Supplementary Material (ESI) for Journal of Materials Chemistry This journal is © The Royal Society of Chemistry 2001 data_global _journal_coden_Cambridge 1145 _publ_requested_journal 'Journal of Materials Chemistry' loop_ _publ_author_name 'Zheng, Li-Min' 'Wang, Xiqu' 'Wang, Yongsheng' 'Jacobson, Allan J.' _publ_contact_author_name 'Prof Allan J Jacobson' _publ_contact_author_address ; Prof Allan J Jacobson Department of Chemistry University of Houston Houston TX 77204 UNITED STATES OF AMERICA ; data_Co(VO3)2(C4H4N2) (74-7) _database_code_CSD 152985 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C4 H4 Co N2 O6 V2' _chemical_formula_weight 336.90 _chemical_melting_point ? _chemical_compound_source ? 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' 'V' 'V' 0.3005 0.5294 '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 Orthorhombic _symmetry_space_group_name_H-M Pnna loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z' '-x+1/2, y+1/2, -z+1/2' 'x, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z' 'x-1/2, -y-1/2, z-1/2' '-x, y-1/2, z-1/2' _cell_length_a 10.2793(8) _cell_length_b 11.5639(9) _cell_length_c 7.4822(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 889.40(12) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needle _exptl_crystal_colour dark-red _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.516 _exptl_crystal_density_method ? _exptl_crystal_F_000 652 _exptl_absorpt_coefficient_mu 3.909 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 ? _diffrn_measurement_method ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4967 _diffrn_reflns_av_R_equivalents 0.0355 _diffrn_reflns_av_sigmaI/netI 0.0294 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.24 _diffrn_reflns_theta_max 28.62 _reflns_number_total 1072 _reflns_number_observed 934 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens SMART software (Siemens, 1996)' _computing_cell_refinement 'Bruker SAINT software (Bruker, 1999)' _computing_data_reduction 'Bruker SAINT software (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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^)+(0.0324P)^2^+0.6090P] where P=(Fo^2^+2Fc^2^)/3 ; _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0011(6) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1072 _refine_ls_number_parameters 77 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0360 _refine_ls_R_factor_obs 0.0273 _refine_ls_wR_factor_all 0.0626 _refine_ls_wR_factor_obs 0.0596 _refine_ls_goodness_of_fit_all 1.058 _refine_ls_goodness_of_fit_obs 1.085 _refine_ls_restrained_S_all 1.058 _refine_ls_restrained_S_obs 1.085 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group