# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/ data_cobpye # Paper complex no 1 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Cobalt 4,4'-azopyridine Nitrate Complex, Dichloromethane solvate ; _chemical_name_common '{[Co2(4-apy)3(NO3)4]CH2Cl2}' _chemical_formula_moiety ? _chemical_formula_sum 'C15.50 H13 Cl Co N8 O6' _chemical_formula_weight 501.72 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Co' 'Co' 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'Monoclinic' _symmetry_space_group_name_H-M 'C2/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 20.802(9) _cell_length_b 11.124(4) _cell_length_c 20.806(9) _cell_angle_alpha 90.00 _cell_angle_beta 119.27(4) _cell_angle_gamma 90.00 _cell_volume 4200(3) _cell_formula_units_Z 8 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 27 _cell_measurement_theta_min 12.5 _cell_measurement_theta_max 14 _exptl_crystal_description Plate _exptl_crystal_colour Red _exptl_crystal_size_max 0.47 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.587 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2032 _exptl_absorpt_coefficient_mu 0.995 _exptl_absorpt_correction_type 'Psi scans' _exptl_absorpt_correction_T_min 0.6519 _exptl_absorpt_correction_T_max 0.8411 _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE STADI-4 FOUR-CIRCLE' _diffrn_measurement_method 'omega-theta' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% '+/- 4.4' _diffrn_reflns_number 5502 _diffrn_reflns_av_R_equivalents 0.0328 _diffrn_reflns_av_sigmaI/netI 0.0494 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.67 _diffrn_reflns_theta_max 24.99 _reflns_number_total 3609 _reflns_number_gt 2681 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STADI-4 (stoe & cie, 1996a)' _computing_cell_refinement 'STADI-4 (stoe & cie, 1996a)' _computing_data_reduction 'X-RED (stoe & cie, 1996b)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL/PC (version 5.03)(Sheldrick,1994)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0598P)^2^+60.4364P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary 'Direct Methods' _atom_sites_solution_secondary 'Difference Fourier Map' _atom_sites_solution_hydrogens 'Geometrically Placed ' _refine_ls_hydrogen_treatment 'Riding Model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3609 _refine_ls_number_parameters 293 _refine_ls_number_restraints 99 _refine_ls_R_factor_all 0.1076 _refine_ls_R_factor_gt 0.0740 _refine_ls_wR_factor_ref 0.1942 _refine_ls_wR_factor_gt 0.1639 _refine_ls_goodness_of_fit_ref 1.121 _refine_ls_restrained_S_all 1.134 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Co Co 0.71781(4) 0.88374(7) 0.84279(5) 0.0225(3) Uani 1 d U . . N1 N 0.6244(3) 0.9897(5) 0.7667(3) 0.0276(11) Uani 1 d U . . C2 C 0.6236(4) 1.1093(7) 0.7675(4) 0.0363(15) Uani 1 d U . . H2 H 0.6648 1.1505 0.8052 0.044 Uiso 1 calc R . . C3 C 0.5644(4) 1.1766(7) 0.7149(4) 0.0458(18) Uani 1 d U . . H3 H 0.5656 1.2620 0.7167 0.055 Uiso 1 calc R . . C4 C 0.5037(4) 1.1167(8) 0.6598(4) 0.0421(16) Uani 1 d U . . C5 C 0.5035(4) 0.9947(8) 0.6592(4) 0.0399(16) Uani 1 d U . . H5 H 0.4626 0.9511 0.6229 0.048 Uiso 1 calc R . . C6 C 0.5643(3) 0.9360(7) 0.7128(4) 0.0326(15) Uani 1 d U . . H6 H 0.5638 0.8507 0.7115 0.039 Uiso 1 calc R . . N7 N 0.4403(4) 1.1735(7) 0.5950(4) 0.0483(16) Uani 1 d U . . N10 N 0.6254(3) 0.7659(6) 0.8732(3) 0.0350(13) Uani 1 d U . . O11 O 0.6422(3) 0.7356(4) 0.8237(3) 0.0408(11) Uani 1 d U . . O12 O 0.6606(3) 0.8535(5) 0.9131(3) 0.0408(11) Uani 1 d U . . O13 O 0.5770(3) 0.7145(6) 0.8794(4) 0.0641(18) Uani 1 d U . . N20 N 0.7560(3) 0.8691(5) 0.7359(3) 0.0332(12) Uani 1 d U . . O21 O 0.7777(3) 0.9498(4) 0.7878(3) 0.0348(10) Uani 1 d U . . O22 O 0.7092(3) 0.7961(4) 0.7342(3) 0.0372(10) Uani 1 d U . . O23 O 0.7803(3) 0.8668(5) 0.6920(3) 0.0539(15) Uani 1 d U . . N31 N 0.7756(3) 1.0200(5) 0.9272(3) 0.0289(11) Uani 1 d U . . C32 C 0.8076(3) 1.1145(6) 0.9139(4) 0.0324(14) Uani 1 d U . . H32 H 0.7982 1.1290 0.8651 0.039 Uiso 1 calc R . . C33 C 0.8549(4) 1.1927(7) 0.9710(5) 0.0410(16) Uani 1 d U . . H33 H 0.8763 1.2602 0.9605 0.049 Uiso 1 calc R . . C34 C 0.8702(4) 1.1695(8) 1.0438(5) 