Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name 'Jon Zubieta' 'R.S.Rarig Junior' _publ_contact_author_name 'Prof Jon Zubieta' _publ_contact_author_address ; Department of Chemistry Syracuse University Syracuse New York 13244 UNITED STATES OF AMERICA ; _publ_contact_author_email JAZUBIET@SYR.EDU _publ_section_title ; Solid state coordination chemistry: secondary metal-ligand influences on the structures of vanadium oxides. Hydrothermal syntheses and structures of [Zn(tpytrz)2V2O6], [Zn3(tpytrz)2(H2O)2V6O18]. 6H2) and [Cu3(tpytrz)2(H2O)2V8O23]. 3H2O (tpytrz=2,4,6-tri(4-pyridyl)-1,3,5-triazine) ; data_fdd2 _database_code_CSD 198637 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H12 N6 O3 V Zn0.50' _chemical_formula_weight 443.96 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Fdd2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'x+1/4, -y+1/4, z+1/4' '-x+1/4, y+1/4, z+1/4' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' 'x+1/4, -y+3/4, z+3/4' '-x+1/4, y+3/4, z+3/4' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' 'x+3/4, -y+1/4, z+3/4' '-x+3/4, y+1/4, z+3/4' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' 'x+3/4, -y+3/4, z+1/4' '-x+3/4, y+3/4, z+1/4' _cell_length_a 15.8249(11) _cell_length_b 81.248(6) _cell_length_c 5.3089(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 6825.9(9) _cell_formula_units_Z 16 _cell_measurement_temperature 90(2) _cell_measurement_reflns_used 5990 _cell_measurement_theta_min 2.01 _cell_measurement_theta_max 33.03 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.09 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.728 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3584 _exptl_absorpt_coefficient_mu 1.303 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6237 _exptl_absorpt_correction_T_max 0.9871 _exptl_absorpt_process_details 'SADABS SHELXL-97 (Sheldrick, 1997)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 90(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 'APEX CCD area detector' _diffrn_measurement_method 'Phi and omega scans' _diffrn_detector_area_resol_mean '512 x 512' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1% _diffrn_reflns_number 22301 _diffrn_reflns_av_R_equivalents 0.0432 _diffrn_reflns_av_sigmaI/netI 0.0483 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -121 _diffrn_reflns_limit_k_max 119 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 2.01 _diffrn_reflns_theta_max 