O(5)-Mo(2)-O(2)#4 80.74(15) O(8)-Mo(2)-O(2)#4 79.3(2) O(4)-Mo(2)-N(6) 170.1(3) O(6)-Mo(2)-N(6) 79.2(2) O(5)-Mo(2)-N(6) 91.60(16) O(8)-Mo(2)-N(6) 77.4(2) O(2)#4-Mo(2)-N(6) 79.6(2) Mo(1)-O(1)-Co(1) 152.9(3) Mo(1)-O(2)-Mo(2)#4 156.1(3) Mo(2)-O(5)-Mo(2)#5 180.00(4) Mo(2)-O(6)-Co(1)#6 168.5(4) Mo(1)-O(8)-Mo(2) 146.9(3) N(1)-C(1)-C(2) 123.3(7) C(3)-C(2)-C(1) 119.2(7) C(2)-C(3)-C(4) 118.7(8) C(2)-C(3)-C(6) 119.6(7) C(4)-C(3)-C(6) 121.7(7) C(3)-C(4)-C(5) 118.5(7) N(1)-C(5)-C(4) 122.8(7) N(2)-C(6)-N(3) 125.8(7) N(2)-C(6)-C(3) 119.4(7) N(3)-C(6)-C(3) 114.8(7) N(4)-C(7)-N(3) 124.7(7) N(4)-C(7)-C(9) 117.9(7) N(3)-C(7)-C(9) 117.4(7) N(4)-C(8)-N(2) 125.4(7) N(4)-C(8)-C(16)#7 116.1(7) N(2)-C(8)-C(16)#7 118.5(7) C(13)-C(9)-C(10) 118.2(7) C(13)-C(9)-C(7) 121.4(7) C(10)-C(9)-C(7) 120.5(7) C(9)-C(10)-C(11) 118.3(7) N(5)-C(11)-C(10) 124.4(7) N(5)-C(12)-C(13) 124.4(8) C(9)-C(13)-C(12) 118.8(7) N(6)-C(14)-C(15) 122.5(7) C(16)-C(15)-C(14) 118.9(7) C(15)-C(16)-C(17) 119.0(7) C(15)-C(16)-C(8)#7 121.9(7) C(17)-C(16)-C(8)#7 119.1(7) C(16)-C(17)-C(18) 118.6(7) N(6)-C(18)-C(17) 123.3(7) C(1)-N(1)-C(5) 117.3(7) C(1)-N(1)-Co(1) 116.6(5) C(5)-N(1)-Co(1) 125.0(6) C(6)-N(2)-C(8) 114.0(7) C(6)-N(3)-C(7) 114.6(7) C(8)-N(4)-C(7) 115.4(7) C(11)-N(5)-C(12) 116.0(7) C(14)-N(6)-C(18) 117.7(7) C(14)-N(6)-Mo(2) 126.0(5) C(18)-N(6)-Mo(2) 115.5(5) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,-y+2,-z+1 #2 -x+1,-y+2,-z+1 #3 x-1,y,z #4 -x+1,-y+1,-z+1 #5 -x+2,-y+1,-z+1 #6 x+1,y,z #7 -x+1,-y+2,-z Table 4. Anisotropic displacement parameters (Å2x 103) for p-1. The anisotropic displacement factor exponent takes the form: -2?2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ________________________________________________________________________ U11 U22 U33 U23 U13 U12 ________________________________________________________________________ Co(1) 8(1) 7(1) 4(1) 3(1) 1(1) -2(1) Mo(1) 7(1) 8(1) 7(1) 3(1) 1(1) -2(1) Mo(2) 7(1) 7(1) 5(1) 2(1) 1(1) -2(1) O(1) 8(2) 7(2) 17(3) 0(2) -1(2) 1(2) O(2) 13(3) 14(3) 6(3) -3(2) 6(2) 0(2) O(3) 16(3) 20(3) 13(3) 2(2) 4(2) -4(2) O(4) 20(3) 10(3) 14(3) 5(2) -2(2) -4(2) O(5) 11(4) 8(4) 16(4) 2(3) 2(3) -1(3) O(6) 5(2) 7(2) 14(3) 3(2) 1(2) -1(2) O(8) 8(3) 9(3) 14(3) 2(2) 1(2) -1(2) C(1) 13(4) 4(3) 12(4) 6(3) -1(3) -2(3) C(2) 10(3) 9(3) 9(4) 4(3) 1(3) 1(3) C(3) 12(4) 12(4) 10(4) 2(3) -2(3) -4(3) C(4) 16(4) 11(4) 9(4) 4(3) -3(3) 1(3) C(5) 17(4) 8(3) 13(4) 2(3) -3(3) 2(3) C(6) 8(3) 12(4) 9(4) 4(3) 2(3) -3(3) C(7) 6(3) 11(4) 11(4) 0(3) 2(3) -3(3) C(8) 9(3) 10(3) 8(3) 4(3) 2(3) -2(3) C(9) 11(4) 7(3) 10(4) 5(3) -2(3) -1(3) C(10) 7(3) 17(4) 7(4) 3(3) 5(3) -5(3) C(11) 10(3) 11(4) 11(4) 6(3) 4(3) -3(3) C(12) 10(4) 15(4) 8(4) 1(3) 4(3) -1(3) C(13) 13(4) 10(4) 12(4) 4(3) -1(3) -2(3) C(14) 13(4) 8(3) 8(4) 5(3) 2(3) -2(3) C(15) 9(3) 14(4) 6(3) 2(3) 0(3) -2(3) C(16) 9(3) 11(3) 9(4) 3(3) -1(3) -6(3) C(17) 17(4) 9(3) 8(4) 4(3) 4(3) -1(3) C(18) 11(3) 9(3) 6(3) 4(3) 3(3) -2(3) N(1) 12(3) 13(3) 3(3) 2(2) 0(2) -3(3) N(2) 14(3) 9(3) 7(3) 5(2) -1(3) -4(3) N(3) 11(3) 11(3) 7(3) 3(2) 3(2) -2(3) N(4) 11(3) 10(3) 10(3) 1(2) 3(3) -2(2) N(5) 15(3) 10(3) 14(3) 2(3) -1(3) 0(3) N(6) 9(3) 10(3) 7(3) 4(2) 3(2) -9(2) ________________________________________________________________________ #END Table 1. Crystal data and structure refinement for [NiMo4O13(tpytrz)2] Identification code p-1 Empirical formula C18 H12 Mo2 N6 Ni0.50 O6.50 Formula weight 637.57 Temperature 90(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.0747(4) Å ?=79.959(1)°. b = 8.8350(4) Å ?=84.275(1)°. c = 13.7011(7) Å ? = 80.583(1)°. Volume 946.94(8) Å3 Z 2 Density (calculated) 2.236 Mg/m3 Absorption coefficient 1.865 mm-1 F(000) 624 Crystal size 0.35x 0.35 x 0.2 mm3 Theta range for data collection 2.37 to 28.29°. Index ranges -10<=h<=9, -11<=k<=11, -18<=l<=15 Reflections collected 6470 Independent reflections 4426 [R(int) = 0.0213] Completeness to theta = 28.29° 93.9 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4426 / 0 / 349 Goodness-of-fit on F2 1.010 Final R indices [I>2sigma(I)] R1 = 0.0328, wR2 = 0.0773 R indices (all data) R1 = 0.0450, wR2 = 0.0813 Largest diff. peak and hole 1.214 and -1.204 e.Å-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for p-1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________ x y z U(eq) Ni(1) 0 5000 5000 7(1) Mo(1) 3456(1) 1833(1) 5745(1) 9(1) Mo(2) 1935(1) -1263(1) 4525(1) 7(1) O(1) 2223(3) 3624(3) 5365(2) 11(1) O(2) 5647(3) 2163(3) 5655(2) 12(1) O(3) 2824(4) 1174(3) 6953(2) 18(1) O(4) 3115(3) 474(3) 4980(2) 12(1) O(5) 0 0 5000 13(1) O(6) 1103(3) -2977(3) 4624(2) 9(1) O(7) 1844(3) -501(3) 3299(2) 15(1) C(1) 1478(5) 3299(4) 3364(3) 11(1) C(2) 2282(5) 3030(4) 2464(3) 13(1) C(3) 2137(5) 4220(4) 1646(3) 11(1) C(4) 1161(5) 5631(4) 1779(3) 12(1) C(5) 472(5) 5824(4) 2736(3) 13(1) C(6) 3053(5) 3954(4) 686(3) 12(1) C(7) 3552(5) 4583(4) -972(3) 13(1) C(8) 5102(5) 2489(4) -140(3) 12(1) C(9) 6458(5) 1157(4) -130(3) 12(1) C(10) 7336(5) 814(4) -1022(3) 14(1) C(11) 8579(5) -469(5) -977(3) 17(1) C(12) 8159(5) -1071(5) 710(3) 17(1) C(13) 6888(5) 187(4) 750(3) 15(1) C(14) 3651(5) -3865(4) 6299(3) 