0.0495(18) Uani 1 d U . . C35 C 0.8382(5) 1.0736(10) 1.0584(5) 0.061(3) Uani 1 d U . . H35 H 0.8483 1.0562 1.1071 0.073 Uiso 1 calc R . . C36 C 0.7902(4) 1.0023(8) 0.9989(4) 0.0453(19) Uani 1 d U . . H36 H 0.7660 0.9377 1.0082 0.054 Uiso 1 calc R . . N37 N 0.9286(4) 1.2307(7) 1.1120(4) 0.059(2) Uani 1 d U . . N61 N 0.8066(3) 0.7572(5) 0.8997(3) 0.0327(12) Uani 1 d U . . C62 C 0.7954(5) 0.6386(7) 0.8865(5) 0.0457(18) Uani 1 d U . . H62 H 0.7463 0.6114 0.8561 0.055 Uiso 1 calc R . . C63 C 0.8506(6) 0.5546(8) 0.9143(5) 0.059(2) Uani 1 d U . . H63 H 0.8393 0.4720 0.9028 0.071 Uiso 1 calc R . . C64 C 0.9215(5) 0.5897(10) 0.9585(5) 0.060(2) Uani 1 d U . . C65 C 0.9354(4) 0.7111(10) 0.9731(5) 0.057(2) Uani 1 d U . . H65 H 0.9844 0.7389 1.0032 0.069 Uiso 1 calc R . . C66 C 0.8762(4) 0.7929(8) 0.9428(4) 0.0466(18) Uani 1 d U . . H66 H 0.8860 0.8761 0.9534 0.056 Uiso 1 calc R . . N67 N 0.9755(4) 0.4723(7) 0.9812(4) 0.0538(16) Uani 1 d U . . C1 C 0.9309(9) 1.0671(16) 0.8117(8) 0.052(4) Uiso 0.50 d PDU . . H1A H 0.9436 1.1529 0.8115 0.062 Uiso 0.50 calc PR . . H1B H 0.8767 1.0608 0.7885 0.062 Uiso 0.50 calc PR . . Cl1 Cl 0.9618(6) 0.9827(10) 0.7592(7) 0.189(4) Uani 0.50 d PDU . . Cl2 Cl 0.9705(4) 1.0165(7) 0.9011(6) 0.140(3) Uani 0.50 d PDU . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Co 0.0164(4) 0.0187(4) 0.0238(5) 0.0002(4) 0.0033(3) 0.0022(4) N1 0.022(2) 0.031(2) 0.024(2) 0.002(2) 0.0068(18) 0.004(2) C2 0.026(3) 0.031(3) 0.043(4) 0.005(3) 0.010(3) 0.007(3) C3 0.046(4) 0.036(4) 0.050(4) 0.018(3) 0.019(3) 0.013(3) C4 0.027(3) 0.064(4) 0.036(4) 0.020(3) 0.015(2) 0.014(3) C5 0.025(3) 0.060(4) 0.026(3) 0.014(3) 0.006(3) 0.001(3) C6 0.021(3) 0.044(4) 0.025(3) 0.006(3) 0.006(2) 0.002(2) N7 0.044(3) 0.045(4) 0.054(4) 0.007(3) 0.022(3) 0.008(3) N10 0.028(3) 0.039(3) 0.030(3) 0.007(2) 0.007(2) -0.005(2) O11 0.040(2) 0.030(2) 0.053(3) 0.001(2) 0.023(2) -0.002(2) O12 0.033(2) 0.047(3) 0.036(3) -0.002(2) 0.013(2) -0.013(2) O13 0.058(4) 0.065(4) 0.081(5) -0.006(3) 0.043(3) -0.031(3) N20 0.036(3) 0.029(3) 0.036(3) 0.001(2) 0.019(3) 0.006(2) O21 0.036(2) 0.032(3) 0.037(3) -0.0020(18) 0.019(2) 0.0000(19) O22 0.039(3) 0.032(3) 0.038(2) -0.004(2) 0.017(2) -0.0012(19) O23 0.070(4) 0.054(4) 0.061(4) -0.004(3) 0.050(3) 0.004(3) N31 0.019(2) 0.030(3) 0.030(2) -0.004(2) 0.006(2) -0.0011(19) C32 0.025(3) 0.022(3) 0.039(3) -0.002(3) 0.007(3) 0.003(2) C33 0.027(3) 0.029(4) 0.060(3) -0.012(3) 0.015(3) -0.008(3) C34 0.032(4) 0.058(5) 0.051(3) -0.023(4) 0.015(3) -0.008(3) C35 0.049(5) 0.096(7) 0.036(4) -0.028(4) 0.019(4) -0.034(5) C36 0.037(4) 0.064(5) 0.029(3) -0.013(3) 0.011(3) -0.017(4) N37 0.065(5) 0.057(5) 0.055(4) -0.016(4) 0.029(4) -0.018(4) N61 0.030(2) 0.031(2) 0.033(3) 0.006(2) 0.012(2) 0.012(2) C62 0.057(4) 0.028(3) 0.049(5) 0.003(3) 0.023(4) 0.016(3) C63 0.087(4) 0.041(4) 0.057(5) 0.020(4) 0.042(4) 0.035(3) C64 0.070(4) 0.084(4) 0.043(5) 0.038(4) 0.041(4) 0.045(4) C65 0.027(3) 0.094(4) 0.047(5) 0.022(5) 0.015(3) 0.027(3) C66 0.023(3) 0.061(4) 0.045(5) 0.004(4) 0.009(3) 0.010(3) N67 0.060(4) 0.058(4) 0.048(4) -0.010(3) 0.030(4) -0.021(3) Cl1 0.165(10) 0.149(9) 0.215(9) 0.080(8) 0.063(9) -0.011(7) Cl2 0.073(4) 0.080(5) 0.286(10) -0.016(6) 0.104(6) -0.015(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Co N61 2.159(5) . y Co N1 2.159(5) . y Co O11 2.176(5) . y Co N31 2.182(6) . y Co O21 2.191(5) . y Co O12 2.318(5) . y Co O22 2.387(5) . y N1 C2 1.330(9) . ? N1 C6 1.345(8) . ? C2 C3 1.400(10) . ? C3 C4 1.392(11) . ? C4 C5 1.358(12) . ? C4 N7 1.489(9) . ? C5 C6 1.373(9) . ? N7 N37 1.184(10) 8_475 ? N10 O13 1.219(8) . ? N10 O12 1.256(8) . ? N10 O11 1.285(8) . ? N20 O23 1.242(7) . ? N20 O22 1.254(7) . ? N20 O21 1.303(7) . ? N31 C32 1.344(9) . ? N31 C36 1.383(9) . ? C32 C33 1.412(10) . ? C33 C34 1.412(12) . ? C34 C35 1.366(13) . ? C34 N37 1.506(10) . ? C35 C36 1.397(11) . ? N37 N7 1.184(10) 8_576 ? N61 C66 1.337(9) . ? N61 C62 1.344(9) . ? C62 C63 1.369(11) . ? C63 C64 1.360(14) . ? C64 C65 1.383(15) . ? C64 N67 1.634(12) . ? C65 C66 1.409(11) . ? N67 N67 1.118(13) 5_767 ? C1 Cl2 1.720(14) . ? C1 Cl1 1.781(15) . ? Cl1 Cl1 1.81(2) 2_756 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N61 