V1 V 0.22493(4) 0.35378(3) 0.09809(5) 0.01089(14) Uani 1 d . . Co1 Co -0.07271(4) 0.2500 0.2500 0.01047(14) Uani 1 d S . O1 O 0.0672(2) 0.3294(2) 0.0878(2) 0.0167(4) Uani 1 d . . O2 O 0.2872(2) 0.3318(2) -0.1022(2) 0.0200(4) Uani 1 d . . O3 O 0.2500 0.5000 0.1705(4) 0.0225(6) Uani 1 d S . O4 O 0.2927(3) 0.2500 0.2500 0.0189(6) Uani 1 d S . N1 N -0.0438(2) 0.1006(2) 0.0839(3) 0.0163(5) Uani 1 d . . C1 C 0.0188(3) 0.1038(2) -0.0719(4) 0.0208(6) Uani 1 d . . H1 H 0.0293(34) 0.1729(31) -0.1278(40) 0.031 Uiso 1 d . . C2 C -0.0618(3) -0.0045(2) 0.1565(4) 0.0204(6) Uani 1 d . . H2 H -0.0970(31) -0.0071(31) 0.2716(43) 0.031 Uiso 1 d . . 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 V1 0.0112(2) 0.0087(2) 0.0128(2) 0.00125(14) 0.00207(15) -0.00053(15) Co1 0.0099(2) 0.0108(2) 0.0107(2) -0.0009(2) 0.000 0.000 O1 0.0132(9) 0.0179(9) 0.0190(9) 0.0016(7) 0.0036(7) -0.0010(7) O2 0.0183(10) 0.0226(10) 0.0191(9) 0.0017(7) 0.0070(7) 0.0047(8) O3 0.031(2) 0.0119(13) 0.0251(14) 0.000 0.000 -0.0040(11) O4 0.0167(13) 0.0165(13) 0.0236(13) 0.0068(10) 0.000 0.000 N1 0.0188(12) 0.0153(11) 0.0147(10) -0.0029(8) -0.0013(8) -0.0017(9) C1 0.030(2) 0.0139(13) 0.0180(13) 0.0001(10) 0.0022(11) -0.0019(11) C2 0.028(2) 0.0159(13) 0.0169(12) -0.0019(10) 0.0079(12) -0.0019(11) _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 V1 O1 1.647(2) . ? V1 O2 1.650(2) . ? V1 O4 1.7937(11) . ? V1 O3 1.7942(9) . ? Co1 O2 2.047(2) 6 ? Co1 O2 2.047(2) 7_566 ? Co1 O1 2.094(2) 4 ? Co1 O1 2.094(2) . ? Co1 N1 2.148(2) 4 ? Co1 N1 2.148(2) . ? O2 Co1 2.047(2) 6_655 ? O3 V1 1.7942(9) 2_565 ? O4 V1 1.7937(11) 4 ? N1 C1 1.332(3) . ? N1 C2 1.344(3) . ? C1 C2 1.385(4) 5 ? C2 C1 1.385(4) 5 ? 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 O1 V1 O2 108.27(9) . . ? O1 V1 O4 107.31(10) . . ? O2 V1 O4 108.79(8) . . ? O1 V1 O3 108.45(7) . . ? O2 V1 O3 111.32(10) . . ? O4 V1 O3 112.54(8) . . ? O2 Co1 O2 90.62(11) 6 7_566 ? O2 Co1 O1 177.21(7) 6 4 ? O2 Co1 O1 88.13(7) 7_566 4 ? O2 Co1 O1 88.13(7) 6 . ? O2 Co1 O1 177.21(7) 7_566 . ? O1 Co1 O1 93.23(10) 4 . ? O2 Co1 N1 92.18(8) 6 4 ? O2 Co1 N1 99.00(8) 7_566 4 ? O1 Co1 N1 85.56(8) 4 4 ? O1 Co1 N1 83.54(8) . 4 ? O2 Co1 N1 99.00(8) 6 . ? O2 Co1 N1 92.18(8) 7_566 . ? O1 Co1 N1 83.54(8) 4 . ? O1 Co1 N1 85.56(8) . . ? N1 Co1 N1 164.11(12) 4 . ? V1 O1 Co1 136.39(10) . . ? V1 O2 Co1 146.60(11) . 6_655 ? V1 O3 V1 144.8(2) . 2_565 ? V1 O4 V1 134.3(2) . 4 ? C1 N1 C2 116.5(2) . . ? C1 N1 Co1 123.4(2) . . ? C2 N1 Co1 118.3(2) . . ? N1 C1 C2 122.1(3) . 5 ? N1 C2 C1 121.4(3) . 5 ? _refine_diff_density_max 0.400 _refine_diff_density_min -0.364 _refine_diff_density_rms 0.098 data_Co(4,4'-bipy)(VO3)2 _database_code_CSD 152986 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C10 H8 Co N2 O6 V2' _chemical_formula_weight 412.99 _chemical_melting_point ? _chemical_compound_source ? 