14(1) C(15) 4002(5) -4803(4) 7182(3) 14(1) C(16) 3193(5) -4378(4) 8060(3) 11(1) C(17) 2088(5) -3007(5) 8003(3) 13(1) C(18) 1828(5) -2094(5) 7071(3) 13(1) N(1) 625(4) 4684(3) 3519(2) 9(1) N(2) 4269(4) 2721(4) 731(2) 13(1) N(3) 4764(4) 3384(3) -1015(2) 12(1) N(4) 2648(4) 4944(4) -146(2) 12(1) N(5) 2597(4) -2507(3) 6225(2) 10(1) N(6) 9024(4) -1429(4) -131(3) 17(1) Table 5. Hydrogen coordinates ( x104) and isotropic displacement parameters (Å2x 10 3) for p-1. ______________________________________________________________ x y z U(eq) ______________________________________________________________ H(1) 1540(40) 2520(40) 3920(30) 0(9) H(2) 3030(50) 2040(50) 2400(30) 8(10) H(4) 960(50) 6490(50) 1270(30) 14(11) H(5) -180(50) 6820(40) 2870(30) 6(10) H(10) 7060(50) 1430(40) -1650(30) 4(9) H(11) 9330(50) -690(40) -1590(30) 6(10) H(12) 8560(60) -1760(50) 1320(30) 26(13) H(13) 6160(60) 340(50) 1370(30) 31(13) H(14) 4220(60) -4050(50) 5780(30) 28(13) H(15) 4620(50) -5590(40) 7200(30) 0(9) H(17) 1520(50) -2760(50) 8550(30) 12(11) H(18) 1210(50) -1210(50) 6960(30) 14(11) Table 3. Bond lengths [Å] and angles [°] for p-1. _____________________________________________________ Ni(1)-O(1)#1 2.050(2) Ni(1)-O(1) 2.050(2) Ni(1)-O(6)#2 2.088(2) Ni(1)-O(6)#3 2.088(2) Ni(1)-N(1) 2.096(3) Ni(1)-N(1)#1 2.096(3) Mo(1)-O(3) 1.712(3) Mo(1)-O(1) 1.751(2) Mo(1)-O(4) 1.795(2) Mo(1)-O(2) 1.828(2) Mo(2)-O(7) 1.701(3) Mo(2)-O(6) 1.734(2) Mo(2)-O(5) 1.8945(3) Mo(2)-O(2)#4 1.992(2) Mo(2)-O(4) 2.141(2) Mo(2)-N(5) 2.467(3) O(2)-Mo(2)#4 1.992(2) O(5)-Mo(2)#3 1.8945(3) O(6)-Ni(1)#5 2.088(2) C(1)-N(1) 1.343(5) C(1)-C(2) 1.375(5) C(2)-C(3) 1.397(5) C(3)-C(4) 1.392(5) C(3)-C(6) 1.479(5) C(4)-C(5) 1.399(5) C(5)-N(1) 1.338(5) C(6)-N(2) 1.339(5) C(6)-N(4) 1.343(5) C(7)-N(3) 1.324(5) C(7)-N(4) 1.342(5) C(7)-C(16)#6 1.500(5) C(8)-N(2) 1.341(5) C(8)-N(3) 1.342(5) C(8)-C(9) 1.470(5) C(9)-C(13) 1.390(5) C(9)-C(10) 1.406(5) C(10)-C(11) 1.384(5) C(11)-N(6) 1.354(5) C(12)-N(6) 1.346(5) C(12)-C(13) 1.388(5) C(14)-N(5) 1.347(5) C(14)-C(15) 1.368(5) C(15)-C(16) 1.391(5) C(16)-C(17) 1.377(5) C(16)-C(7)#7 1.500(5) C(17)-C(18) 1.401(5) C(18)-N(5) 1.337(5) O(1)#1-Ni(1)-O(1) 180.00(14) O(1)#1-Ni(1)-O(6)#2 86.45(10) O(1)-Ni(1)-O(6)#2 93.55(10) O(1)#1-Ni(1)-O(6)#3 93.55(10) O(1)-Ni(1)-O(6)#3 86.45(10) O(6)#2-Ni(1)-O(6)#3 180.0 O(1)#1-Ni(1)-N(1) 91.54(11) O(1)-Ni(1)-N(1) 88.46(11) O(6)#2-Ni(1)-N(1) 86.21(10) O(6)#3-Ni(1)-N(1) 93.79(10) O(1)#1-Ni(1)-N(1)#1 88.46(11) O(1)-Ni(1)-N(1)#1 91.54(11) O(6)#2-Ni(1)-N(1)#1 93.79(10) O(6)#3-Ni(1)-N(1)#1 86.21(10) N(1)-Ni(1)-N(1)#1 180.000(1) O(3)-Mo(1)-O(1) 108.28(12) O(3)-Mo(1)-O(4) 108.97(13) O(1)-Mo(1)-O(4) 108.89(12) O(3)-Mo(1)-O(2) 110.08(13) O(1)-Mo(1)-O(2) 107.57(11) O(4)-Mo(1)-O(2) 112.93(11) O(7)-Mo(2)-O(6) 103.39(12) O(7)-Mo(2)-O(5) 97.26(9) O(6)-Mo(2)-O(5) 98.72(8) O(7)-Mo(2)-O(2)#4 92.71(12) O(6)-Mo(2)-O(2)#4 97.43(11) O(5)-Mo(2)-O(2)#4 158.48(7) O(7)-Mo(2)-O(4) 98.51(11) O(6)-Mo(2)-O(4) 157.99(10) O(5)-Mo(2)-O(4) 80.47(7) O(2)#4-Mo(2)-O(4) 79.22(10) O(7)-Mo(2)-N(5) 169.90(11) O(6)-Mo(2)-N(5) 78.93(11) O(5)-Mo(2)-N(5) 92.04(7) O(2)#4-Mo(2)-N(5) 77.22(10) O(4)-Mo(2)-N(5) 79.11(10) Mo(1)-O(1)-Ni(1) 153.14(15) Mo(1)-O(2)-Mo(2)#4 146.94(14) Mo(1)-O(4)-Mo(2) 157.27(14) Mo(2)#3-O(5)-Mo(2) 180.0 Mo(2)-O(6)-Ni(1)#5 170.12(14) N(1)-C(1)-C(2) 123.4(3) C(1)-C(2)-C(3) 119.1(3) C(4)-C(3)-C(2) 118.0(3) C(4)-C(3)-C(6) 122.7(3) C(2)-C(3)-C(6) 119.3(3) C(3)-C(4)-C(5) 118.6(3) N(1)-C(5)-C(4) 123.0(3) N(2)-C(6)-N(4) 125.0(3) N(2)-C(6)-C(3) 115.6(3) N(4)-C(6)-C(3) 119.4(3) N(3)-C(7)-N(4) 125.8(3) N(3)-C(7)-C(16)#6 116.0(3) N(4)-C(7)-C(16)#6 118.2(3) N(2)-C(8)-N(3) 124.2(3) N(2)-C(8)-C(9) 117.5(3) N(3)-C(8)-C(9) 118.3(3) C(13)-C(9)-C(10) 118.2(4) C(13)-C(9)-C(8) 121.5(3) C(10)-C(9)-C(8) 120.3(3) C(11)-C(10)-C(9) 118.2(4) N(6)-C(11)-C(10) 124.8(4) N(6)-C(12)-C(13) 124.4(4) C(12)-C(13)-C(9) 118.9(4) N(5)-C(14)-C(15) 123.8(3) C(14)-C(15)-C(16) 119.1(4) C(17)-C(16)-C(15) 118.2(4) C(17)-C(16)-C(7)#7 122.5(3) C(15)-C(16)-C(7)#7 119.2(3) C(16)-C(17)-C(18) 119.1(3) N(5)-C(18)-C(17) 122.7(4) C(5)-N(1)-C(1) 117.5(3) C(5)-N(1)-Ni(1) 124.5(2) C(1)-N(1)-Ni(1) 117.1(2) C(6)-N(2)-C(8) 115.4(3) C(7)-N(3)-C(8) 115.4(3) C(7)-N(4)-C(6) 114.2(3) C(18)-N(5)-C(14) 117.0(3) C(18)-N(5)-Mo(2) 126.3(3) C(14)-N(5)-Mo(2) 115.8(2) C(12)-N(6)-C(11) 115.6(3) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,-y+1,-z+1 #2 x,y+1,z #3 -x,-y,-z+1 #4 -x+1,-y,-z+1 #5 x,y-1,z #6 x,y+1,z-1 #7 x,y-1,z+1 Table 4. Anisotropic displacement parameters (Å2x 103) for p-1. The anisotropic displacement factor exponent takes the form: -2?2[ h2 a*2U11 + ..