Co N1 168.6(2) . . y N61 Co O11 87.4(2) . . ? N1 Co O11 88.2(2) . . ? N61 Co N31 91.4(2) . . y N1 Co N31 98.9(2) . . y O11 Co N31 137.5(2) . . ? N61 Co O21 87.3(2) . . ? N1 Co O21 88.4(2) . . ? O11 Co O21 134.7(2) . . ? N31 Co O21 87.5(2) . . ? N61 Co O12 97.2(2) . . ? N1 Co O12 89.2(2) . . ? O11 Co O12 57.12(19) . . ? N31 Co O12 81.00(19) . . ? O21 Co O12 167.78(18) . . ? N61 Co O22 84.3(2) . . ? N1 Co O22 84.55(19) . . ? O11 Co O22 78.74(19) . . ? N31 Co O22 143.4(2) . . ? O21 Co O22 55.99(18) . . ? O12 Co O22 135.61(18) . . ? C2 N1 C6 116.2(6) . . ? C2 N1 Co 123.3(5) . . ? C6 N1 Co 120.4(5) . . ? N1 C2 C3 122.5(7) . . ? C4 C3 C2 119.0(8) . . ? C5 C4 C3 118.9(7) . . ? C5 C4 N7 114.8(7) . . ? C3 C4 N7 126.0(8) . . ? C4 C5 C6 118.1(7) . . ? N1 C6 C5 125.3(7) . . ? N37 N7 C4 109.4(7) 8_475 . ? O13 N10 O12 122.6(7) . . ? O13 N10 O11 121.6(6) . . ? O12 N10 O11 115.8(6) . . ? N10 O11 Co 96.3(4) . . ? N10 O12 Co 90.5(4) . . ? O23 N20 O22 123.7(6) . . ? O23 N20 O21 121.4(6) . . ? O22 N20 O21 114.9(5) . . ? N20 O21 Co 98.4(4) . . ? N20 O22 Co 90.6(4) . . ? C32 N31 C36 117.6(6) . . ? C32 N31 Co 120.7(5) . . ? C36 N31 Co 120.9(5) . . ? N31 C32 C33 121.4(7) . . ? C34 C33 C32 119.3(7) . . ? C35 C34 C33 120.2(7) . . ? C35 C34 N37 113.6(8) . . ? C33 C34 N37 125.6(8) . . ? C34 C35 C36 117.5(8) . . ? N31 C36 C35 124.0(8) . . ? N7 N37 C34 108.4(8) 8_576 . ? C66 N61 C62 116.9(7) . . ? C66 N61 Co 122.0(5) . . ? C62 N61 Co 120.7(5) . . ? N61 C62 C63 123.8(9) . . ? C64 C63 C62 119.9(9) . . ? C63 C64 C65 118.0(8) . . ? C63 C64 N67 109.4(9) . . ? C65 C64 N67 132.6(9) . . ? C64 C65 C66 119.3(9) . . ? N61 C66 C65 122.0(9) . . ? N67 N67 C64 91.4(10) 5_767 . ? Cl2 C1 Cl1 111.4(10) . . ? C1 Cl1 Cl1 138.4(9) . 2_756 ? _diffrn_measured_fraction_theta_max 0.462 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.462 _refine_diff_density_max 1.174 _refine_diff_density_min -1.024 _refine_diff_density_rms 0.121 #===end data_cdaznt # Paper complex no. 2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Cadmium 4,4'-azopyridine Nitrate Complex, water/dichloromethane solvate ; _chemical_name_common '[Cd2(4-apy)3(NO3)4](CH2Cl2)(H2O)2' _chemical_formula_moiety ? _chemical_formula_sum 'C15.50 H15 Cd Cl N8 O7' _chemical_formula_weight 573.21 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cd' 'Cd' -0.8075 1.2024 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'Monoclinic' _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 21.197(5) _cell_length_b 11.166(12) _cell_length_c 21.389(4) _cell_angle_alpha 90.00 _cell_angle_beta 122.24(2) _cell_angle_gamma 90.00 _cell_volume 4282(5) _cell_formula_units_Z 8 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 35 _cell_measurement_theta_min 12.5 _cell_measurement_theta_max 17.5 _exptl_crystal_description 'Irregular Tablet' _exptl_crystal_colour 'Red' _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.27 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.778 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2280 _exptl_absorpt_coefficient_mu 1.201 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_min 0.683 _exptl_absorpt_correction_T_max 0.765 _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE STADI-4 FOUR-CIRCLE' _diffrn_measurement_method 'omega-theta' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% ? _diffrn_reflns_number 3801 _diffrn_reflns_av_R_equivalents 0.0182 _diffrn_reflns_av_sigmaI/netI 0.0196 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.64 _diffrn_reflns_theta_max 26.08 _reflns_number_total 3771 _reflns_number_gt 3210 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STADI-4 (stoe & cie, 1996a)' _computing_cell_refinement 'STADI-4 (stoe & cie, 1996a)' _computing_data_reduction 'X-RED (stoe & cie, 1996b)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL/PC (version 5.03)(Sheldrick,1994)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0342P)^2^+53.6746P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary 'Direct Methods' _atom_sites_solution_secondary 'Difference Fourier Maps' _atom_sites_solution_hydrogens 'Geometrically Placed' _refine_ls_hydrogen_treatment 'Riding