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' 'V' 'V' 0.3005 0.5294 '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 triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.164(2) _cell_length_b 8.587(2) _cell_length_c 10.162(2) _cell_angle_alpha 87.04(3) _cell_angle_beta 75.72(3) _cell_angle_gamma 75.02(3) _cell_volume 666.9(2) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needle _exptl_crystal_colour dark red _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.057 _exptl_crystal_density_method ? _exptl_crystal_F_000 406 _exptl_absorpt_coefficient_mu 2.628 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'Siemens SMART CCD' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 1K _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 4241 _diffrn_reflns_av_R_equivalents 0.0155 _diffrn_reflns_av_sigmaI/netI 0.0335 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 28.49 _reflns_number_total 2930 _reflns_number_observed 2593 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens SMART software (Siemens, 1996)' _computing_cell_refinement 'Bruker SAINT software (Bruker, 1999)' _computing_data_reduction 'Bruker SAINT software (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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^)+(0.0430P)^2^+0.8331P] where P=(Fo^2^+2Fc^2^)/3 ; _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2930 _refine_ls_number_parameters 214 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0401 _refine_ls_R_factor_obs 0.0327 _refine_ls_wR_factor_all 0.0822 _refine_ls_wR_factor_obs 0.0784 _refine_ls_goodness_of_fit_all 1.029 _refine_ls_goodness_of_fit_obs 1.049 _refine_ls_restrained_S_all 1.029 _refine_ls_restrained_S_obs 1.049 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Co1 Co 0.34427(5) -0.16122(4) -0.05821(4) 0.01258(11) Uani 1 d . . V1 V 0.26850(6) 0.27282(5) -0.03010(5) 0.01388(12) Uani 1 d . . V2 V -0.12774(6) 0.41028(5) 0.19726(4) 0.01280(12) Uani 1 d . . N1 N 0.1672(3) -0.1643(3) 0.1341(2) 0.0165(5) Uani 1 d . . N2 N -0.4785(3) -0.1549(3) 0.7483(2) 0.0179(5) Uani 1 d . . O1 O 0.2815(3) 0.0784(2) -0.0478(2) 0.0227(5) Uani 1 d . . O2 O 0.1038(3) 0.3554(3) 0.1147(2) 0.0221(4) Uani 1 d . . O3 O 0.4587(3) 0.2928(3) -0.0120(2) 0.0229(5) Uani 1 d . . O4 O 0.2195(3) 0.3774(2) -0.1770(2) 0.0203(4) Uani 1 d . . O5 O -0.1530(3) 0.3712(3) 0.3572(2) 0.0246(5) Uani 1 d . . O6 O -0.2299(3) 0.3029(3) 0.1293(2) 0.0222(4) Uani 1 d . . C1 C 0.0374(4) -0.0332(4) 0.1804(3) 0.0208(6) Uani 1 d . . H1 H 0.0318(49) 0.0579(48) 0.1314(39) 0.031 