+ 2 h k a* b* U12 ] ______________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________ Ni(1) 8(1) 5(1) 7(1) 0(1) 0(1) 0(1) Mo(1) 8(1) 7(1) 11(1) 0(1) -1(1) -1(1) Mo(2) 6(1) 5(1) 8(1) 0(1) 0(1) 0(1) O(1) 13(1) 8(1) 12(1) -1(1) -5(1) 2(1) O(2) 8(1) 11(1) 15(1) -4(1) -2(1) 2(1) O(3) 21(2) 17(2) 14(1) 0(1) 2(1) -4(1) O(4) 8(1) 11(1) 17(1) -5(1) 0(1) 0(1) O(5) 11(2) 8(2) 21(2) -6(2) -1(2) 1(1) O(6) 7(1) 7(1) 12(1) -1(1) 0(1) -2(1) O(7) 18(2) 15(1) 11(1) 2(1) -3(1) -1(1) C(1) 16(2) 11(2) 6(2) 1(1) -5(1) -3(1) C(2) 16(2) 8(2) 14(2) -2(2) -2(2) -2(2) C(3) 12(2) 13(2) 8(2) -1(1) -1(1) -2(1) C(4) 13(2) 11(2) 9(2) 4(1) 1(1) -1(1) C(5) 13(2) 10(2) 15(2) 0(2) 1(2) -1(2) C(6) 12(2) 14(2) 10(2) -2(1) -2(1) -3(1) C(7) 14(2) 13(2) 12(2) 0(2) -1(2) -4(2) C(8) 15(2) 12(2) 9(2) -1(1) -2(1) -1(2) C(9) 14(2) 12(2) 11(2) -2(1) -1(1) -2(1) C(10) 16(2) 12(2) 12(2) 0(2) -1(2) 1(2) C(11) 15(2) 18(2) 17(2) -5(2) 1(2) -2(2) C(12) 16(2) 17(2) 17(2) 0(2) -4(2) -1(2) C(13) 15(2) 15(2) 13(2) 1(2) 0(2) -2(2) C(14) 17(2) 15(2) 10(2) -6(2) 1(2) -2(2) C(15) 20(2) 7(2) 13(2) 2(2) -1(2) 4(2) C(16) 12(2) 13(2) 10(2) -3(1) -1(1) -5(1) C(17) 15(2) 16(2) 8(2) -2(2) 1(2) -3(2) C(18) 11(2) 12(2) 16(2) -1(2) -1(2) -2(2) N(1) 11(2) 8(2) 10(2) -2(1) 2(1) -4(1) N(2) 12(2) 13(2) 11(2) -1(1) 2(1) 0(1) N(3) 16(2) 10(2) 7(2) 3(1) 1(1) -1(1) N(4) 15(2) 11(2) 10(2) -1(1) 0(1) -1(1) N(5) 13(2) 7(2) 9(2) 2(1) -4(1) 0(1) N(6) 17(2) 16(2) 18(2) -4(1) -3(1) 0(1) #END Table 1. Crystal data and structure refinement for [ZnMo4O13(tpytrz)2] Identification code p-1 Empirical formula C18 H12 Cl0 Mo2 N6 O6.5 Zn0.50 Formula weight 640.90 Temperature 90(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.0888(6) Å ?=79.711(2)°. b = 8.9531(7) Å ?= 84.193(1)°. c = 13.680(1) Å ? =80.275(2)°. Volume 958.2(1) Å3 Z 2 Density (calculated) 2.221 Mg/m3 Absorption coefficient 1.977 mm-1 F(000) 626 Crystal size 0.3 x 0.2 x 0.02 mm3 Theta range for data collection 2.34 to 28.30°. Index ranges -10<=h<=10, -5<=k<=11, -18<=l<=17 Reflections collected 6571 Independent reflections 4458 [R(int) = 0.0427] Completeness to theta = 28.30° 93.5 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4458 / 0 / 301 Goodness-of-fit on F2 0.992 Final R indices [I>2sigma(I)] R1 = 0.0557, wR2 = 0.1170 R indices (all data) R1 = 0.0952, wR2 = 0.1318 Largest diff. peak and hole 2.410 and -1.198 e.Å-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for p-1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________ x y z U(eq) ______________________________________________________________ Zn(1) 5000 10000 5000 10(1) Mo(1) 1550(1) 3190(1) 4233(1) 10(1) Mo(2) 3063(1) 6217(1) 5491(1) 10(1) O(1) 2717(6) 1402(5) 4618(3) 13(1) O(2) -656(6) 2904(5) 4315(3) 13(1) O(3) 2202(6) 3829(6) 3028(4) 20(1) O(4) 1885(5) 4517(5) 4996(4) 13(1) O(5) 5000 5000 5000 17(2) O(6) 3158(6) 5402(6) 6711(4) 19(1) O(7) 3883(5) 7912(5) 5426(3) 11(1) C(1) 3504(8) 11701(7) 6651(5) 9(1) C(2) 2691(8) 11955(7) 7562(5) 9(1) C(3) 2861(8) 10790(8) 8371(5) 8(1) C(4) 3832(8) 9398(8) 8246(5) 10(1) C(5) 4540(8) 9198(8) 7292(5) 15(2) C(6) 1918(8) 11058(7) 9323(5) 9(1) C(7) 1426(8) 10415(8) 10997(5) 9(1) C(8) -124(8) 12512(8) 10157(5) 11(1) C(9) 1770(8) 9393(7) 11964(5) 9(1) C(10) 983(8) 9805(8) 12846(5) 9(1) C(11) 1326(8) 8843(8) 13737(5) 11(1) C(12) 3152(8) 7107(8) 12938(5) 10(1) C(13) 2873(8) 8007(8) 12011(5) 9(1) C(14) -2352(8) 14194(8) 11036(5) 12(2) C(15) -3590(8) 15470(8) 10974(5) 11(1) C(16) -3152(8) 16068(8) 9309(5) 13(2) C(17) -1887(8) 14809(8) 9263(5) 11(1) C(18) -1467(8) 13850(8) 10154(5) 11(1) N(1) 4367(6) 10326(6) 6506(4) 8(1) N(2) 2313(7) 10063(6) 10167(4) 11(1) N(3) 723(7) 12281(6) 9295(4) 8(1) N(4) 215(7) 11616(6) 11033(4) 9(1) N(5) 2401(7) 7493(6) 13790(4) 10(1) N(6) -4009(7) 16411(7) 10144(4) 15(1) ______________________________________________________________ Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for p-1. ______________________________________________________________ x y z U(eq) _____________________________________________________________ H(1) 3451 12512 6120 11 H(2) 2040 12897 7626 10 H(4) 4010 8609 8785 13 H(5) 5152 8249 7201 18 H(10) 233 10716 12839 11 H(11) 798 9133 14325 13 H(12) 3899 6191 12964 12 H(13) 3413 7691 11433 11 H(14) -2117 13585 11647 15 H(15) -4178 15686 11565 13 H(16) -3414 16714 8716 15 H(17) -1340 14614 8657 14 Table 3. Bond lengths [Å] and angles [°] for p-1. _____________________________________________________ Zn(1)-O(1)#1 2.107(5) Zn(1)-O(1)#2 2.107(5) Zn(1)-N(1)#3 2.132(5) Zn(1)-N(1) 2.132(5) Zn(1)-O(7)#3 2.174(4) Zn(1)-O(7) 2.174(4) Mo(1)-O(3) 1.707(5) Mo(1)-O(1) 1.737(5) Mo(1)-O(4) 1.785(5) Mo(1)-O(2) 1.835(4) Mo(2)-O(6) 1.702(5) Mo(2)-O(7) 1.741(4) Mo(2)-O(5) 1.8878(6) Mo(2)-O(2)#4 1.983(5) Mo(2)-O(4) 2.161(5) Mo(2)-N(5)#5 2.470(5) O(1)-Zn(1)#6 2.107(4) O(2)-Mo(2)#4 1.983(4) O(5)-Mo(2)#1 1.8878(6) C(1)-N(1) 1.345(8) C(1)-C(2) 1.386(9) C(2)-C(3) 1.379(9) C(3)-C(4) 1.385(9) C(3)-C(6) 1.478(9) C(4)-C(5) 1.400(9) C(5)-N(1) 1.338(9) C(6)-N(3) 1.330(8) C(6)-N(2) 1.356(8) C(7)-N(4) 1.331(8) C(7)-N(2) 1.338(8) C(7)-C(9) 1.490(9) C(8)-N(3) 1.334(8) C(8)-N(4) 1.343(8) C(8)-C(18) 1.475(9) C(9)-C(10) 1.386(9) C(9)-C(13) 1.396(9) C(10)-C(11) 1.385(9) C(11)-N(5) 1.360(8) C(12)-N(5) 1.333(8) C(12)-C(13) 1.393(9) C(14)-C(15) 1.382(9) C(14)-C(18) 1.396(9) C(15)-N(6) 1.324(9) C(16)-N(6) 1.331(9) C(16)-C(17) 1.394(9) C(17)-C(18) 1.397(9) N(5)-Mo(2)#7 2.470(5) O(1)#1-Zn(1)-O(1)#2 180.000(1) O(1)#1-Zn(1)-N(1)#3 88.57(19) O(1)#2-Zn(1)-N(1)#3 91.43(19) O(1)#1-Zn(1)-N(1) 91.43(19) O(1)#2-Zn(1)-N(1) 88.57(19) N(1)#3-Zn(1)-N(1) 180.000(1) O(1)#1-Zn(1)-O(7)#3 