Model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3771 _refine_ls_number_parameters 306 _refine_ls_number_restraints 101 _refine_ls_R_factor_all 0.0577 _refine_ls_R_factor_gt 0.0450 _refine_ls_wR_factor_ref 0.1184 _refine_ls_wR_factor_gt 0.1024 _refine_ls_goodness_of_fit_ref 1.164 _refine_ls_restrained_S_all 1.160 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cd Cd 0.21593(2) 0.88306(3) 0.84283(2) 0.02657(14) Uani 1 1 d U . . N61 N 0.3064(2) 0.7427(4) 0.8976(3) 0.0308(10) Uani 1 1 d U . . C1 C 0.0577(7) 0.5509(12) 0.6847(7) 0.059(3) Uani 0.50 1 d PDU A -1 H1A H 0.0445 0.6367 0.6812 0.070 Uiso 0.50 1 calc PR A -1 H1B H 0.1128 0.5453 0.7142 0.070 Uiso 0.50 1 calc PR A -1 Cl1 Cl 0.0261(2) 0.4989(4) 0.5975(2) 0.0611(10) Uani 0.50 1 d PDU A -1 O1W O 0.0777(7) 0.6741(12) 0.6453(7) 0.075(3) Uiso 0.50 1 d P B -2 C62 C 0.2938(3) 0.6266(5) 0.8796(3) 0.0395(15) Uani 1 1 d U . . H62 H 0.2439 0.6026 0.8453 0.047 Uiso 1 1 calc R . . N67 N 0.4697(3) 0.4811(5) 0.9783(3) 0.0360(11) Uani 1 1 d U . . Cl2 Cl 0.0217(3) 0.4724(5) 0.7352(3) 0.0899(15) Uani 0.50 1 d PDU A -1 O2W O 0.0045(13) 0.496(2) 0.5322(11) 0.141(7) Uiso 0.50 1 d P C -2 C63 C 0.3473(3) 0.5406(6) 0.9066(3) 0.0408(15) Uani 1 1 d U . . H63 H 0.3357 0.4590 0.8927 0.049 Uiso 1 1 calc R . . C64 C 0.4164(3) 0.5763(5) 0.9533(3) 0.0332(13) Uani 1 1 d U . . C65 C 0.4300(3) 0.6951(6) 0.9722(4) 0.0401(15) Uani 1 1 d U . . H65 H 0.4797 0.7213 1.0058 0.048 Uiso 1 1 calc R . . C66 C 0.3737(3) 0.7751(6) 0.9437(4) 0.0393(15) Uani 1 1 d U . . H66 H 0.3842 0.8568 0.9580 0.047 Uiso 1 1 calc R . . N10 N 0.1236(3) 0.7489(5) 0.8771(3) 0.0466(13) Uani 1 1 d U . . O13 O 0.0778(4) 0.6968(7) 0.8865(4) 0.098(3) Uani 1 1 d U . . O12 O 0.1585(2) 0.8360(4) 0.9180(3) 0.0479(11) Uani 1 1 d U . . O11 O 0.1350(2) 0.7219(4) 0.8246(2) 0.0396(10) Uani 1 1 d U . . N20 N 0.2647(3) 0.8717(5) 0.7357(3) 0.0404(12) Uani 1 1 d U . . O22 O 0.2169(3) 0.7997(4) 0.7307(2) 0.0464(11) Uani 1 1 d U . . O23 O 0.2922(3) 0.8641(5) 0.6941(3) 0.0564(13) Uani 1 1 d U . . O21 O 0.2842(2) 0.9534(4) 0.7845(2) 0.0422(10) Uani 1 1 d U . . N1 N 0.1172(2) 0.9915(5) 0.7604(3) 0.0328(11) Uani 1 1 d U . . C2 C 0.0585(3) 0.9342(7) 0.7104(3) 0.0442(16) Uani 1 1 d U . . H2 H 0.0579 0.8492 0.7117 0.053 Uiso 1 1 calc R . . C3 C -0.0011(3) 0.9929(8) 0.6571(4) 0.0518(18) Uani 1 1 d U . . H3 H -0.0437 0.9498 0.6207 0.062 Uiso 1 1 calc R . . C4 C -0.0004(3) 1.1125(8) 0.6553(3) 0.0509(17) Uani 1 1 d U . . C5 C 0.0584(4) 1.1742(7) 0.7061(4) 0.0568(19) Uani 1 1 d U . . H5 H 0.0589 1.2593 0.7059 0.068 Uiso 1 1 calc R . . C6 C 0.1173(3) 1.1105(6) 0.7583(3) 0.0417(15) Uani 1 1 d U . . H6 H 0.1604 1.1523 0.7948 0.050 Uiso 1 1 calc R . . N31 N 0.2733(2) 1.0322(4) 0.9301(3) 0.0342(11) Uani 1 1 d U . . C32 C 0.2834(4) 1.0197(8) 0.9989(4) 0.060(2) Uani 1 1 d U . . H32 H 0.2567 0.9581 1.0056 0.072 Uiso 1 1 calc R . . N37 N 0.4192(4) 1.2444(7) 1.1080(4) 0.068(2) Uani 1 1 d U . . C33 C 0.3295(5) 1.0904(9) 1.0577(5) 0.075(3) Uani 1 1 d U . . H33 H 0.3371 1.0786 1.1052 0.090 Uiso 1 1 calc R . . C34 C 0.3649(4) 1.1822(7) 1.0429(4) 0.0513(18) Uani 1 1 d U . . C35 C 0.3549(3) 1.1978(6) 0.9731(4) 0.0447(15) Uani 1 1 d U . . H35 H 0.3798 1.2604 0.9646 0.054 Uiso 1 1 calc R . . C36 C 0.3085(3) 1.1207(6) 0.9174(4) 0.0432(15) Uani 1 1 d U . . H36 H 0.3010 1.1296 0.8697 0.052 Uiso 1 1 calc R . . N7 N -0.0620(4) 1.1674(7) 0.5938(4) 0.068(2) Uani 1 1 d U . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cd 0.01569(19) 0.0251(2) 0.0249(2) 0.00058(16) 0.00144(15) 0.00158(15) N61 0.018(2) 0.030(2) 0.031(2) 0.0035(19) 0.0038(18) 0.0039(18) C1 0.031(7) 0.032(7) 0.082(8) -0.009(6) 0.010(6) 0.003(5) Cl1 0.0411(18) 0.069(3) 0.071(2) -0.012(2) 0.0287(18) 0.0049(17) C62 0.022(3) 0.030(3) 0.044(3) -0.003(3) 0.003(2) 0.001(2) N67 0.027(2) 0.036(3) 0.034(3) 0.005(2) 0.009(2) 0.007(2) Cl2 0.111(4) 0.071(3) 0.087(4) -0.012(3) 0.052(3) -0.006(3) C63 0.031(3) 0.028(3) 0.042(3) 0.001(3) 0.005(3) 0.005(2) C64 0.026(3) 0.033(3) 0.033(3) 0.009(2) 0.010(2) 0.011(2) C65 0.021(3) 0.037(3) 0.043(3) 0.001(3) 0.005(2) 0.004(2) C66 0.022(3) 0.032(3) 0.048(4) 0.000(3) 0.007(3) 0.002(2) N10 0.036(3) 0.049(3) 