Uiso 1 d . . C2 C -0.0875(4) -0.0288(4) 0.3000(3) 0.0223(6) Uani 1 d . . H2 H -0.1805(53) 0.0678(49) 0.3273(38) 0.033 Uiso 1 d . . C3 C -0.0831(4) -0.1665(4) 0.3786(3) 0.0172(6) Uani 1 d . . C4 C 0.0509(4) -0.3039(4) 0.3318(3) 0.0209(6) Uani 1 d . . H4 H 0.0640(49) -0.4031(48) 0.3853(38) 0.031 Uiso 1 d . . C5 C 0.1730(4) -0.2980(4) 0.2101(3) 0.0202(6) Uani 1 d . . H5 H 0.2643(50) -0.3920(47) 0.1697(37) 0.030 Uiso 1 d . . C6 C -0.2182(4) -0.1645(4) 0.5066(3) 0.0178(6) Uani 1 d . . C7 C -0.2850(5) -0.0274(4) 0.5899(3) 0.0286(7) Uani 1 d . . H7 H -0.2375(56) 0.0673(52) 0.5653(42) 0.043 Uiso 1 d . . C8 C -0.4117(5) -0.0278(4) 0.7073(3) 0.0292(7) Uani 1 d . . H8 H -0.4505(56) 0.0587(54) 0.7636(43) 0.044 Uiso 1 d . . C9 C -0.4157(4) -0.2867(4) 0.6669(3) 0.0261(7) Uani 1 d . . H9 H -0.4611(54) -0.3690(52) 0.6914(41) 0.039 Uiso 1 d . . C10 C -0.2882(4) -0.2962(4) 0.5474(3) 0.0243(7) Uani 1 d . . H10 H -0.2415(53) -0.3859(51) 0.4980(40) 0.037 Uiso 1 d . . 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 Co1 0.0109(2) 0.0130(2) 0.0131(2) -0.00168(13) -0.00015(13) -0.00396(14) V1 0.0098(2) 0.0128(2) 0.0170(2) -0.0003(2) -0.0006(2) -0.0016(2) V2 0.0119(2) 0.0137(2) 0.0120(2) -0.0016(2) -0.0009(2) -0.0033(2) N1 0.0139(11) 0.0174(12) 0.0159(11) -0.0018(9) 0.0014(9) -0.0045(9) N2 0.0150(11) 0.0209(12) 0.0154(11) -0.0014(9) 0.0013(9) -0.0046(9) O1 0.0248(11) 0.0156(10) 0.0216(11) 0.0000(8) 0.0043(9) -0.0039(8) O2 0.0138(10) 0.0233(11) 0.0265(11) -0.0080(9) 0.0009(8) -0.0041(8) O3 0.0138(10) 0.0286(12) 0.0257(11) 0.0046(9) -0.0049(8) -0.0048(8) O4 0.0241(11) 0.0154(10) 0.0214(11) -0.0001(8) -0.0082(9) -0.0021(8) O5 0.0318(12) 0.0251(11) 0.0143(10) 0.0004(8) -0.0033(9) -0.0047(9) O6 0.0193(11) 0.0233(11) 0.0252(11) -0.0057(9) -0.0038(9) -0.0081(9) C1 0.0192(14) 0.0181(14) 0.0199(15) 0.0022(12) 0.0016(11) -0.0020(11) C2 0.0176(14) 0.0198(15) 0.024(2) -0.0014(12) 0.0026(12) -0.0013(12) C3 0.0145(13) 0.0231(14) 0.0148(13) -0.0028(11) 0.0007(10) -0.0095(11) C4 0.0209(15) 0.0187(14) 0.0202(14) 0.0016(12) 0.0006(11) -0.0055(12) C5 0.0161(14) 0.0190(14) 0.0214(15) -0.0021(12) 0.0032(11) -0.0040(11) C6 0.0134(13) 0.0220(14) 0.0151(13) -0.0012(11) 0.0021(10) -0.0043(11) C7 0.031(2) 0.027(2) 0.026(2) -0.0093(13) 0.0096(14) -0.0188(14) C8 0.032(2) 0.028(2) 0.025(2) -0.0146(14) 0.0092(14) -0.0153(14) C9 0.028(2) 0.020(2) 0.025(2) -0.0025(12) 0.0088(13) -0.0091(13) C10 0.026(2) 0.0172(14) 0.023(2) -0.0062(12) 0.0071(13) -0.0050(12) _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 Co1 O6 1.971(2) 2 ? Co1 O3 1.979(2) 2_655 ? Co1 O1 1.989(2) . ? Co1 N1 2.128(2) . ? Co1 N2 2.142(2) 1_654 ? V1 O3 1.660(2) . ? V1 O1 1.662(2) . ? V1 O2 1.765(2) . ? V1 O4 1.779(2) . ? V2 