94.35(17) O(1)#2-Zn(1)-O(7)#3 85.65(17) N(1)#3-Zn(1)-O(7)#3 85.58(19) N(1)-Zn(1)-O(7)#3 94.42(19) O(1)#1-Zn(1)-O(7) 85.65(17) O(1)#2-Zn(1)-O(7) 94.35(17) N(1)#3-Zn(1)-O(7) 94.42(19) N(1)-Zn(1)-O(7) 85.58(19) O(7)#3-Zn(1)-O(7) 180.000(1) O(3)-Mo(1)-O(1) 108.5(2) O(3)-Mo(1)-O(4) 109.2(2) O(1)-Mo(1)-O(4) 109.9(2) O(3)-Mo(1)-O(2) 110.1(2) O(1)-Mo(1)-O(2) 106.7(2) O(4)-Mo(1)-O(2) 112.4(2) O(6)-Mo(2)-O(7) 103.5(2) O(6)-Mo(2)-O(5) 96.98(17) O(7)-Mo(2)-O(5) 98.72(15) O(6)-Mo(2)-O(2)#4 92.7(2) O(7)-Mo(2)-O(2)#4 97.3(2) O(5)-Mo(2)-O(2)#4 158.84(14) O(6)-Mo(2)-O(4) 98.2(2) O(7)-Mo(2)-O(4) 158.18(19) O(5)-Mo(2)-O(4) 80.66(12) O(2)#4-Mo(2)-O(4) 79.35(18) O(6)-Mo(2)-N(5)#5 170.2(2) O(7)-Mo(2)-N(5)#5 79.6(2) O(5)-Mo(2)-N(5)#5 91.70(13) O(2)#4-Mo(2)-N(5)#5 77.65(18) O(4)-Mo(2)-N(5)#5 78.61(18) Mo(1)-O(1)-Zn(1)#6 151.2(3) Mo(1)-O(2)-Mo(2)#4 147.9(3) Mo(1)-O(4)-Mo(2) 158.2(3) Mo(2)#1-O(5)-Mo(2) 180.0 Mo(2)-O(7)-Zn(1) 167.5(3) N(1)-C(1)-C(2) 122.6(6) C(3)-C(2)-C(1) 119.1(6) C(2)-C(3)-C(4) 118.8(6) C(2)-C(3)-C(6) 118.3(6) C(4)-C(3)-C(6) 122.8(6) C(3)-C(4)-C(5) 118.8(6) N(1)-C(5)-C(4) 122.2(7) N(3)-C(6)-N(2) 124.0(6) N(3)-C(6)-C(3) 117.1(6) N(2)-C(6)-C(3) 118.9(6) N(4)-C(7)-N(2) 124.9(6) N(4)-C(7)-C(9) 116.2(6) N(2)-C(7)-C(9) 118.9(6) N(3)-C(8)-N(4) 123.4(6) N(3)-C(8)-C(18) 118.3(6) N(4)-C(8)-C(18) 118.2(6) C(10)-C(9)-C(13) 118.3(6) C(10)-C(9)-C(7) 120.1(6) C(13)-C(9)-C(7) 121.6(6) C(11)-C(10)-C(9) 119.2(6) N(5)-C(11)-C(10) 122.9(6) N(5)-C(12)-C(13) 123.2(6) C(12)-C(13)-C(9) 118.9(6) C(15)-C(14)-C(18) 117.9(6) N(6)-C(15)-C(14) 125.6(6) N(6)-C(16)-C(17) 124.6(6) C(16)-C(17)-C(18) 118.0(6) C(14)-C(18)-C(17) 118.2(6) C(14)-C(18)-C(8) 121.2(6) C(17)-C(18)-C(8) 120.6(6) C(5)-N(1)-C(1) 118.2(6) C(5)-N(1)-Zn(1) 124.1(5) C(1)-N(1)-Zn(1) 116.8(4) C(7)-N(2)-C(6) 114.9(6) C(6)-N(3)-C(8) 116.7(6) C(7)-N(4)-C(8) 116.1(6) C(12)-N(5)-C(11) 117.5(6) C(12)-N(5)-Mo(2)#7 126.6(4) C(11)-N(5)-Mo(2)#7 115.2(4) C(15)-N(6)-C(16) 115.9(6) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+1,-z+1 #2 x,y+1,z #3 -x+1,-y+2,-z+1 #4 -x,-y+1,-z+1 #5 x,y,z-1 #6 x,y-1,z #7 x,y,z+1 Table 4. Anisotropic displacement parameters (Å2x 103) for p-1. The anisotropic displacement factor exponent takes the form: -2?2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________ Zn(1) 10(1) 11(1) 8(1) -2(1) -1(1) 2(1) Mo(1) 8(1) 11(1) 11(1) -1(1) -1(1) 1(1) Mo(2) 7(1) 8(1) 12(1) -1(1) -1(1) 2(1) O(1) 10(2) 13(3) 14(3) -4(2) -4(2) 3(2) O(2) 7(2) 17(3) 15(3) -8(2) 0(2) 2(2) O(3) 22(3) 23(3) 13(3) 0(2) -1(2) -1(2) O(4) 4(2) 14(3) 21(3) -1(2) -5(2) 1(2) O(5) 7(3) 18(4) 27(4) -13(3) 0(3) 8(3) O(6) 16(3) 20(3) 19(3) 2(2) -4(2) -1(2) O(7) 7(2) 7(2) 20(3) -5(2) -4(2) 0(2) C(1) 10(3) 6(3) 12(3) -2(3) -4(3) -1(3) C(2) 11(3) 7(3) 8(3) 0(3) -4(2) 0(3) C(3) 4(3) 12(3) 8(3) -4(3) -1(2) 1(3) C(4) 8(3) 8(3) 12(3) 6(3) -2(3) 1(3) C(5) 9(3) 18(4) 18(4) -5(3) 3(3) -4(3) C(6) 10(3) 5(3) 14(4) -4(3) -3(3) -2(3) C(7) 6(3) 10(3) 15(4) -6(3) 0(3) -7(3) C(8) 9(3) 13(4) 14(4) -8(3) -1(3) -3(3) C(9) 9(3) 6(3) 12(3) -1(3) -1(3) 0(3) C(10) 9(3) 12(4) 5(3) -2(3) -1(2) 2(3) C(11) 12(3) 12(4) 4(3) 0(3) 0(2) 6(3) C(12) 8(3) 12(3) 9(3) -3(3) -1(2) 3(3) C(13) 7(3) 15(4) 8(3) -6(3) 3(2) -4(3) C(14) 12(4) 8(3) 14(4) 2(3) -1(3) 2(3) C(15) 9(3) 16(4) 9(3) -8(3) -1(3) 4(3) C(16) 14(4) 14(4) 9(3) 2(3) -6(3) 1(3) C(17) 5(3) 21(4) 8(3) -1(3) -1(2) -1(3) C(18) 7(3) 11(4) 13(4) -7(3) -5(3) 7(3) N(1) 3(3) 12(3) 9(3) -3(2) -1(2) -2(2) N(2) 13(3) 9(3) 10(3) -2(2) 0(2) -2(2) N(3) 10(3) 10(3) 5(3) 0(2) -3(2) -5(2) N(4) 10(3) 8(3) 10(3) -1(2) -3(2) -1(2) N(5) 9(3) 10(3) 10(3) 0(2) -2(2) -1(2) N(6) 13(3) 17(3) 16(3) -6(3) -3(2) -3(3) ______________________________________________________________ #END Table 1. Crystal data and structure refinement for [Ni(H2O)4(Htpytrz)2][Mo8O26)1.2H2O Identification code c2c Empirical formula C18 H18.20 Mo4 N6 Ni0.50 O15.60 Formula weight 981.30 Temperature 90(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group C2/c Unit cell dimensions a = 28.0815(14) Å ?= 90°. b = 13.7086(7) Å ?= 111.345(1)°. c = 15.7078(8) Å ? = 90°. Volume 5632.1(5) Å3 Z 8 Density (calculated) 2.315 Mg/m3 Absorption coefficient 2.149 mm-1 F(000) 3800 Crystal size 0.34 x 0.34 x 0.25 mm3 Theta range for data collection 1.68 to 23.25°. Index ranges -24<=h<=31, -15<=k<=14, -16<=l<=17 Reflections collected 12944 Independent reflections 4059 [R(int) = 0.0316] Completeness to theta = 23.25° 100.0 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4059 / 0 / 404 Goodness-of-fit on F2 1.229 Final R indices [I>2sigma(I)] R1 = 0.0332, wR2 = 0.0892 R indices (all data) R1 = 0.0414, wR2 = 0.0928 Largest diff. peak and hole 2.223 and -0.577 e.Å-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for c2c. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ Ni(1) 7500 2500 5000 19(1) Mo(1) 3079(1) 9056(1) 1080(1) 19(1) Mo(2) 3057(1) 6801(1) 583(1) 17(1) Mo(3) 2068(1) 6431(1) 1132(1) 20(1) Mo(4) 2077(1) 8744(1) 1628(1) 22(1) O(1) 2537(1) 7777(3) 869(2) 19(1) O(2) 2510(2) 6261(3) 2203(3) 25(1) O(3) 1636(2) 5513(3) 968(3) 28(1) O(4) 1713(2) 7534(3) 1334(3) 24(1) O(5) 2507(2) 8452(3) 2702(3) 29(1) O(6) 1649(2) 9503(3) 1805(3) 30(1) O(7) 2513(1) 9638(3) 1282(2) 20(1) O(8) 3458(2) 8737(3) 2163(3) 24(1) O(9) 2509(1) 9082(3) -453(2) 19(1) O(10) 3357(2) 10078(3) 839(3) 24(1) O(11) 3310(1) 8078(3) 383(2) 19(1) O(12) 3450(2) 6583(3) 1674(3) 23(1) O(13) 3317(1) 6130(3) -90(3) 21(1) O(14) 7135(2) 1431(3) 5450(3) 23(1) O(15) 7579(2) 1602(3) 3987(3) 26(1) O(16) 4477(5) 427(8) 1368(11) 113(7) C(1) 5264(3) 8174(5) 1727(5) 40(2) C(2) 5327(3) 7167(5) 1817(4) 32(2) C(3) 4964(2) 6565(5) 1245(4) 31(2) C(4) 4531(3) 6992(6) 568(5) 42(2) C(5) 4505(3) 8004(6) 536(6) 54(2) C(6) 5013(2) 5495(5) 1315(4) 26(1) C(7) 5457(2) 4155(5) 2020(4) 25(2) C(8) 4730(2) 3986(6) 801(4) 29(2) C(9) 4339(2) 3346(6) 127(4) 31(2) C(10) 4363(2) 2350(6) 214(4) 37(2) C(11) 4014(3) 1781(7) -455(5) 50(2) C(12) 3625(3) 3202(8) -1269(5) 51(2) C(13) 3962(3) 3767(6) -611(4) 42(2) C(14) 5910(2) 3722(4) 2746(4) 22(1) C(15) 6016(2) 2741(5) 2793(4) 26(1) C(16) 6464(2) 2401(5) 3455(4) 25(1) C(17) 6681(2) 3937(4) 4036(4) 23(1) C(18) 6249(2) 4337(5) 3398(4) 22(1) N(1) 4860(2) 8597(5) 1102(5) 51(2) N(2) 6797(2) 2987(4) 4067(3) 21(1) N(3) 4661(2) 4945(4) 692(3) 30(1) N(4) 5118(2) 3537(4) 1449(3) 25(1) N(5) 5418(2) 5130(4) 1989(3) 24(1) N(6) 3662(2) 2240(7) -1188(4) 54(2) Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for c2c. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ H(2) 5516 8572 2124 47 H(3) 5616 6906 2265 38 H(5) 4274 6610 162 51 H(6) 4223 8290 92 65 H(17) 4610 2060 716 45 H(18) 4019 1104 -406 60 H(19) 3372 3487 -1768 62 H(12) 3939 4443 -660 50 H(15) 5790 2310 2387 31 H(16) 6536 1738 3473 30 H(14) 6905 4348 4470 27 H(13) 6184 5002 3401 26 ________________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for c2c. ________________________________________________________________________ Ni(1)-O(14)#1 2.055(4) Ni(1)-O(14) 2.055(4) Ni(1)-O(15)#1 2.085(4) Ni(1)-O(15) 2.085(4) Ni(1)-N(2)#1 2.093(5) Ni(1)-N(2) 2.093(5) Mo(1)-O(8) 1.704(4) Mo(1)-O(10) 1.713(4) Mo(1)-O(7) 1.905(4) Mo(1)-O(11) 1.983(4) Mo(1)-O(1) 2.265(4) Mo(1)-O(9) 2.356(4) Mo(1)-Mo(2) 3.1829(7) Mo(2)-O(12) 1.693(4) Mo(2)-O(13) 1.750(4) Mo(2)-O(9)#2 1.949(4) Mo(2)-O(11) 1.957(4) Mo(2)-O(1) 2.145(4) Mo(2)-O(1)#2 2.356(4) Mo(3)-O(3) 1.701(4) Mo(3)-O(2) 1.704(4) Mo(3)-O(4) 1.901(4) Mo(3)-O(9)#2 1.992(4) Mo(3)-O(11)#2 2.324(4) Mo(3)-O(1) 2.388(4) Mo(4)-O(6) 1.687(4) Mo(4)-O(5) 1.727(4) Mo(4)-O(4) 1.915(4) Mo(4)-O(7) 1.944(4) Mo(4)-O(13)#2 2.268(4) Mo(4)-O(1) 2.442(4) O(1)-Mo(2)#2 2.356(4) O(9)-Mo(2)#2 1.949(4) O(9)-Mo(3)#2 1.992(4) O(11)-Mo(3)#2 2.324(4) O(13)-Mo(4)#2 2.268(4) C(1)-N(1) 1.333(9) C(1)-C(2) 1.393(10) C(2)-C(3) 1.365(10) C(3)-C(4) 1.418(9) C(3)-C(6) 1.474(10) C(4)-C(5) 1.389(11) C(5)-N(1) 1.341(11) C(6)-N(3) 1.340(8) C(6)-N(5) 1.339(7) C(7)-N(5) 1.340(8) C(7)-N(4) 1.344(8) C(7)-C(14) 1.489(8) C(8)-N(3) 1.330(9) C(8)-N(4) 1.340(8) C(8)-C(9) 1.499(9) C(9)-C(10) 1.371(10) C(9)-C(13) 1.380(9) C(10)-C(11) 1.387(10) C(11)-N(6) 1.368(10) C(12)-N(6) 1.326(11) C(12)-C(13) 1.361(11) C(14)-C(15) 1.373(9) C(14)-C(18) 1.400(8) C(15)-C(16) 1.390(8) C(16)-N(2) 1.337(8) C(17)-N(2) 1.339(8) C(17)-C(18) 1.375(8) O(14)#1-Ni(1)-O(14) 180.0(2) O(14)#1-Ni(1)-O(15)#1 92.62(16) O(14)-Ni(1)-O(15)#1 87.38(16) O(14)#1-Ni(1)-O(15) 87.38(16) O(14)-Ni(1)-O(15) 92.62(16) O(15)#1-Ni(1)-O(15) 180.000(1) O(14)#1-Ni(1)-N(2)#1 90.43(17) O(14)-Ni(1)-N(2)#1 89.57(17) O(15)#1-Ni(1)-N(2)#1 89.34(17) O(15)-Ni(1)-N(2)#1 90.66(17) O(14)#1-Ni(1)-N(2) 89.57(17) O(14)-Ni(1)-N(2) 90.43(17) O(15)#1-Ni(1)-N(2) 90.66(17) O(15)-Ni(1)-N(2) 89.34(17) N(2)#1-Ni(1)-N(2) 180.0(2) O(8)-Mo(1)-O(10) 105.12(19) O(8)-Mo(1)-O(7) 101.38(18) O(10)-Mo(1)-O(7) 99.80(18) O(8)-Mo(1)-O(11) 99.57(17) O(10)-Mo(1)-O(11) 99.42(17) O(7)-Mo(1)-O(11) 146.64(16) O(8)-Mo(1)-O(1) 95.14(17) O(10)-Mo(1)-O(1) 159.61(16) O(7)-Mo(1)-O(1) 77.98(15) O(11)-Mo(1)-O(1) 74.53(15) O(8)-Mo(1)-O(9) 165.82(17) O(10)-Mo(1)-O(9) 87.53(16) O(7)-Mo(1)-O(9) 82.34(14) O(11)-Mo(1)-O(9) 71.53(14) O(1)-Mo(1)-O(9) 72.08(13) O(8)-Mo(1)-Mo(2) 86.80(14) O(10)-Mo(1)-Mo(2) 135.22(14) O(7)-Mo(1)-Mo(2) 120.31(12) O(11)-Mo(1)-Mo(2) 35.83(11) O(1)-Mo(1)-Mo(2) 42.33(10) O(9)-Mo(1)-Mo(2) 79.59(9) O(12)-Mo(2)-O(13) 104.86(19) O(12)-Mo(2)-O(9)#2 101.73(18) O(13)-Mo(2)-O(9)#2 96.49(17) O(12)-Mo(2)-O(11) 100.38(18) O(13)-Mo(2)-O(11) 96.78(17) O(9)#2-Mo(2)-O(11) 150.28(15) O(12)-Mo(2)-O(1) 98.13(17) O(13)-Mo(2)-O(1) 156.99(16) O(9)#2-Mo(2)-O(1) 79.55(15) O(11)-Mo(2)-O(1) 77.87(15) O(12)-Mo(2)-O(1)#2 173.87(17) O(13)-Mo(2)-O(1)#2 81.25(15) O(9)#2-Mo(2)-O(1)#2 77.73(14) O(11)-Mo(2)-O(1)#2 78.17(14) O(1)-Mo(2)-O(1)#2 75.75(14) O(12)-Mo(2)-Mo(1) 88.66(14) O(13)-Mo(2)-Mo(1) 133.16(13) O(9)#2-Mo(2)-Mo(1) 124.86(11) O(11)-Mo(2)-Mo(1) 36.39(11) O(1)-Mo(2)-Mo(1) 45.32(10) O(1)#2-Mo(2)-Mo(1) 86.73(10) O(3)-Mo(3)-O(2) 105.6(2) O(3)-Mo(3)-O(4) 103.01(19) O(2)-Mo(3)-O(4) 100.45(18) O(3)-Mo(3)-O(9)#2 100.88(18) O(2)-Mo(3)-O(9)#2 96.83(17) O(4)-Mo(3)-O(9)#2 145.34(16) O(3)-Mo(3)-O(11)#2 91.44(17) O(2)-Mo(3)-O(11)#2 161.33(17) O(4)-Mo(3)-O(11)#2 82.51(15) O(9)#2-Mo(3)-O(11)#2 72.11(14) O(3)-Mo(3)-O(1) 162.39(16) O(2)-Mo(3)-O(1) 