0.051(3) -0.004(3) 0.021(3) -0.012(2) O13 0.106(5) 0.115(6) 0.109(5) -0.048(5) 0.081(5) -0.076(5) O12 0.035(2) 0.056(3) 0.047(3) -0.011(2) 0.018(2) -0.014(2) O11 0.028(2) 0.038(2) 0.043(2) 0.0000(19) 0.0128(18) -0.0039(17) N20 0.039(3) 0.042(3) 0.036(3) 0.011(2) 0.017(2) 0.020(2) O22 0.044(2) 0.043(3) 0.038(2) -0.004(2) 0.013(2) -0.001(2) O23 0.063(3) 0.055(3) 0.061(3) 0.012(3) 0.040(3) 0.017(3) O21 0.038(2) 0.040(2) 0.045(3) 0.0003(19) 0.021(2) 0.0003(19) N1 0.018(2) 0.039(3) 0.028(2) 0.005(2) 0.0031(18) 0.0023(19) C2 0.026(3) 0.054(4) 0.033(3) 0.013(3) 0.003(2) -0.004(3) C3 0.023(3) 0.080(5) 0.034(3) 0.023(3) 0.003(3) 0.001(3) C4 0.027(3) 0.085(5) 0.029(3) 0.015(3) 0.007(2) 0.023(3) C5 0.056(4) 0.048(4) 0.046(4) 0.017(3) 0.014(3) 0.023(3) C6 0.030(3) 0.038(3) 0.036(3) 0.004(3) 0.004(3) 0.006(3) N31 0.021(2) 0.033(3) 0.033(2) -0.005(2) 0.0038(19) -0.0024(19) C32 0.050(4) 0.083(6) 0.049(4) -0.026(4) 0.028(4) -0.037(4) N37 0.064(4) 0.084(5) 0.059(4) -0.038(4) 0.034(4) -0.044(4) C33 0.072(5) 0.111(7) 0.051(4) -0.043(5) 0.038(4) -0.058(5) C34 0.033(3) 0.065(5) 0.046(4) -0.028(3) 0.015(3) -0.017(3) C35 0.032(3) 0.033(3) 0.048(3) -0.003(3) 0.007(3) -0.006(3) C36 0.037(3) 0.033(3) 0.033(3) -0.001(3) 0.001(3) -0.004(3) N7 0.058(4) 0.087(5) 0.045(4) 0.016(3) 0.018(3) 0.032(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cd N1 2.240(5) . y Cd N61 2.260(5) . y Cd N31 2.305(5) . y Cd O11 2.370(4) . y Cd O21 2.489(5) . y Cd O12 2.535(5) . y Cd O22 2.583(5) . y N61 C66 1.280(7) . ? N61 C62 1.339(8) . ? C1 Cl1 1.713(12) . ? C1 Cl2 1.842(13) . ? C62 C63 1.358(8) . ? N67 N67 1.192(10) 5_667 ? N67 C64 1.431(7) . ? C63 C64 1.319(8) . ? C64 C65 1.372(9) . ? C65 C66 1.349(8) . ? N10 O13 1.237(8) . ? N10 O12 1.252(7) . ? N10 O11 1.303(7) . ? N20 O22 1.252(7) . ? N20 O21 1.277(7) . ? N20 O23 1.300(7) . ? N1 C2 1.296(8) . ? N1 C6 1.329(8) . ? C2 C3 1.338(9) . ? C3 C4 1.337(11) . ? C4 C5 1.328(11) . ? C4 N7 1.406(8) . ? C5 C6 1.351(9) . ? N31 C36 1.349(8) . ? N31 C32 1.376(9) . ? C32 C33 1.360(10) . ? N37 N7 1.163(10) 8_576 ? N37 C34 1.427(8) . ? C33 C34 1.402(11) . ? C34 C35 1.403(10) . ? C35 C36 1.371(9) . ? N7 N37 1.163(9) 8_475 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Cd N61 163.93(18) . . y N1 Cd N31 96.57(18) . . y N61 Cd N31 98.38(18) . . y N1 Cd O11 89.47(17) . . ? N61 Cd O11 84.15(17) . . ? N31 Cd O11 134.79(18) . . ? N1 Cd O21 89.07(16) . . ? N61 Cd O21 85.38(17) . . ? N31 Cd O21 88.92(17) . . ? O11 Cd O21 136.08(15) . . ? N1 Cd O12 92.76(17) . . ? N61 Cd O12 95.08(17) . . ? N31 Cd O12 82.01(17) . . ? O11 Cd O12 52.90(15) . . ? O21 Cd O12 170.90(15) . . ? N1 Cd O22 86.05(17) . . ? N61 Cd O22 78.86(16) . . ? N31 Cd O22 138.57(17) . . ? O11 Cd O22 86.42(16) . . ? O21 Cd O22 49.70(15) . . ? O12 Cd O22 139.32(16) . . ? C66 N61 C62 117.7(5) . . ? C66 N61 Cd 119.5(4) . . ? C62 N61 Cd 122.6(4) . . ? Cl1 C1 Cl2 115.7(7) . . ? N61 C62 C63 124.7(5) . . ? N67 N67 C64 109.6(7) 5_667 . ? C64 C63 C62 116.5(6) . . ? C63 C64 C65 119.3(5) . . ? C63 C64 N67 113.2(5) . . ? C65 C64 N67 127.5(5) . . ? C66 C65 C64 120.7(6) . . ? N61 C66 C65 121.0(6) . . ? O13 N10 O12 118.4(6) . . ? O13 N10 O11 123.6(6) . . ? O12 N10 O11 117.9(5) . . ? N10 O12 Cd 91.3(4) . . ? N10 O11 Cd 97.7(3) . . ? O22 N20 O21 115.0(5) . . ? O22 N20 O23 122.4(6) . . ? O21 N20 O23 122.5(6) . . ? N20 O22 Cd 95.5(3) . . ? N20 O21 Cd 99.4(4) . . ? C2 N1 C6 118.9(5) . . ? C2 N1 Cd 117.7(4) . . ? C6 N1 Cd 123.3(4) . . ? N1 C2 C3 121.0(7) . . ? C4 C3 C2 119.6(7) . . ? C5 C4 C3 121.0(6) . . ? C5 C4 N7 122.5(8) . . ? C3 C4 N7 116.3(7) . . ? C4 C5 C6 116.9(7) . . ? N1 C6 C5 122.5(6) . . ? C36 N31 C32 120.1(5) . . ? C36 N31 Cd 118.4(4) . . ? C32 N31 Cd 120.4(4) . . ? C33 C32 N31 123.7(7) . . ? N7 N37 C34 111.6(7) 8_576 . ? C32 C33 C34 115.0(7) . . ? C33 C34 C35 122.4(6) . . ? C33 C34 N37 112.7(7) . . ? C35 C34 N37 124.3(7) . . ? C36 C35 C34 118.6(6) . . ? N31 C36 C35 120.2(6) . . ? N37 N7 C4 113.7(7) 8_475 . ? _diffrn_measured_fraction_theta_max 0.887 _diffrn_reflns_theta_full 26.08 _diffrn_measured_fraction_theta_full 0.887 _refine_diff_density_max 1.091 _refine_diff_density_min -0.815 _refine_diff_density_rms 0.117 #===end