O5 1.616(2) . ? V2 O6 1.665(2) . ? V2 O4 1.805(2) 2_565 ? V2 O2 1.816(2) . ? N1 C1 1.343(4) . ? N1 C5 1.348(4) . ? N2 C8 1.346(4) . ? N2 C9 1.347(4) . ? N2 Co1 2.142(2) 1_456 ? O3 Co1 1.979(2) 2_655 ? O4 V2 1.805(2) 2_565 ? O6 Co1 1.971(2) 2 ? C1 C2 1.375(4) . ? C2 C3 1.390(4) . ? C3 C4 1.396(4) . ? C3 C6 1.481(4) . ? C4 C5 1.391(4) . ? C6 C7 1.395(4) . ? C6 C10 1.395(4) . ? C7 C8 1.373(4) . ? C9 C10 1.381(4) . ? 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 O6 Co1 O3 109.92(9) 2 2_655 ? O6 Co1 O1 128.75(9) 2 . ? O3 Co1 O1 121.31(10) 2_655 . ? O6 Co1 N1 88.41(9) 2 . ? O3 Co1 N1 91.13(9) 2_655 . ? O1 Co1 N1 89.30(9) . . ? O6 Co1 N2 92.01(9) 2 1_654 ? O3 Co1 N2 89.27(9) 2_655 1_654 ? O1 Co1 N2 89.99(10) . 1_654 ? N1 Co1 N2 179.29(9) . 1_654 ? O3 V1 O1 109.07(12) . . ? O3 V1 O2 108.89(11) . . ? O1 V1 O2 110.49(11) . . ? O3 V1 O4 109.64(11) . . ? O1 V1 O4 109.30(11) . . ? O2 V1 O4 109.44(10) . . ? O5 V2 O6 109.20(12) . . ? O5 V2 O4 109.15(11) . 2_565 ? O6 V2 O4 109.72(10) . 2_565 ? O5 V2 O2 109.06(11) . . ? O6 V2 O2 109.42(10) . . ? O4 V2 O2 110.27(10) 2_565 . ? C1 N1 C5 117.3(2) . . ? C1 N1 Co1 120.3(2) . . ? C5 N1 Co1 122.3(2) . . ? C8 N2 C9 116.6(3) . . ? C8 N2 Co1 122.7(2) . 1_456 ? C9 N2 Co1 120.4(2) . 1_456 ? V1 O1 Co1 168.04(14) . . ? V1 O2 V2 147.46(13) . . ? V1 O3 Co1 136.78(13) . 2_655 ? V1 O4 V2 129.13(12) . 2_565 ? V2 O6 Co1 175.34(14) . 2 ? N1 C1 C2 123.7(3) . . ? C1 C2 C3 119.4(3) . . ? C2 C3 C4 117.6(3) . . ? C2 C3 C6 120.1(3) . . ? C4 C3 C6 122.3(3) . . ? C5 C4 C3 119.4(3) . . ? N1 C5 C4 122.6(3) . . ? C7 C6 C10 117.0(3) . . ? C7 C6 C3 120.9(3) . . ? C10 C6 C3 122.1(3) . . ? C8 C7 C6 119.8(3) . . ? N2 C8 C7 123.6(3) . . ? N2 C9 C10 123.3(3) . . ? C9 C10 C6 119.6(3) . . ? _refine_diff_density_max 0.988 _refine_diff_density_min -0.432 _refine_diff_density_rms 0.101 data_Co2(pzc)(H2O)(VO3)3 _database_code_CSD 152987 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C5 H5 Co2 N2 O12 V3' _chemical_formula_weight 555.79 _chemical_melting_point ? _chemical_compound_source ? 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' 'V' 'V' 0.3005 0.5294 '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 Orthorhombic _symmetry_space_group_name_H-M Pna2(1) 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' _cell_length_a 15.2530(12) _cell_length_b 8.2554(7) _cell_length_c 10.6784(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1344.6(2) _cell_formula_units_Z 4 _cell_measurement_temperature 295(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description flat column _exptl_crystal_colour brown _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.015 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 