91.59(16) O(4)-Mo(3)-O(1) 76.74(15) O(9)#2-Mo(3)-O(1) 72.95(14) O(11)#2-Mo(3)-O(1) 71.00(13) O(6)-Mo(4)-O(5) 105.5(2) O(6)-Mo(4)-O(4) 102.96(19) O(5)-Mo(4)-O(4) 98.99(19) O(6)-Mo(4)-O(7) 102.47(19) O(5)-Mo(4)-O(7) 97.55(18) O(4)-Mo(4)-O(7) 144.54(16) O(6)-Mo(4)-O(13)#2 91.61(17) O(5)-Mo(4)-O(13)#2 162.75(17) O(4)-Mo(4)-O(13)#2 78.42(15) O(7)-Mo(4)-O(13)#2 76.56(15) O(6)-Mo(4)-O(1) 161.80(17) O(5)-Mo(4)-O(1) 92.58(17) O(4)-Mo(4)-O(1) 75.15(14) O(7)-Mo(4)-O(1) 72.96(14) O(13)#2-Mo(4)-O(1) 70.23(13) Mo(2)-O(1)-Mo(1) 92.35(14) Mo(2)-O(1)-Mo(2)#2 104.25(14) Mo(1)-O(1)-Mo(2)#2 98.79(14) Mo(2)-O(1)-Mo(3) 90.83(14) Mo(1)-O(1)-Mo(3) 162.94(17) Mo(2)#2-O(1)-Mo(3) 96.66(13) Mo(2)-O(1)-Mo(4) 164.12(18) Mo(1)-O(1)-Mo(4) 87.44(13) Mo(2)#2-O(1)-Mo(4) 91.46(13) Mo(3)-O(1)-Mo(4) 84.96(12) Mo(3)-O(4)-Mo(4) 117.5(2) Mo(1)-O(7)-Mo(4) 115.5(2) Mo(2)#2-O(9)-Mo(3)#2 110.26(18) Mo(2)#2-O(9)-Mo(1) 108.84(16) Mo(3)#2-O(9)-Mo(1) 103.06(15) Mo(2)-O(11)-Mo(1) 107.79(17) Mo(2)-O(11)-Mo(3)#2 111.52(17) Mo(1)-O(11)-Mo(3)#2 104.52(16) Mo(2)-O(13)-Mo(4)#2 117.02(19) N(1)-C(1)-C(2) 123.3(8) C(3)-C(2)-C(1) 119.6(7) C(2)-C(3)-C(4) 118.5(7) C(2)-C(3)-C(6) 121.7(6) C(4)-C(3)-C(6) 119.8(7) C(5)-C(4)-C(3) 117.3(7) N(1)-C(5)-C(4) 124.4(7) N(3)-C(6)-N(5) 123.8(6) N(3)-C(6)-C(3) 118.8(5) N(5)-C(6)-C(3) 117.4(6) N(5)-C(7)-N(4) 125.2(6) N(5)-C(7)-C(14) 117.4(5) N(4)-C(7)-C(14) 117.4(6) N(3)-C(8)-N(4) 126.2(6) N(3)-C(8)-C(9) 117.0(6) N(4)-C(8)-C(9) 116.9(6) C(10)-C(9)-C(13) 119.7(7) C(10)-C(9)-C(8) 121.0(6) C(13)-C(9)-C(8) 119.2(7) C(9)-C(10)-C(11) 119.3(7) N(6)-C(11)-C(10) 118.3(8) N(6)-C(12)-C(13) 119.0(8) C(12)-C(13)-C(9) 120.6(8) C(15)-C(14)-C(18) 118.3(6) C(15)-C(14)-C(7) 122.6(6) C(18)-C(14)-C(7) 119.0(6) C(14)-C(15)-C(16) 119.2(6) N(2)-C(16)-C(15) 122.9(6) N(2)-C(17)-C(18) 123.6(6) C(17)-C(18)-C(14) 118.5(6) C(5)-N(1)-C(1) 116.9(7) C(16)-N(2)-C(17) 117.4(5) C(16)-N(2)-Ni(1) 123.1(4) C(17)-N(2)-Ni(1) 119.3(4) C(8)-N(3)-C(6) 115.4(5) C(8)-N(4)-C(7) 113.6(6) C(7)-N(5)-C(6) 115.8(5) C(12)-N(6)-C(11) 123.1(7) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+3/2,-y+1/2,-z+1 #2 -x+1/2,-y+3/2,-z Table 4. Anisotropic displacement parameters (Å2x 103) for c2c. The anisotropic displacement factor exponent takes the form: -2?2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ________________________________________________________________________ U11 U22 U33 U23 U13 U12 ________________________________________________________________________ Ni(1) 17(1) 22(1) 13(1) 0(1) 2(1) 0(1) Mo(1) 18(1) 21(1) 14(1) 1(1) 2(1) 1(1) Mo(2) 15(1) 21(1) 13(1) 2(1) 2(1) 3(1) Mo(3) 20(1) 25(1) 14(1) 2(1) 5(1) 2(1) Mo(4) 24(1) 26(1) 15(1) 0(1) 8(1) 2(1) O(1) 18(2) 25(2) 13(2) 1(2) 4(2) 0(2) O(2) 22(2) 33(3) 17(2) 4(2) 3(2) 2(2) O(3) 25(2) 34(3) 26(2) 3(2) 11(2) -2(2) O(4) 21(2) 31(2) 20(2) 1(2) 9(2) 3(2) O(5) 35(3) 36(3) 15(2) -1(2) 8(2) -3(2) O(6) 32(3) 33(3) 30(2) -3(2) 17(2) 4(2) O(7) 19(2) 25(2) 14(2) -1(2) 3(2) 4(2) O(8) 27(2) 27(2) 14(2) 0(2) 2(2) 1(2) O(9) 18(2) 22(2) 14(2) 4(2) 2(2) 3(2) O(10) 22(2) 24(2) 23(2) 0(2) 5(2) 0(2) O(11) 15(2) 23(2) 15(2) 2(2) 3(2) 2(2) O(12) 21(2) 26(2) 17(2) 3(2) 0(2) 5(2) O(13) 14(2) 27(2) 20(2) 2(2) 5(2) 2(2) O(14) 19(2) 28(2) 22(2) -1(2) 7(2) -3(2) O(15) 26(2) 31(2) 20(2) -1(2) 9(2) 0(2) O(16) 107(11) 45(8) 204(17) 31(8) 75(11) 24(7) C(1) 34(4) 45(5) 45(4) 10(4) 21(4) 7(3) C(2) 29(4) 42(4) 31(4) 10(3) 19(3) 11(3) C(3) 19(4) 49(4) 31(4) 16(3) 17(3) 11(3) C(4) 22(4) 61(5) 42(4) 22(4) 9(3) 7(3) C(5) 31(5) 63(6) 68(6) 34(5) 17(4) 17(4) C(6) 13(3) 47(4) 18(3) 6(3) 7(3) 6(3) C(7) 18(3) 46(5) 13(3) 1(3) 9(3) 3(3) C(8) 14(3) 64(5) 11(3) 1(3) 6(3) 1(3) C(9) 19(4) 54(5) 21(3) 0(3) 8(3) -1(3) C(10) 17(4) 72(6) 21(3) -14(3) 4(3) -7(3) C(11) 39(5) 77(6) 36(4) -18(4) 16(4) -4(4) C(12) 19(4) 102(8) 30(4) -10(5) 6(3) 10(4) C(13) 22(4) 85(6) 17(4) 0(4) 4(3) 1(4) C(14) 18(3) 31(4) 17(3) 5(3) 7(3) 0(3) C(15) 25(4) 29(4) 18(3) -2(3) 1(3) -3(3) C(16) 25(4) 21(3) 21(3) 1(3) 0(3) 3(3) C(17) 17(3) 27(4) 18(3) 0(3) 0(3) -2(3) C(18) 21(3) 23(3) 19(3) 0(3) 5(3) 3(3) N(1) 27(4) 62(5) 65(4) 23(4) 20(3) 20(3) N(2) 17(3) 26(3) 18(3) 1(2) 5(2) -4(2) N(3) 18(3) 51(4) 22(3) 11(3) 8(2) 9(3) N(4) 13(3) 42(3) 18(3) -1(2) 3(2) 0(2) N(5) 17(3) 34(3) 23(3) 8(2) 9(2) 7(2) N(6) 22(3) 116(7) 25(3) -25(4) 11(3) -5(4) #END Table 1. Crystal data and structure refinement for [Ni(Mo2O7)(tpytrz)]. Identification code Pnma Empirical formula C18 H12 N6 Ni Mo2 O7 Formula weight 674.93 Temperature 90(2) K Wavelength 0.71073 Å Crystal system Orthorhombic Space group Pmna Unit cell dimensions a = 8.5954(5) Å ?= 90°. b = 26.861(1) Å ?= 90°. c = 9.1687(5) Å ? = 90°. Volume 2116.9(2) Å3 Z 4 Density (calculated) 2.118 Mg/m3 Absorption coefficient 2.103 mm-1 F(000) 1320 Crystal size 0.1 x 0.1 x 0.05 mm3 Theta range for data collection 2.35 to 28.30°. Index ranges -8<=h<=11, -35<=k<=32, -12<=l<=12 Reflections collected 13162 Independent reflections 2651 [R(int) = 0.0494] Completeness to theta = 28.30° 98.6 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2651 / 0 / 163 Goodness-of-fit on F2 1.056 Final R indices [I>2sigma(I)] R1 = 0.0332, wR2 = 0.0688 R indices (all data) R1 = 0.0476, wR2 = 0.0727 Largest diff. peak and hole 0.640 and -0.650 e.