33.03 _reflns_number_total 5990 _reflns_number_gt 5709 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL and CrystalMAker 5.x' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0457P)^2^+13.2645P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.022(11) _refine_ls_number_reflns 5990 _refine_ls_number_parameters 306 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0435 _refine_ls_R_factor_gt 0.0413 _refine_ls_wR_factor_ref 0.1026 _refine_ls_wR_factor_gt 0.1015 _refine_ls_goodness_of_fit_ref 1.132 _refine_ls_restrained_S_all 1.132 _refine_ls_shift/su_max 0.002 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zn1 Zn 0.5000 0.5000 -0.11941(7) 0.01225(8) Uani 1 2 d S . . V1 V 0.29834(2) 0.492772(4) -0.38100(8) 0.01341(8) Uani 1 1 d . . . O1 O 0.39617(11) 0.49912(2) -0.3036(4) 0.0190(3) Uani 1 1 d . . . O2 O 0.22090(11) 0.50421(2) -0.2107(4) 0.0192(3) Uani 1 1 d . . . O3 O 0.28789(12) 0.47358(2) -0.3154(4) 0.0247(4) Uani 1 1 d . . . C1 C 0.43531(15) 0.52234(3) 0.2618(5) 0.0174(4) Uani 1 1 d . . . C2 C 0.43123(15) 0.53493(3) 0.4359(5) 0.0168(4) Uani 1 1 d . . . C3 C 0.49804(14) 0.54601(3) 0.4531(5) 0.0150(4) Uani 1 1 d . . . C4 C 0.56730(15) 0.54380(3) 0.2948(5) 0.0181(4) Uani 1 1 d . . . C5 C 0.56740(14) 0.53074(3) 0.1271(5) 0.0173(4) Uani 1 1 d . . . C6 C 0.49396(13) 0.55997(3) 0.6324(5) 0.0152(4) Uani 1 1 d . . . C7 C 0.42911(15) 0.57300(3) 0.9532(5) 0.0153(4) Uani 1 1 d . . . C8 C 0.36249(14) 0.57370(3) 1.1478(5) 0.0151(4) Uani 1 1 d . . . C9 C 0.29974(15) 0.56173(3) 1.1621(5) 0.0182(5) Uani 1 1 d . . . C10 C 0.24009(15) 0.56287(3) 1.3528(6) 0.0207(5) Uani 1 1 d . . . C11 C 0.29943(16) 0.58620(3) 1.5075(5) 0.0205(5) Uani 1 1 d . . . C12 C 0.36200(15) 0.58635(3) 1.3245(5) 0.0180(4) Uani 1 1 d . . . C13 C 0.54219(15) 0.58455(3) 0.7630(5) 0.0154(4) Uani 1 1 d . . . C14 C 0.60270(14) 0.59843(3) 0.7416(5) 0.0151(4) Uani 1 1 d . . . C15 C 0.60453(15) 0.61068(3) 0.9249(5) 0.0171(4) Uani 1 1 d . . . C16 C 0.66097(15) 0.62365(3) 0.8952(5) 0.0194(4) Uani 1 1 d . . . C17 C 0.71056(17) 0.61316(3) 0.5254(5) 0.0211(5) Uani 1 1 d . . . C18 C 0.65773(16) 0.59958(3) 0.5386(5) 0.0180(4) Uani 1 1 d . . . H1 H 0.387(2) 0.5147(4) 0.242(7) 0.017(8) Uiso 1 1 d . . . H2 H 0.389(2) 0.5353(4) 0.538(6) 0.013(7) Uiso 1 1 d . . . H4 H 0.611(2) 0.5514(5) 0.305(7) 0.025(9) Uiso 1 1 d . . . H5 H 0.613(2) 0.5285(4) 0.026(7) 0.026(9) Uiso 1 1 d . . . H9 H 0.298(2) 0.5531(5) 1.054(8) 0.035(11) Uiso 1 1 d . . . H10 H 0.196(2) 