data_cuapyb # Paper complex no 3 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Copper(I) trans-4,4-azobis(pyridine) tetrafluoroborate complex ; _chemical_name_common '{[Cu(4-apy)2]BF4}n' _chemical_formula_moiety ? _chemical_formula_sum 'C20 H16 B Cu F4 N8' _chemical_formula_weight 518.76 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'B' 'B' 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cu' 'Cu' 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/a loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 17.327(3) _cell_length_b 17.327(3) _cell_length_c 7.7288(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2320.4(7) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 39 _cell_measurement_theta_min 9.5 _cell_measurement_theta_max 15 _exptl_crystal_description Sphenoid _exptl_crystal_colour Black _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.485 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1048 _exptl_absorpt_coefficient_mu 0.998 _exptl_absorpt_correction_type 'Psi-Scans' _exptl_absorpt_correction_T_min 0.757 _exptl_absorpt_correction_T_max 0.873 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE STADI-4 FOUR-CIRCLE' _diffrn_measurement_method 'omega theta' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% '+/- 4.3' _diffrn_reflns_number 3219 _diffrn_reflns_av_R_equivalents 0.0586 _diffrn_reflns_av_sigmaI/netI 0.0442 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 2.89 _diffrn_reflns_theta_max 24.98 _reflns_number_total 1019 _reflns_number_gt 856 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STADI-4 (stoe & cie, 1996a)' _computing_cell_refinement 'STADI-4 (stoe & cie, 1996a)' _computing_data_reduction 'X-RED (stoe & cie, 1996b)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL/PC (version 5.03)(Sheldrick,1994)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0553P)^2^+7.3671P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary 'Direct Methods' _atom_sites_solution_secondary 'Difference Fourier Maps' _atom_sites_solution_hydrogens 'Geometrically Placed' _refine_ls_hydrogen_treatment 'Riding Model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1019 _refine_ls_number_parameters 93 _refine_ls_number_restraints 23 _refine_ls_R_factor_all 0.0576 _refine_ls_R_factor_gt 0.0453 _refine_ls_wR_factor_ref 0.1260 _refine_ls_wR_factor_gt 0.1162 _refine_ls_goodness_of_fit_ref 1.105 _refine_ls_restrained_S_all 1.107 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu Cu 0.0000 0.2500 0.1250 0.0291(3) Uani 1 4 d SU . . N31 N 0.00159(17) 0.34230(17) -0.0376(4) 0.0297(7) Uani 1 1 d U . . C34 C -0.0054(2) 0.4529(2) -0.2971(5) 0.0289(8) Uani 1 1 d U . . N37 N -0.01177(18) 0.51111(17) -0.4274(4) 0.0304(7) Uani 1 1 d U . . C35 C -0.0575(2) 0.4540(2) -0.1628(5) 0.0305(8) Uani 1 1 d U . . H35 H -0.0959 0.4930 -0.1562 0.037 Uiso 1 1 calc R . . C36 C -0.0529(2) 0.3973(2) -0.0381(5) 0.0294(8) Uani 1 1 d U . . H36 H -0.0902 0.3971 0.0520 0.035 Uiso 1 1 calc R . . C32 C 0.0535(2) 0.3441(2) -0.1651(5) 0.0383(10) Uani 1 1 d U . . H32 H 0.0932 0.3064 -0.1648 0.046 Uiso 1 1 calc R . . C33 C 0.0528(2) 0.3976(2) -0.2969(5) 0.0367(9) Uani 1 1 d U . . H33 H 0.0910 0.3967 -0.3851 0.044 Uiso 1 1 calc R . . B B -0.2194(9) 0.4828(12) 0.3829(16) 0.075(7) Uani 0.25 1 d PDU A -1 F1 F -0.1861(4) 0.4974(4) 0.5467(13) 0.113(3) Uani 0.50 1 d PDU A -1 F2 F -0.1858(4) 0.4584(4) 0.2276(15) 0.126(4) Uani 0.50 1 d PDU A -1 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu 0.0349(4) 0.0349(4) 0.0175(5) 0.000 0.000 0.000 N31 0.0326(16) 0.0339(16) 0.0226(16) 0.0009(13) 0.0013(13) 0.0012(12) C34 0.0356(19) 0.0287(19) 0.0225(18) -0.0010(14) -0.0013(15) -0.0006(15) N37 0.0364(17) 0.0313(16) 0.0235(14) 0.0014(13) 0.0013(13) 0.0000(13) C35 0.0333(19) 0.0302(19) 0.028(2) -0.0026(15) 0.0028(15) 0.0042(15) C36 0.0303(19) 0.035(2) 0.0233(18) -0.0029(15) 0.0045(15) -0.0001(15) C32 0.039(2) 0.046(2) 0.031(2) 0.0108(18) 0.0084(17) 0.0107(17) C33 0.037(2) 0.045(2) 0.029(2) 0.0054(17) 0.0084(17) 0.0090(17) B 0.035(11) 0.030(10) 0.158(19) -0.031(15) -0.023(13) 0.000(8) F1 0.095(5) 0.072(4) 0.173(8) 0.030(5) -0.069(6) -0.027(4) F2 0.065(4) 