Å-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for pnma. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ Ni(1) 5000 5000 10000 9(1) Mo(1) 1156(1) 4614(1) 8693(1) 14(1) O(1) 3076(3) 4619(1) 9282(2) 15(1) O(2) 501(4) 4018(1) 8648(3) 43(1) O(3) 1032(3) 4869(1) 6951(2) 14(1) O(4) 0 5000 10000 48(1) C(1) 4414(4) 6109(1) 9903(3) 13(1) C(2) 4103(4) 6570(1) 9302(4) 13(1) C(3) 3522(3) 6598(1) 7882(3) 11(1) C(4) 3247(4) 6151(1) 7148(3) 13(1) C(5) 3596(4) 5711(1) 7832(3) 13(1) C(6) 3240(4) 7081(1) 7143(3) 11(1) C(7) 2469(5) 7500 5135(5) 10(1) C(8) 1940(5) 7500 3590(5) 10(1) C(9) 1684(4) 7057(1) 2845(4) 15(1) C(10) 1136(4) 7078(1) 1417(4) 16(1) N(1) 4196(3) 5678(1) 9176(3) 11(1) N(2) 3571(4) 7500 7877(4) 12(1) N(3) 2686(3) 7059(1) 5782(3) 11(1) N(4) 864(5) 7500 685(4) 17(1) ________________________________________________________________________ Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for pnma. ________________________________________________________________________ x y z U(eq) H(1) 4792 6095 10853 15 H(2) 4278 6859 9837 16 H(4) 2835 6152 6210 15 H(5) 3403 5416 7331 15 H(9) 1873 6752 3292 18 H(10) 948 6778 939 19 ________________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for pnma. _____________________________________________________ Ni(1)-O(3)#1 2.027(2) Ni(1)-O(3)#2 2.027(2) Ni(1)-O(1)#3 2.053(2) Ni(1)-O(1) 2.053(2) Ni(1)-N(1) 2.090(3) Ni(1)-N(1)#3 2.090(3) Mo(1)-O(2) 1.698(3) Mo(1)-O(1) 1.736(2) Mo(1)-O(3) 1.741(2) Mo(1)-O(4) 1.8694(3) O(3)-Ni(1)#4 2.027(2) O(4)-Mo(1)#5 1.8694(3) C(1)-N(1) 1.348(4) C(1)-C(2) 1.384(4) C(2)-C(3) 1.396(4) C(3)-C(4) 1.396(4) C(3)-C(6) 1.483(4) C(4)-C(5) 1.372(4) C(5)-N(1) 1.338(4) C(6)-N(3) 1.337(4) C(6)-N(2) 1.343(4) C(7)-N(3)#6 1.338(3) C(7)-N(3) 1.338(3) C(7)-C(8) 1.487(6) C(8)-C(9)#6 1.390(4) C(8)-C(9) 1.390(4) C(9)-C(10) 1.393(5) C(10)-N(4) 1.339(4) N(2)-C(6)#6 1.343(4) N(4)-C(10)#6 1.339(4) O(3)#1-Ni(1)-O(3)#2 180.000(1) O(3)#1-Ni(1)-O(1)#3 89.04(9) O(3)#2-Ni(1)-O(1)#3 90.96(9) O(3)#1-Ni(1)-O(1) 90.96(9) O(3)#2-Ni(1)-O(1) 89.04(9) O(1)#3-Ni(1)-O(1) 180.00(11) O(3)#1-Ni(1)-N(1) 91.33(9) O(3)#2-Ni(1)-N(1) 88.67(9) O(1)#3-Ni(1)-N(1) 87.03(9) O(1)-Ni(1)-N(1) 92.97(9) O(3)#1-Ni(1)-N(1)#3 88.67(9) O(3)#2-Ni(1)-N(1)#3 91.33(9) O(1)#3-Ni(1)-N(1)#3 92.97(9) O(1)-Ni(1)-N(1)#3 87.03(9) N(1)-Ni(1)-N(1)#3 180.000(1) O(2)-Mo(1)-O(1) 109.26(14) O(2)-Mo(1)-O(3) 109.15(12) O(1)-Mo(1)-O(3) 109.88(10) O(2)-Mo(1)-O(4) 111.22(12) O(1)-Mo(1)-O(4) 107.57(8) O(3)-Mo(1)-O(4) 109.74(7) Mo(1)-O(1)-Ni(1) 150.35(13) Mo(1)-O(3)-Ni(1)#4 154.72(13) Mo(1)#5-O(4)-Mo(1) 180.0 N(1)-C(1)-C(2) 123.0(3) C(1)-C(2)-C(3) 119.2(3) C(4)-C(3)-C(2) 117.7(3) C(4)-C(3)-C(6) 120.2(3) C(2)-C(3)-C(6) 122.1(3) C(5)-C(4)-C(3) 118.9(3) N(1)-C(5)-C(4) 124.1(3) N(3)-C(6)-N(2) 125.4(3) N(3)-C(6)-C(3) 116.6(3) N(2)-C(6)-C(3) 118.0(3) N(3)#6-C(7)-N(3) 124.6(4) N(3)#6-C(7)-C(8) 117.7(2) N(3)-C(7)-C(8) 117.7(2) C(9)#6-C(8)-C(9) 117.8(4) C(9)#6-C(8)-C(7) 121.1(2) C(9)-C(8)-C(7) 121.1(2) C(8)-C(9)-C(10) 118.8(3) N(4)-C(10)-C(9) 124.3(3) C(5)-N(1)-C(1) 116.9(3) C(5)-N(1)-Ni(1) 121.1(2) C(1)-N(1)-Ni(1) 121.5(2) C(6)#6-N(2)-C(6) 114.1(4) C(6)-N(3)-C(7) 115.2(3) C(10)#6-N(4)-C(10) 115.9(4) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1/2,-y+1,z+1/2 #2 x+1/2,y,-z+3/2 #3 -x+1,-y+1,-z+2 #4 -x+1/2,-y+1,z-1/2 #5 -x,-y+1,-z+2 #6 x,-y+3/2,z Table 4. Anisotropic displacement parameters (Å2x 103) for pnma. The anisotropic displacement factor exponent takes the form: -2?2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ________________________________________________________________________ U11 U22 U33 U23 U13 U12 ________________________________________________________________________ Ni(1) 13(1) 8(1) 7(1) 1(1) 0(1) 1(1) Mo(1) 13(1) 21(1) 8(1) 2(1) -1(1) -2(1) O(1) 16(1) 15(1) 15(1) 3(1) -4(1) -1(1) O(2) 63(2) 37(2) 30(2) 16(1) -20(2) -37(2) O(3) 19(1) 15(1) 9(1) 0(1) -2(1) 2(1) O(4) 38(2) 94(4) 11(2) -2(2) 7(2) 40(3) C(1) 16(2) 12(2) 10(2) 1(1) -2(1) 1(1) C(2) 15(2) 12(2) 13(2) -1(1) -1(1) -1(1) C(3) 13(2) 9(1) 12(2) 1(1) -1(1) -2(1) C(4) 18(2) 11(2) 10(2) 0(1) -5(1) 1(1) C(5) 17(2) 11(2) 10(2) 0(1) -3(1) -3(1) C(6) 11(1) 11(2) 11(2) 0(1) 0(1) -1(1) C(7) 12(2) 8(2) 12(2) 0 0(2) 0 C(8) 9(2) 12(2) 10(2) 0 -1(2) 0 C(9) 20(2) 12(2) 13(2) 1(1) -2(1) 0(1) C(10) 19(2) 15(2) 15(2) -4(1) -1(1) -4(1) N(1) 11(1) 10(1) 11(1) 2(1) 1(1) 0(1) N(2) 16(2) 8(2) 12(2) 0 -3(2) 0 N(3) 15(1) 9(1) 11(1) 1(1) -1(1) -1(1) N(4) 18(2) 18(2) 14(2) 0 -1(2) 0 ________________________________________________________________________ #END Table 1. Crystal data and structure refinement for [Zn2Mo2O8(tpytrz)]. Identification code pnma Empirical formula C18 H12 Mo2 N6 O8 Zn2 Formula weight 762.96 Temperature 90(2) K Wavelength 0.71073 Å Crystal system Orthorhombic Space group Pnma Unit cell dimensions a = 7.0350(6) Å ?= 90°. b = 30.007(3) Å ?