0.5554(5) 1.354(9) 0.029(9) Uiso 1 1 d . . . H11 H 0.301(2) 0.5945(4) 1.640(8) 0.023(8) Uiso 1 1 d . . . H12 H 0.403(2) 0.5946(4) 1.312(7) 0.022(9) Uiso 1 1 d . . . H15 H 0.5738(18) 0.6103(3) 1.059(5) 0.001(6) Uiso 1 1 d . . . H16 H 0.664(2) 0.6311(4) 1.024(6) 0.012(7) Uiso 1 1 d . . . H17 H 0.7457(17) 0.6148(4) 0.392(7) 0.010(7) Uiso 1 1 d . . . H18 H 0.659(2) 0.5929(4) 0.421(7) 0.023(9) Uiso 1 1 d . . . N1 N 0.50197(11) 0.52013(2) 0.1096(4) 0.0149(3) Uani 1 1 d . . . N2 N 0.23890(14) 0.57474(3) 1.5263(5) 0.0214(4) Uani 1 1 d . . . N3 N 0.71282(14) 0.62525(3) 0.6967(5) 0.0214(4) Uani 1 1 d . . . N4 N 0.43236(13) 0.55969(2) 0.8046(4) 0.0161(4) Uani 1 1 d . . . N5 N 0.48194(13) 0.58578(2) 0.9382(4) 0.0163(4) Uani 1 1 d . . . N6 N 0.55138(12) 0.57195(2) 0.6033(4) 0.0165(4) Uani 1 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 Zn1 0.00749(14) 0.01435(15) 0.01492(16) 0.000 0.000 -0.00130(11) V1 0.00792(14) 0.01746(16) 0.01485(16) 0.00083(14) -0.00089(14) -0.00136(12) O1 0.0098(7) 0.0247(9) 0.0225(9) 0.0017(7) -0.0028(7) -0.0024(6) O2 0.0122(7) 0.0308(9) 0.0145(7) 0.0015(7) 0.0002(6) 0.0027(7) O3 0.0241(9) 0.0185(8) 0.0314(11) 0.0043(7) -0.0069(8) -0.0042(7) C1 0.0132(10) 0.0175(10) 0.0215(11) -0.0024(8) 0.0028(8) -0.0025(8) C2 0.0128(9) 0.0183(10) 0.0192(11) -0.0010(8) 0.0049(8) -0.0024(8) C3 0.0127(9) 0.0152(10) 0.0173(10) 0.0001(7) 0.0008(8) -0.0012(7) C4 0.0125(10) 0.0193(11) 0.0225(11) -0.0041(8) 0.0011(8) -0.0027(8) C5 0.0109(8) 0.0196(10) 0.0213(10) -0.0027(9) 0.0036(9) -0.0016(7) C6 0.0125(9) 0.0146(9) 0.0185(10) -0.0008(8) -0.0002(9) -0.0006(6) C7 0.0137(9) 0.0134(10) 0.0187(10) 0.0013(7) 0.0027(8) 0.0015(7) C8 0.0145(9) 0.0136(9) 0.0171(10) 0.0010(8) 0.0032(8) 0.0005(7) C9 0.0159(10) 0.0162(10) 0.0225(12) -0.0006(8) 0.0040(8) -0.0007(7) C10 0.0160(10) 0.0202(11) 0.0259(13) 0.0011(10) 0.0062(10) -0.0004(8) C11 0.0183(11) 0.0197(11) 0.0234(13) -0.0029(9) 0.0044(9) 0.0029(9) C12 0.0165(10) 0.0168(10) 0.0206(12) -0.0014(8) 0.0017(8) 0.0016(8) C13 0.0128(10) 0.0153(10) 0.0179(10) -0.0004(8) 0.0007(8) 0.0005(7) C14 0.0124(9) 0.0123(10) 0.0205(11) 0.0005(7) 0.0015(8) 0.0004(7) C15 0.0148(10) 0.0173(10) 0.0194(12) -0.0004(7) 0.0011(8) 0.0015(7) C16 0.0185(10) 0.0160(9) 0.0237(12) -0.0019(9) 0.0009(10) -0.0010(7) C17 0.0197(11) 0.0176(11) 0.0259(12) -0.0008(9) 0.0060(10) -0.0036(8) C18 0.0194(11) 0.0138(10) 0.0210(11) -0.0018(8) 0.0032(9) -0.0009(8) N1 0.0104(7) 0.0165(9) 0.0176(9) -0.0002(7) 