2.745 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1072 _exptl_absorpt_coefficient_mu 4.495 _exptl_absorpt_correction_type 'empirical' _exptl_absorpt_correction_T_min 0.822 _exptl_absorpt_correction_T_max 1.000 _exptl_special_details ; ? ; _diffrn_ambient_temperature 295(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 'Siemens Smart-CCD diffractometer' _diffrn_measurement_method '\w scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 'no decay' _diffrn_reflns_number 2203 _diffrn_reflns_av_R_equivalents 0.0425 _diffrn_reflns_av_sigmaI/netI 0.0332 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.67 _diffrn_reflns_theta_max 23.52 _reflns_number_total 2203 _reflns_number_observed 1782 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens SMART software (Siemens, 1996)' _computing_cell_refinement 'Bruker SAINT software (Bruker, 1999)' _computing_data_reduction 'Bruker SAINT software (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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^)+(0.0355P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3 ; _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment 'riding mode' _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0006(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.06(3) _refine_ls_number_reflns 2203 _refine_ls_number_parameters 224 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0322 _refine_ls_R_factor_obs 0.0265 _refine_ls_wR_factor_all 0.0597 _refine_ls_wR_factor_obs 0.0581 _refine_ls_goodness_of_fit_all 1.040 _refine_ls_goodness_of_fit_obs 1.070 _refine_ls_restrained_S_all 1.039 _refine_ls_restrained_S_obs 1.069 _refine_ls_shift/esd_max 0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Co1 Co 0.36478(5) 0.06147(10) 0.82439(7) 0.0146(2) Uani 1 d . . Co2 Co 0.38768(5) 0.43531(11) 0.23165(7) 0.0138(2) Uani 1 d . . V1 V 0.60660(6) 0.30306(12) 0.16134(10) 0.0128(2) Uani 1 d . . V2 V 0.80035(6) 0.45409(12) 0.14365(9) 0.0129(2) Uani 1 d . . V3 V 0.91729(6) 0.68156(12) 0.36996(9) 0.0129(3) Uani 1 d . . N1 N 0.3892(3) 0.1514(6) 0.6350(5) 0.0144(12) Uani 1 d . . N2 N 0.3873(3) 0.3066(7) 0.4052(5) 0.0158(12) Uani 1 d . . O1 O 0.1659(3) 0.0721(5) 0.5650(4) 0.0218(11) Uani 1 d . . O1W O 0.3391(3) 0.3007(6) 0.8762(5) 0.0332(13) Uani 1 d . . H1WA H 0.3498(49) 0.3166(88) 0.9577(75) 0.040 Uiso 1 d . . H1WB H 0.3312(43) 0.3919(87) 0.8040(70) 0.040 Uiso 1 d . . O2 O 0.2418(2) 0.0408(5) 0.7396(4) 0.0184(9) Uani 1 d . . O3 O 0.5069(3) 0.3798(5) 0.1616(5) 0.0223(10) Uani 1 d . . O4 O 0.6317(3) 0.1934(5) 0.0221(4) 0.0225(11) Uani 1 d . . O5 O 0.6171(3) 0.1798(5) 0.2805(4) 0.0221(11) Uani 1 d . . O6 O 0.6844(3) 0.4682(5) 0.1743(4) 0.0209(10) Uani 1 