= 90°. c = 10.3080(9) Å ? = 90°. Volume 2176.0(3) Å3 Z 4 Density (calculated) 2.329 Mg/m3 Absorption coefficient 3.366 mm-1 F(000) 1480 Crystal size 0.6 x 0.2 x 0.03 mm3 Theta range for data collection 1.36 to 28.29°. Index ranges -8<=h<=9, -33<=k<=39, -13<=l<=13 Reflections collected 12893 Independent reflections 2690 [R(int) = 0.0573] Completeness to theta = 28.29° 97.4 % Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2690 / 0 / 169 Goodness-of-fit on F2 1.160 Final R indices [I>2sigma(I)] R1 = 0.0548, wR2 = 0.1283 R indices (all data) R1 = 0.0695, wR2 = 0.1339 Largest diff. peak and hole 0.969 and -1.567 e.Å-3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for pnma. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________ x y z U(eq) ______________________________________________________________ Zn(1) 3497(1) 4633(1) 4625(1) 14(1) Mo(1) -1551(1) 4441(1) 3869(1) 15(1) O(1) -3396(5) 4763(1) 4671(4) 17(1) O(2) -2193(7) 3891(2) 3932(5) 34(1) O(3) -1261(6) 4604(2) 2249(4) 39(1) O(4) 610(5) 4502(1) 4701(4) 19(1) C(1) 4162(8) 4097(2) 7070(5) 18(1) C(2) 4323(8) 3713(2) 7812(5) 19(1) C(3) 4260(8) 3303(2) 7192(5) 16(1) C(4) 4050(8) 3294(2) 5843(5) 19(1) C(5) 3891(8) 3692(2) 5179(5) 19(1) C(6) 4419(8) 2879(2) 7906(5) 17(1) C(8) 5068(11) 2500 9758(7) 19(2) C(9) 5631(12) 2500 11140(7) 19(2) C(10) 5851(9) 2897(2) 11806(6) 21(1) C(11) 6222(8) 2881(2) 13133(6) 24(1) N(1) 3946(6) 4088(2) 5771(4) 15(1) N(2) 4889(7) 2897(2) 9167(5) 18(1) N(3) 4136(9) 2500 7230(6) 16(1) N(4) 6385(10) 2500 13802(6) 25(2) ______________________________________________________________ Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for pnma. ______________________________________________________________ x y z U(eq) ______________________________________________________________ H(1) 4205 4372 7487 22 H(2) 4470 3730 8707 22 H(4) 4018 3024 5399 23 H(5) 3739 3684 4283 23 H(10) 5754 3169 11378 25 H(11) 6364 3149 13577 28 Table 3. Bond lengths [Å] and angles [°] for pnma. _____________________________________________________ Zn(1)-O(3)#1 1.941(4) Zn(1)-O(1)#2 1.953(4) Zn(1)-N(1) 2.042(5) Zn(1)-O(4) 2.070(4) Zn(1)-O(1)#3 2.221(4) Zn(1)-Zn(1)#4 3.1498(13) Mo(1)-O(2) 1.711(5) Mo(1)-O(3) 1.753(4) Mo(1)-O(4) 1.755(4) Mo(1)-O(1) 1.818(4) O(1)-Zn(1)#2 1.953(4) O(1)-Zn(1)#5 2.221(4) O(3)-Zn(1)#6 1.941(4) C(1)-N(1) 1.349(7) C(1)-C(2) 1.387(8) C(2)-C(3) 1.389(8) C(3)-C(4) 1.399(7) C(3)-C(6) 1.474(8) C(4)-C(5) 1.381(8) C(5)-N(1) 1.336(7) C(6)-N(2) 1.342(7) C(6)-N(3) 1.347(6) C(8)-N(2)#7 1.344(6) C(8)-N(2) 1.344(6) C(8)-C(9) 1.479(10) C(9)-C(10) 1.384(7) C(9)-C(10)#7 1.384(7) C(10)-C(11) 1.393(8) C(11)-N(4) 1.340(7) N(3)-C(6)#7 1.347(6) N(4)-C(11)#7 1.340(7) O(3)#1-Zn(1)-O(1)#2 114.5(2) O(3)#1-Zn(1)-N(1) 121.8(2) O(1)#2-Zn(1)-N(1) 122.25(17) O(3)#1-Zn(1)-O(4) 96.62(17) O(1)#2-Zn(1)-O(4) 97.28(16) N(1)-Zn(1)-O(4) 88.74(17) O(3)#1-Zn(1)-O(1)#3 86.70(17) O(1)#2-Zn(1)-O(1)#3 82.21(16) N(1)-Zn(1)-O(1)#3 88.65(16) O(4)-Zn(1)-O(1)#3 176.53(14) O(3)#1-Zn(1)-Zn(1)#4 102.49(16) O(1)#2-Zn(1)-Zn(1)#4 44.32(11) N(1)-Zn(1)-Zn(1)#4 108.31(13) O(4)-Zn(1)-Zn(1)#4 141.48(12) O(1)#3-Zn(1)-Zn(1)#4 37.89(10) O(2)-Mo(1)-O(3) 109.7(3) O(2)-Mo(1)-O(4) 108.1(2) O(3)-Mo(1)-O(4) 109.6(2) O(2)-Mo(1)-O(1) 107.90(19) O(3)-Mo(1)-O(1) 111.5(2) O(4)-Mo(1)-O(1) 109.90(17) Mo(1)-O(1)-Zn(1)#2 133.5(2) Mo(1)-O(1)-Zn(1)#5 126.8(2) Zn(1)#2-O(1)-Zn(1)#5 97.79(15) Mo(1)-O(3)-Zn(1)#6 161.9(3) Mo(1)-O(4)-Zn(1) 148.4(2) N(1)-C(1)-C(2) 122.7(5) C(1)-C(2)-C(3) 118.7(5) C(2)-C(3)-C(4) 118.5(5) C(2)-C(3)-C(6) 122.3(4) C(4)-C(3)-C(6) 119.2(5) C(5)-C(4)-C(3) 119.0(5) N(1)-C(5)-C(4) 122.8(5) N(2)-C(6)-N(3) 124.9(5) N(2)-C(6)-C(3) 117.8(5) N(3)-C(6)-C(3) 117.3(4) N(2)#7-C(8)-N(2) 124.9(7) N(2)#7-C(8)-C(9) 117.5(3) N(2)-C(8)-C(9) 117.5(3) C(10)-C(9)-C(10)#7 118.8(7) C(10)-C(9)-C(8) 120.6(4) C(10)#7-C(9)-C(8) 120.6(4) C(9)-C(10)-C(11) 118.6(6) N(4)-C(11)-C(10) 123.4(6) C(5)-N(1)-C(1) 118.3(5) C(5)-N(1)-Zn(1) 116.4(4) C(1)-N(1)-Zn(1) 125.2(4) C(6)-N(2)-C(8) 115.1(5) C(6)-N(3)-C(6)#7 114.9(6) C(11)#7-N(4)-C(11) 117.1(7) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x+1/2,y,-z+1/2 #2 -x,-y+1,-z+1 #3 x+1,y,z #4 -x+1,-y+1,-z+1 #5 x-1,y,z #6 x-1/2,y,-z+1/2 #7 x,-y+1/2,z Table 4. Anisotropic displacement parameters (Å2x 103) for pnma. The anisotropic displacement factor exponent takes the form: -2?2[ h2 a*2U11 + ... 2 h k a* b* U12 ] ______________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________ Zn(1) 16(1) 15(1) 12(1) -1(1) -1(1) -1(1) Mo(1) 14(1) 17(1) 13(1) -1(1) 1(1) -1(1) O(1) 15(2) 16(2) 20(2) -4(2) -1(2) 0(2) O(2) 22(2) 19(2) 62(3) -16(2) 10(2) -1(2) O(3) 18(2) 88(4) 12(2) 5(2) 2(2) 1(2) O(4) 15(2) 22(2) 20(2) 2(2) 0(2) 0(2) C(1) 18(3) 20(3) 16(3) -4(2) -4(2) 2(2) C(2) 18(3) 21(3) 16(3) -1(2) -3(2) 2(2) C(3) 14(3) 20(3) 14(3) 0(2) 0(2) -1(2) C(4) 25(3) 17(3) 16(3) -1(2) 2(2) -3(2) C(5) 26(3) 17(3) 14(3) 0(2) 0(2) -4(2) C(6) 17(3) 18(3) 14(2) -2(2) 2(2) -1(2) C(8) 23(4) 17(4) 17(4) 0 -2(3) 0 C(9) 20(4) 19(4) 17(4) 0 2(3) 0 C(10) 28(3) 15(3) 21(3) 0(2) 2(2) -4(2) C(11) 25(3) 25(3) 21(3) -4(2) 2(2) -1(2) N(1) 14(2) 15(2) 15(2) 1(2) 1(2) 1(2) N(2) 22(2) 13(2) 20(2) 3(2) 2(2) -2(2) N(3) 17(3) 18(3) 14(3) 0 1(2) 0 N(4) 28(4) 29(4) 19(3) 0 2(3) 0 ______________________________________________________________