0.0012(8) -0.0015(6) N2 0.0178(10) 0.0225(11) 0.0240(11) 0.0002(8) 0.0052(8) 0.0030(8) N3 0.0181(10) 0.0179(9) 0.0282(11) -0.0011(8) 0.0028(8) -0.0039(7) N4 0.0131(8) 0.0149(8) 0.0203(9) -0.0010(7) 0.0023(7) 0.0003(7) N5 0.0155(8) 0.0158(9) 0.0176(9) -0.0013(7) 0.0033(7) 0.0002(7) N6 0.0132(8) 0.0160(8) 0.0202(9) -0.0028(8) 0.0016(8) -0.0006(6) _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 Zn1 O1 1.9134(17) . ? Zn1 O1 1.9134(17) 2_665 ? Zn1 N1 2.038(2) . ? Zn1 N1 2.038(2) 2_665 ? V1 O3 1.6063(19) . ? V1 O1 1.6826(18) . ? V1 O2 1.7840(19) . ? V1 O2 1.794(2) 10_564 ? O2 V1 1.794(2) 10_565 ? C1 N1 1.341(3) . ? C1 C2 1.381(3) . ? C2 C3 1.391(3) . ? C3 C4 1.393(3) . ? C3 C6 1.482(3) . ? C4 C5 1.385(3) . ? C5 N1 1.350(3) . ? C6 N4 1.337(3) . ? C6 N6 1.341(3) . ? C7 N5 1.335(3) . ? C7 N4 1.340(3) . ? C7 C8 1.477(3) . ? C8 C9 1.392(3) . ? C8 C12 1.392(3) . ? C9 C10 1.387(3) . ? C10 N2 1.334(4) . ? C11 N2 1.340(3) . ? C11 C12 1.387(4) . ? C13 N5 1.336(3) . ? C13 N6 1.337(3) . ? C13 C14 1.484(3) . ? C14 C18 1.389(3) . ? C14 C15 1.392(3) . ? C15 C16 1.390(3) . ? C16 N3 1.342(4) . ? C17 N3 1.339(4) . ? C17 C18 1.386(3) . ? 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 Zn1 O1 118.53(12) . 2_665 ? O1 Zn1 N1 110.37(8) . . ? O1 Zn1 N1 105.16(7) 2_665 . ? O1 Zn1 N1 105.16(7) . 2_665 ? O1 Zn1 N1 110.37(8) 2_665 2_665 ? N1 Zn1 N1 106.76(12) . 2_665 ? O3 V1 O1 109.83(10) . . ? O3 V1 O2 108.97(11) . . ? O1 V1 O2 110.41(10) . . ? O3 V1 O2 109.07(10) . 10_564 ? O1 V1 O2 110.65(9) . 10_564 ? O2 V1 O2 107.86(5) . 10_564 ? V1 O1 Zn1 157.88(12) . . ? V1 O2 V1 133.03(11) . 10_565 ? N1 C1 C2 122.6(2) . . ? C1 C2 C3 119.2(2) . . ? C2 C3 C4 118.4(2) . . ? C2 C3 C6 120.3(2) . . ? C4 C3 C6 121.4(2) . . ? C5 C4 C3 119.2(2) . . ? N1 C5 C4 122.1(2) . . ? N4 C6 N6 125.8(2) . . ? N4 C6 C3 117.27(19) . . ? N6 C6 C3 116.9(2) . . ? N5 C7 N4 124.6(2) . . ? N5 C7 C8 117.3(2) . . ? N4 C7 C8 118.0(2) . . ? C9 C8 C12 118.4(2) . . ? C9 C8 C7 121.4(2) . . ? C12 C8 C7 120.2(2) . . ? C10 C9 C8 118.6(2) . . ? N2 C10 C9 124.2(2) . . ? N2 C11 C12 124.6(2) . . ? C11 C12 C8 118.0(2) . . ? N5 C13 N6 125.2(2) . . ? N5 C13 C14 117.2(2) . . ? N6 C13 C14 117.6(2) . . ? C18 C14 C15 118.8(2) . . ? C18 C14 C13 121.0(2) . . ? C15 C14 C13 120.2(2) . . ? C16 C15 C14 118.4(2) . . ? N3 C16 C15 123.8(2) . . ? N3 C17 C18 124.5(2) . . ? C17 C18 C14 118.1(2) . . ? C1 N1 C5 118.5(2) . . ? C1 N1 Zn1 117.03(15) . . ? C5 N1 Zn1 124.39(16) . . ? C10 N2 C11 