0.065(4) 0.246(11) -0.068(6) 0.047(6) -0.005(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu N31 2.034(3) 6_454 ? Cu N31 2.034(3) 15 ? Cu N31 2.034(3) 12_666 ? Cu N31 2.034(3) . y N31 C32 1.334(5) . ? N31 C36 1.341(5) . ? C34 C35 1.376(5) . ? C34 C33 1.392(5) . ? C34 N37 1.430(5) . ? N37 N37 1.254(6) 9_564 ? C35 C36 1.379(5) . ? C32 C33 1.376(5) . ? B F2 1.400(10) . ? B F1 1.414(9) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N31 Cu N31 112.44(9) 6_454 15 y N31 Cu N31 112.44(9) 6_454 12_666 y N31 Cu N31 103.69(17) 15 12_666 y N31 Cu N31 103.69(17) 6_454 . y N31 Cu N31 112.44(9) 15 . y N31 Cu N31 112.44(9) 12_666 . y C32 N31 C36 117.1(3) . . ? C32 N31 Cu 119.0(2) . . ? C36 N31 Cu 123.4(2) . . ? C35 C34 C33 119.0(3) . . ? C35 C34 N37 118.1(3) . . ? C33 C34 N37 122.9(3) . . ? N37 N37 C34 112.9(4) 9_564 . ? C36 C35 C34 118.6(3) . . ? N31 C36 C35 123.3(3) . . ? N31 C32 C33 123.9(3) . . ? C32 C33 C34 118.0(3) . . ? F2 B F1 130.6(14) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 24.98 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.506 _refine_diff_density_min -0.246 _refine_diff_density_rms 0.074 #===end data_cuapyw # Paper complex no 5 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Copper(II) trans-azobis(4-pyridine) Hexafluorosilicate Water Adduct ; _chemical_name_common '{[Cu(4-apy)2(OH2)2](SiF6)(H2O)' _chemical_formula_moiety ? _chemical_formula_sum 'C20 H22 Cu F6 N8 O3 Si' _chemical_formula_weight 628.09 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Si' 'Si' 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cu' 'Cu' 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M P4/ncc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z' '-y+1/2, x, z' 'y, -x+1/2, z' '-x, y+1/2, -z+1/2' 'x+1/2, -y, -z+1/2' 'y+1/2, x+1/2, -z+1/2' '-y, -x, -z+1/2' '-x, -y, -z' 'x-1/2, y-1/2, -z' 'y-1/2, -x, -z' '-y, x-1/2, -z' 'x, -y-1/2, z-1/2' '-x-1/2, y, z-1/2' '-y-1/2, -x-1/2, z-1/2' 'y, x, z-1/2' _cell_length_a 10.767(2) _cell_length_b 10.767(2) _cell_length_c 21.030(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2438.0(7) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 3994 _cell_measurement_theta_min 3 _cell_measurement_theta_max 29.5 _exptl_crystal_description Tablet _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.06 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.711 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1276 _exptl_absorpt_coefficient_mu 1.033 _exptl_absorpt_correction_type None _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; BF4- used as starting anion but SiF6- in product ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.6917 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'Daresbury SRS Station 9.8' _diffrn_radiation_monochromator 'Silicon 111' _diffrn_measurement_device_type 'Siemens SMART CCD diffractometer' _diffrn_measurement_method '\w Rotation With Narrow Frames' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6849 _diffrn_reflns_av_R_equivalents 0.0371 _diffrn_reflns_av_sigmaI/netI 0.0312 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 3 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 2.68 _diffrn_reflns_theta_max 30.24 _reflns_number_total 1650 _reflns_number_gt 1292 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Local Programs' _computing_data_reduction 'Siemens SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL/PC (version 5.03)(Sheldrick,1994)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0483P)^2^+0.8717P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary 'Direct Methods' _atom_sites_solution_secondary 'Difference Fourier Maps' _atom_sites_solution_hydrogens 'Found' _refine_ls_hydrogen_treatment 'Riding on Parent Atom' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1650 _refine_ls_number_parameters 109 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0487 _refine_ls_R_factor_gt 0.0350 _refine_ls_wR_factor_ref 0.0937 _refine_ls_wR_factor_gt 0.0879 _refine_ls_goodness_of_fit_ref 1.071 _refine_ls_restrained_S_all 1.070 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu1 Cu 0.7500 0.2500 0.2500 0.01133(13) Uani 1 