d . . O7 O 0.8311(3) 0.2635(5) 0.1550(5) 0.0233(10) Uani 1 d . . O8 O 0.8233(3) 0.5157(5) 0.0012(4) 0.0213(11) Uani 1 d . . O9 O 0.8497(3) 0.5789(5) 0.2603(4) 0.0252(11) Uani 1 d . . O10 O 0.9380(3) 0.8646(5) 0.3165(4) 0.0211(10) Uani 1 d . . O11 O 1.0096(3) 0.5810(5) 0.3825(4) 0.0219(10) Uani 1 d . . C1 C 0.4628(4) 0.2135(8) 0.5857(6) 0.019(2) Uani 1 d . . H1A H 0.5157(4) 0.2034(8) 0.6282(6) 0.023 Uiso 1 calc R . C2 C 0.4600(4) 0.2922(8) 0.4718(6) 0.023(2) Uani 1 d . . H2A H 0.5114(4) 0.3371(8) 0.4405(6) 0.028 Uiso 1 calc R . C3 C 0.3142(4) 0.2389(8) 0.4519(6) 0.0173(15) Uani 1 d . . H3A H 0.2623(4) 0.2429(8) 0.4063(6) 0.021 Uiso 1 calc R . C4 C 0.3158(4) 0.1631(7) 0.5679(5) 0.0128(14) Uani 1 d . . C5 C 0.2352(4) 0.0901(7) 0.6248(6) 0.019(2) Uani 1 d . . 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 Co1 0.0183(4) 0.0123(4) 0.0131(4) 0.0001(4) -0.0007(4) -0.0008(4) Co2 0.0157(4) 0.0117(5) 0.0139(5) 0.0005(4) 0.0001(4) -0.0005(4) V1 0.0149(5) 0.0114(5) 0.0122(6) -0.0009(5) 0.0006(4) 0.0000(4) V2 0.0167(6) 0.0113(5) 0.0108(5) -0.0020(5) -0.0007(4) -0.0008(4) V3 0.0160(5) 0.0115(5) 0.0110(6) -0.0003(4) -0.0002(4) 0.0008(5) N1 0.018(3) 0.012(3) 0.014(3) -0.001(2) -0.003(2) -0.001(2) N2 0.019(3) 0.018(3) 0.010(3) -0.004(2) 0.000(2) 0.001(2) O1 0.021(3) 0.022(3) 0.022(3) 0.003(2) -0.004(2) -0.003(2) O1W 0.057(3) 0.022(3) 0.020(3) -0.004(2) -0.006(3) 0.011(2) O2 0.021(2) 0.022(2) 0.012(2) 0.003(2) 0.004(2) -0.003(2) O3 0.021(2) 0.018(2) 0.028(3) 0.001(2) 0.003(2) 0.005(2) O4 0.026(3) 0.025(3) 0.017(2) -0.006(2) 0.003(2) 0.006(2) O5 0.033(3) 0.016(2) 0.017(2) 0.005(2) -0.001(2) 0.002(2) O6 0.018(2) 0.013(2) 0.032(3) -0.003(2) 0.001(2) 0.000(2) O7 0.032(3) 0.010(2) 0.028(3) 0.007(2) -0.003(3) 0.006(2) O8 0.027(3) 0.018(3) 0.019(3) 0.001(2) 0.004(2) 0.000(2) O9 0.028(3) 0.028(3) 0.020(3) -0.009(2) -0.003(2) -0.004(2) O10 0.032(3) 0.013(2) 0.018(2) 0.000(2) -0.001(2) 0.003(2) O11 0.021(2) 0.018(3) 0.027(2) 0.003(2) 0.000(2) 0.005(2) C1 0.019(4) 0.024(4) 0.014(4) -0.002(3) 0.003(3) 0.005(3) C2 0.018(4) 0.029(4) 0.023(4) -0.006(3) 0.003(3) -0.005(3) C3 0.014(4) 0.017(4) 0.020(4) 0.002(3) 0.000(3) 0.003(3) C4 0.019(4) 0.007(3) 0.012(4) -0.002(3) 0.007(3) -0.002(3) C5 0.021(4) 0.010(3) 0.025(4) -0.007(3) 0.000(3) 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 Co1 O11 2.021(4) 4_645 ? Co1 O5 2.064(4) 2_655 ? Co1 O1W 2.088(5) . ? Co1 O8 2.090(4) 3_456 ? Co1 O2 2.091(4) . ? Co1 N1 2.186(5) . ? Co2 O3 2.019(4) . ? Co2 O7 2.027(4) 3_455 ? Co2 O10 2.034(4) 3_465 ? Co2 N2 2.136(5) . ? Co2 O2 2.159(4) 4_554 ? Co2 O1 2.260(4) 4_554 ? V1 O5 1.638(4) . ? V1 O3 1.648(4) . ? V1 O4 1.783(4) . ? V1 O6 1.813(4) . ? V2 O8 1.642(4) . ? V2 O7 1.646(4) . ? V2 