116.2(2) . . ? C17 N3 C16 116.4(2) . . ? C6 N4 C7 114.6(2) . . ? C7 N5 C13 115.5(2) . . ? C13 N6 C6 114.2(2) . . ? _diffrn_measured_fraction_theta_max 0.955 _diffrn_reflns_theta_full 33.03 _diffrn_measured_fraction_theta_full 0.955 _refine_diff_density_max 1.790 _refine_diff_density_min -0.665 _refine_diff_density_rms 0.113 data_p21c _database_code_CSD 198638 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H20 N6 O13 V3 Zn1.50' _chemical_formula_weight 779.28 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.8393(3) _cell_length_b 22.8107(9) _cell_length_c 15.1124(6) _cell_angle_alpha 90.00 _cell_angle_beta 102.3630(10) _cell_angle_gamma 90.00 _cell_volume 2639.73(18) _cell_formula_units_Z 4 _cell_measurement_temperature 90(2) _cell_measurement_reflns_used 9352 _cell_measurement_theta_min 1.64 _cell_measurement_theta_max 33.08 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.961 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1552 _exptl_absorpt_coefficient_mu 2.447 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4410 _exptl_absorpt_correction_T_max 0.8874 _exptl_absorpt_process_details 'SADABS SHELXL-97 (Sheldrick, 1997)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 90(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 'APEX CCD area detector' _diffrn_measurement_method 'Phi and omega scans' _diffrn_detector_area_resol_mean '512 x 512' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1% _diffrn_reflns_number 34934 _diffrn_reflns_av_R_equivalents 0.0310 _diffrn_reflns_av_sigmaI/netI 0.0317 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -34 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.64 _diffrn_reflns_theta_max 33.08 _reflns_number_total 9352 _reflns_number_gt 7843 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL and CrytsalMAker 5.x' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0734P)^2^+3.7423P] 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 9352 _refine_ls_number_parameters 433 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0594 _refine_ls_R_factor_gt 0.0488 _refine_ls_wR_factor_ref 0.1387 _refine_ls_wR_factor_gt 0.1316 _refine_ls_goodness_of_fit_ref 1.080 _refine_ls_restrained_S_all 1.080 _refine_ls_shift/su_max 0.003 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zn1 Zn 1.0000 0.5000 0.0000 0.01482(9) Uani 1 2 d S . . Zn2 Zn 0.90013(4) 0.295262(13) 0.18854(2) 0.01598(8) Uani 1 1 d . . . V1 V 0.50158(7) 0.36478(3) -0.06567(4) 