4 d S . . Si1 Si 1.2500 0.2500 0.29654(5) 0.0171(2) Uani 1 4 d S . . F4 F 1.2500 0.2500 0.21614(13) 0.0325(6) Uani 1 4 d S . . F5 F 1.12978(10) 0.14986(10) 0.29619(6) 0.0263(3) Uani 1 1 d . . . F6 F 1.2500 0.2500 0.37581(12) 0.0284(5) Uani 1 4 d S . . N31 N 0.65459(13) 0.16061(13) 0.31970(8) 0.0135(3) Uani 1 1 d . . . C32 C 0.65543(16) 0.03640(16) 0.32289(10) 0.0163(4) Uani 1 1 d . . . H32 H 0.689(2) -0.0071(19) 0.2881(11) 0.020 Uiso 1 1 d . . . C33 C 0.60558(18) -0.02756(17) 0.37375(10) 0.0206(4) Uani 1 1 d . . . H33 H 0.608(2) -0.127(2) 0.3796(11) 0.025 Uiso 1 1 d . . . C34 C 0.55371(17) 0.03988(17) 0.42335(10) 0.0204(4) Uani 1 1 d . . . C35 C 0.55002(18) 0.16862(17) 0.41988(10) 0.0219(4) Uani 1 1 d . . . H35 H 0.504(2) 0.218(2) 0.4530(11) 0.026 Uiso 1 1 d . . . C36 C 0.60106(17) 0.22461(16) 0.36743(10) 0.0183(4) Uani 1 1 d . . . H36 H 0.601(2) 0.315(2) 0.3634(10) 0.022 Uiso 1 1 d . . . N37 N 0.50309(17) -0.02951(17) 0.47503(8) 0.0289(4) Uani 1 1 d . . . O1 O 0.90383(12) 0.09617(12) 0.2500 0.0207(4) Uani 1 2 d S . . H11 H 0.892(2) 0.023(2) 0.2390(11) 0.025 Uiso 1 1 d . . . O2 O 1.2500 0.2500 0.5055(2) 0.092(2) Uani 1 4 d SD . . H21 H 1.2500 0.2500 0.4653(5) 0.110 Uiso 1 4 d SD . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu1 0.01311(15) 0.01311(15) 0.0078(2) 0.000 0.000 -0.00516(14) Si1 0.0151(3) 0.0151(3) 0.0210(6) 0.000 0.000 0.000 F4 0.0384(9) 0.0384(9) 0.0206(15) 0.000 0.000 0.000 F5 0.0184(5) 0.0221(5) 0.0385(8) -0.0042(5) -0.0023(5) -0.0053(4) F6 0.0311(8) 0.0311(8) 0.0230(15) 0.000 0.000 0.000 N31 0.0138(6) 0.0152(6) 0.0116(8) 0.0009(6) 0.0005(5) -0.0041(5) C32 0.0187(8) 0.0156(7) 0.0147(10) -0.0014(7) 0.0013(7) -0.0048(6) C33 0.0254(9) 0.0178(8) 0.0184(11) 0.0033(7) -0.0002(8) -0.0063(7) C34 0.0234(9) 0.0232(8) 0.0145(10) 0.0048(7) 0.0028(7) -0.0064(7) C35 0.0267(9) 0.0222(8) 0.0168(11) 0.0000(8) 0.0064(8) -0.0016(7) C36 0.0228(8) 0.0172(8) 0.0151(10) 0.0015(7) 0.0038(7) -0.0013(6) N37 0.0429(10) 0.0251(8) 0.0186(10) 0.0048(7) 0.0100(9) -0.0086(7) O1 0.0169(5) 0.0169(5) 0.0284(12) -0.0053(5) -0.0053(5) -0.0001(7) O2 0.124(3) 0.124(3) 0.027(3) 0.000 0.000 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 N31 2.0322(15) 7_545 ? Cu1 N31 2.0322(15) 8_665 ? Cu1 N31 2.0322(15) 2_655 ? Cu1 N31 2.0322(15) . y Cu1 O1 2.3424(19) 2_655 ? Cu1 O1 2.3424(19) . y Si1 F6 1.667(3) . ? Si1 F5 1.6847(11) 2_755 ? Si1 F5 1.6847(11) . ? Si1 F5 1.6847(11) 4_665 ? Si1 F5 1.6847(11) 3_645 ? Si1 F4 1.691(3) . ? N31 C32 1.339(2) . ? N31 C36 1.347(2) . ? C32 C33 1.381(3) . ? C33 C34 1.388(3) . ? C34 C35 1.389(3) . ? C34 N37 1.427(2) . ? C35 C36 1.372(3) . ? N37 N37 1.229(4) 9_656 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N31 Cu1 N31 87.68(8) 7_545 8_665 ? N31 Cu1 N31 177.41(8) 7_545 2_655 ? N31 Cu1 N31 92.37(8) 8_665 2_655 ? N31 Cu1 N31 92.37(8) 7_545 . y N31 Cu1 N31 177.41(8) 8_665 . y N31 Cu1 N31 87.68(8) 2_655 . y N31 Cu1 O1 91.29(4) 7_545 2_655 ? N31 Cu1 O1 88.71(4) 8_665 2_655 ? N31 Cu1 O1 91.29(4) 2_655 2_655 ? N31 Cu1 O1 88.71(4) . 2_655 y N31 Cu1 O1 88.71(4) 7_545 . ? N31 Cu1 O1 91.29(4) 8_665 . y N31 Cu1 O1 88.71(4) 2_655 . ? N31 Cu1 O1 91.29(4) . . ? O1 Cu1 O1 180.0 2_655 . ? F6 Si1 F5 90.25(6) . 2_755 ? F6 Si1 F5 90.25(6) . . ? F5 Si1 F5 179.50(12) 2_755 . ? F6 Si1 F5 90.25(6) . 4_665 ? F5 Si1 F5 89.999(1) 2_755 4_665 ? F5 Si1 F5 89.999(1) . 4_665 ? F6 Si1 F5 90.25(6) . 3_645 ? F5 Si1 F5 89.999(1) 2_755 3_645 ? F5 Si1 F5 89.999(1) . 3_645 ? F5 Si1 F5 179.50(12) 4_665 3_645 ? F6 Si1 F4 180.000(1) . . ? F5 Si1 F4 89.75(6) 2_755 . ? F5 Si1 F4 89.75(6) . . ? F5 Si1 F4 89.75(6) 4_665 . ? F5 Si1 F4 89.75(6) 3_645 . ? C32 N31 C36 118.45(16) . . ? C32 N31 Cu1 120.38(13) . . ? C36 N31 Cu1 120.76(11) . . ? N31 C32 C33 122.30(18) . . ? C32 C33 C34 118.52(17) . . ? C33 C34 C35 119.62(18) . . ? C33 C34 N37 116.87(16) . . ? C35 C34 N37 123.48(19) . . ? C36 C35 C34 118.00(18) . . ? N31 C36 C35 123.07(16) . . ? N37 N37 C34 113.6(2) 9_656 . ? _diffrn_measured_fraction_theta_max 0.901 _diffrn_reflns_theta_full 30.24 _diffrn_measured_fraction_theta_full 0.901 _refine_diff_density_max 0.402 _refine_diff_density_min -0.617 _refine_diff_density_rms 0.085 #===end