O9 1.783(4) . ? V2 O6 1.802(4) . ? V3 O11 1.640(4) . ? V3 O10 1.646(4) . ? V3 O9 1.775(4) . ? V3 O4 1.791(4) 4_655 ? N1 C4 1.333(7) . ? N1 C1 1.342(8) . ? N2 C2 1.323(8) . ? N2 C3 1.343(8) . ? O1 C5 1.244(7) . ? O1 Co2 2.260(4) 4_545 ? O2 C5 1.296(7) . ? O2 Co2 2.159(4) 4_545 ? O4 V3 1.791(4) 4_644 ? O5 Co1 2.064(4) 2_654 ? O7 Co2 2.027(4) 3 ? O8 Co1 2.090(4) 3_554 ? O10 Co2 2.034(4) 3_565 ? O11 Co1 2.021(4) 4_654 ? C1 C2 1.379(8) . ? C3 C4 1.388(8) . ? C4 C5 1.497(8) . ? 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 O11 Co1 O5 91.1(2) 4_645 2_655 ? O11 Co1 O1W 91.2(2) 4_645 . ? O5 Co1 O1W 176.1(2) 2_655 . ? O11 Co1 O8 91.9(2) 4_645 3_456 ? O5 Co1 O8 87.2(2) 2_655 3_456 ? O1W Co1 O8 89.6(2) . 3_456 ? O11 Co1 O2 172.2(2) 4_645 . ? O5 Co1 O2 86.7(2) 2_655 . ? O1W Co1 O2 91.3(2) . . ? O8 Co1 O2 95.5(2) 3_456 . ? O11 Co1 N1 95.5(2) 4_645 . ? O5 Co1 N1 95.4(2) 2_655 . ? O1W Co1 N1 87.5(2) . . ? O8 Co1 N1 172.1(2) 3_456 . ? O2 Co1 N1 77.3(2) . . ? O3 Co2 O7 92.8(2) . 3_455 ? O3 Co2 O10 90.6(2) . 3_465 ? O7 Co2 O10 176.4(2) 3_455 3_465 ? O3 Co2 N2 102.2(2) . . ? O7 Co2 N2 86.9(2) 3_455 . ? O10 Co2 N2 91.1(2) 3_465 . ? O3 Co2 O2 158.4(2) . 4_554 ? O7 Co2 O2 87.3(2) 3_455 4_554 ? O10 Co2 O2 90.0(2) 3_465 4_554 ? N2 Co2 O2 99.4(2) . 4_554 ? O3 Co2 O1 98.5(2) . 4_554 ? O7 Co2 O1 86.1(2) 3_455 4_554 ? O10 Co2 O1 94.7(2) 3_465 4_554 ? N2 Co2 O1 158.5(2) . 4_554 ? O2 Co2 O1 59.93(15) 4_554 4_554 ? O5 V1 O3 109.1(2) . . ? O5 V1 O4 108.2(2) . . ? O3 V1 O4 113.3(2) . . ? O5 V1 O6 110.1(2) . . ? O3 V1 O6 108.4(2) . . ? O4 V1 O6 107.7(2) . . ? O8 V2 O7 107.6(2) . . ? O8 V2 O9 112.2(2) . . ? O7 V2 O9 112.4(2) . . ? O8 V2 O6 111.0(2) . . ? O7 V2 O6 109.2(2) . . ? O9 V2 O6 104.5(2) . . ? O11 V3 O10 109.2(2) . . ? O11 V3 O9 108.1(2) . . ? O10 V3 O9 108.7(2) . . ? O11 V3 O4 108.2(2) . 4_655 ? O10 V3 O4 110.2(2) . 4_655 ? O9 V3 O4 112.5(2) . 4_655 ? C4 N1 C1 117.6(5) . . ? C4 N1 Co1 112.3(4) . . ? C1 N1 Co1 129.4(4) . . ? C2 N2 C3 117.3(6) . . ? C2 N2 Co2 120.6(4) . . ? C3 N2 Co2 122.1(4) . . ? C5 O1 Co2 87.9(4) . 4_545 ? C5 O2 Co1 117.0(4) . . ? C5 O2 Co2 91.1(4) . 4_545 ? Co1 O2 Co2 150.5(2) . 4_545 ? V1 O3 Co2 156.8(3) . . ? V1 O4 V3 134.0(2) . 4_644 ? V1 O5 Co1 142.1(3) . 2_654 ? V2 O6 V1 125.5(2) . . ? V2 O7 Co2 157.7(3) . 3 ? V2 O8 Co1 143.8(3) . 3_554 ? V3 O9 V2 169.0(3) . . ? V3 O10 Co2 145.9(2) . 3_565 ? V3 O11 Co1 146.0(3) . 4_654 ? N1 C1 C2 120.0(6) . . ? N2 C2 C1 122.9(6) . . ? N2 C3 C4 120.3(6) . . ? N1 C4 C3 121.8(6) . . ? N1 C4 C5 116.2(5) . . ? C3 C4 C5 121.9(6) . . ? O1 C5 O2 120.9(6) . . ? O1 C5 C4 122.5(6) . . ? O2 C5 C4 116.5(5) . . ? _refine_diff_density_max 0.487 _refine_diff_density_min -0.361 _refine_diff_density_rms 0.088