0.02647(12) Uani 1 1 d . . . V2 V 0.94234(6) 0.347145(19) -0.02522(3) 0.01535(9) Uani 1 1 d . . . V3 V 1.15085(7) 0.20295(2) 0.32254(3) 0.02077(10) Uani 1 1 d . . . O1 O 1.2620(3) 0.51176(9) -0.01760(15) 0.0222(4) Uani 1 1 d . . . O2 O 1.0391(3) 0.41073(8) -0.02328(14) 0.0204(4) Uani 1 1 d . . . O3 O 1.0363(3) 0.29425(10) -0.08629(17) 0.0303(5) Uani 1 1 d . . . O4 O 0.7236(3) 0.35493(13) -0.07938(17) 0.0343(5) Uani 1 1 d . . . O5 O 0.4932(4) 0.35684(14) 0.0397(2) 0.0471(7) Uani 1 1 d . . . O6 O 0.4365(3) 0.43161(12) -0.0987(2) 0.0388(6) Uani 1 1 d . . . O7 O 0.9602(3) 0.32410(10) 0.08056(15) 0.0293(5) Uani 1 1 d . . . O8 O 1.1146(3) 0.26687(9) 0.26588(14) 0.0233(4) Uani 1 1 d . . . O9 O 1.3749(3) 0.19176(12) 0.36726(19) 0.0357(6) Uani 1 1 d . . . O10 O 1.0735(4) 0.15020(10) 0.25459(18) 0.0368(6) Uani 1 1 d . . . O11 O 0.1059(5) 0.17251(18) 0.0666(3) 0.0619(10) Uani 1 1 d . . . O12 O 0.5319(11) 0.2963(3) 0.3077(6) 0.066(2) Uani 0.50 1 d P . . O12A O 0.4484(8) 0.3147(3) 0.2231(5) 0.0443(13) Uani 0.50 1 d P . . O13 O 0.3361(9) 0.2773(4) 0.1271(5) 0.142(3) Uani 1 1 d . . . C1 C 1.1982(4) 0.44387(12) 0.17476(18) 0.0194(5) Uani 1 1 d . . . C2 C 1.2563(4) 0.43492(12) 0.26707(18) 0.0198(5) Uani 1 1 d . . . C3 C 1.2058(4) 0.47460(11) 0.32702(17) 0.0163(4) Uani 1 1 d . . . C4 C 1.0980(4) 0.52115(12) 0.29156(18) 0.0189(5) Uani 1 1 d . . . C5 C 1.0429(4) 0.52592(12) 0.19859(18) 0.0191(5) Uani 1 1 d . . . C6 C 1.2653(3) 0.46778(11) 0.42604(17) 0.0160(4) Uani 1 1 d . . . C7 C 1.2789(4) 0.50191(11) 0.56743(17) 0.0169(4) Uani 1 1 d . . . C8 C 1.4114(4) 0.41699(11) 0.54679(17) 0.0172(4) Uani 1 1 d . . . C9 C 0.7462(4) 0.40877(12) 0.22622(18) 0.0199(5) Uani 1 1 d . . . C10 C 0.7065(4) 0.45461(12) 0.27859(18) 0.0196(5) Uani 1 1 d . . . C11 C 0.7612(3) 0.45087(11) 0.37259(17) 0.0169(4) Uani 1 1 d . . . C12 C 0.8557(4) 0.40218(12) 0.40977(18) 0.0204(5) Uani 1 1 d . . . C13 C 0.8907(4) 0.35836(12) 0.35337(19) 0.0212(5) Uani 1 1 d . . . C14 C 0.6762(4) 0.19236(12) 0.20518(18) 0.0213(5) Uani 1 1 d . . . C15 C 0.5707(4) 0.14427(13) 0.17547(19) 0.0222(5) Uani 1 1 d . . . C16 C 0.5194(4) 0.13420(12) 0.08299(17) 0.0178(5) Uani 1 1 d . . . C17 C 0.5736(4) 0.17311(14) 0.02355(19) 0.0242(6) Uani 1 1 d . . . C18 C 0.6794(4) 0.21957(13) 0.05863(19) 0.0240(6) Uani 1 1 d . . . N1 N 1.0920(3) 0.48845(10) 0.14086(15) 0.0161(4) Uani 1 1 d . . . N2 N 1.3618(3) 0.42089(10) 0.45644(15) 0.0179(4) Uani 1 1 d . . . N3 N 1.2189(3) 0.50946(10) 0.47854(15) 0.0180(4) Uani 1 1 d . . . N4 N 1.3741(3) 0.45639(10) 0.60560(15) 0.0191(4) Uani 1 1 d . . . N5 N 0.8363(3) 0.36146(10) 0.26268(15) 0.0178(4) Uani 1 1 d . . . N6 N 0.7307(3) 0.22913(10) 0.14798(15) 0.0166(4) Uani 1 1 d . . . H1 H 1.236(5) 0.4212(16) 0.132(2) 0.017(8) Uiso 1 1 d . . . H2 H 1.328(4) 0.4036(15) 0.296(2) 0.011(7) Uiso 1 1 d . . . H4 H 1.064(6) 0.5462(19) 0.326(3) 0.031(11) Uiso 1 1 d . . . H5 H 0.966(5) 0.5557(17) 0.174(3) 0.021(9) Uiso 1 1 d . . . H9 H 0.711(5) 0.4084(16) 0.166(3) 0.019(9) Uiso 1 1 d . . . H10 H 0.641(6) 0.4878(19) 0.256(3) 0.033(11) Uiso 1 1 d . . . H12 H 0.887(6) 0.3968(19) 0.468(3) 0.031(11) Uiso 1 1 d . . . H13 H 0.959(5) 0.3277(19) 0.380(3) 0.030(10) Uiso 1 1 d . . . H14 H 0.706(5) 0.2032(17) 0.271(3) 0.029(10) Uiso 1 1 d . . . H15 H 0.533(5) 0.1210(19) 0.216(3) 0.029(10) Uiso 1 1 d . . . H17 H 0.545(6) 0.170(2) -0.039(3) 0.045(13) Uiso 1 1 d . . . H18 H 0.722(5) 0.2481(18) 0.022(3) 0.029(10) Uiso 1 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 Zn1 0.0193(2) 0.01330(18) 0.01061(18) 0.00064(13) 0.00046(14) -0.00085(14) Zn2 0.02266(15) 0.01152(13) 0.01355(14) -0.00147(9) 0.00337(11) -0.00211(10) V1 0.0211(2) 0.0299(3) 0.0280(3) -0.0134(2) 0.00456(19) -0.00633(19) V2 0.0191(2) 0.01426(19) 0.01256(18) -0.00082(14) 0.00300(14) -0.00307(15) V3 0.0237(2) 0.0158(2) 0.0218(2) 0.00519(16) 0.00237(17) 0.00111(16) O1 0.0197(9) 0.0210(9) 0.0252(10) -0.0040(8) 0.0032(8) -0.0031(7) O2 0.0285(10) 0.0143(8) 0.0171(9) 0.0007(7) 0.0019(7) -0.0021(7) O3 0.0389(13) 0.0213(10) 0.0336(12) -0.0098(9) 0.0145(10) -0.0027(9) O4 0.0215(10) 0.0509(16) 0.0289(12) -0.0085(11) 0.0014(9) -0.0028(10) O5 0.0523(17) 0.0570(19) 0.0352(14) -0.0147(13) 0.0166(13) -0.0202(15) O6 0.0339(13) 0.0324(13) 0.0478(16) -0.0131(11) 0.0038(11) 0.0001(10) O7 0.0423(13) 0.0283(11) 0.0180(10) 0.0043(8) 0.0082(9) -0.0089(10) O8 0.0287(10) 0.0170(9) 0.0220(10) 0.0054(7) 0.0006(8) 0.0003(8) O9 0.0248(11) 0.0353(13) 0.0455(15) 0.0210(11) 0.0040(10) 0.0045(9) O10 0.0537(16) 0.0182(10) 0.0345(13) 0.0003(9) 0.0007(11) -0.0040(10) O11 0.059(2) 0.071(2) 0.055(2) -0.0264(18) 0.0120(17) -0.0112(18) O12 0.071(5) 0.068(5) 0.063(5) -0.014(4) 0.026(4) -0.022(4) O12A 0.038(3) 0.037(3) 0.062(4) -0.006(3) 0.019(3) -0.003(2) O13 0.109(5) 0.166(7) 0.162(7) 0.027(6) 0.053(5) 0.039(5) C1 0.0239(12) 0.0189(12) 0.0139(11) -0.0019(9) 0.0007(9) 0.0035(9) C2 0.0238(12) 0.0196(12) 0.0147(11) -0.0005(9) 0.0011(9) 0.0067(10) C3 0.0206(11) 0.0145(10) 0.0127(10) -0.0001(8) 0.0011(8) 0.0011(9) C4 0.0272(13) 0.0159(11) 0.0131(11) 0.0001(9) 0.0035(9) 0.0038(9) C5 0.0264(13) 0.0155(11) 0.0150(11) 0.0018(9) 0.0040(9) 0.0053(9) C6 0.0203(11) 0.0151(10) 0.0117(10) 0.0013(8) 0.0013(8) 0.0027(9) C7 0.0219(12) 0.0160(11) 0.0119(10) -0.0008(8) 0.0014(8) 0.0019(9) C8 0.0217(12) 0.0161(11) 0.0128(10) -0.0004(8) 0.0016(8) 0.0042(9) C9 0.0257(13) 0.0191(12) 0.0135(11) -0.0017(9) 0.0011(9) 0.0020(10) C10 0.0258(13) 0.0181(11) 0.0133(11) -0.0002(9) 0.0010(9) 0.0041(10) C11 0.0201(11) 0.0162(11) 0.0142(10) -0.0017(8) 0.0032(9) 0.0013(9) C12 0.0284(13) 0.0199(12) 0.0120(10) -0.0005(9) 0.0021(9) 0.0060(10) C13 0.0287(13) 0.0177(12) 0.0165(11) 0.0004(9) 0.0032(10) 0.0046(10) C14 0.0309(14) 0.0187(12) 0.0134(11) -0.0012(9) 0.0026(10) -0.0071(10) C15 0.0311(14) 0.0197(12) 0.0143(11) 0.0008(9) 0.0014(10) -0.0108(10) C16 0.0225(12) 0.0159(11) 0.0144(11) -0.0013(8) 0.0024(9) -0.0048(9) C17 0.0322(15) 0.0261(13) 0.0133(11) -0.0009(10) 0.0029(10) -0.0110(11) C18 0.0336(15) 0.0230(13) 0.0148(11) 0.0001(10) 0.0040(10) -0.0111(11) N1 0.0205(10) 0.0142(9) 0.0123(9) 0.0003(7) 0.0008(7) 0.0006(8) N2 0.0236(11) 0.0172(10) 0.0120(9) -0.0001(7) 0.0020(8) 0.0051(8) N3 0.0258(11) 0.0163(10) 0.0112(9) -0.0005(7) 0.0020(8) 0.0041(8) N4 0.0238(11) 0.0182(10) 0.0141(9) 0.0007(8) 0.0015(8) 0.0057(8) N5 0.0221(10) 0.0156(9) 0.0154(10) -0.0018(8) 0.0034(8) -0.0012(8) N6 0.0199(10) 0.0148(9) 0.0147(9) -0.0011(7) 0.0030(8) -0.0028(8) _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 Zn1 O2 2.100(2) . ? Zn1 O2 2.100(2) 3_765 ? Zn1 N1 2.113(2) . ? Zn1 N1 2.113(2) 3_765 ? Zn1 O1 2.144(2) 3_765 ? Zn1 O1 2.144(2) . ? Zn2 O7 1.909(2) . ? Zn2 O8 1.942(2) . ? Zn2 N5 2.007(2) . ? Zn2 N6 2.016(2) . ? V1 O5 1.618(3) . ? V1 O6 1.650(3) . ? V1 O9 1.802(2) 4_465 ? V1 O4 1.810(2) . ? V2 O2 1.634(2) . ? V2 O7 1.660(2) . ? V2 O4 1.744(2) . ? V2 O3 1.772(2) . ? V3 O10 1.613(3) . ? V3 O8 1.684(2) . ? V3 O9 1.760(2) . ? V3 O3 1.800(2) 4_566 ? O3 V3 1.800(2) 4_565 ? O9 V1 1.802(2) 4_666 ? C1 N1 1.344(3) . ? C1 C2 1.387(4) . ? C2 C3 1.396(4) . ? C3 C4 1.391(4) . ? C3 C6 1.477(3) . ? C4 C5 1.383(4) . ? C5 N1 1.336(3) . ? C6 N2 1.334(3) . ? C6 N3 1.338(3) . ? C7 N4 1.335(3) . ? C7 N3 1.336(3) . ? C7 C11 1.484(4) 3_766 ? C8 N4 1.339(3) . ? C8 N2 1.340(3) . ? C8 C16 1.477(4) 4_666 ? C9 N5 1.342(4) . ? C9 C10 1.386(4) . ? C10 C11 1.396(4) . ? C11 C12 1.385(4) . ? C11 C7 1.484(4) 3_766 ? C12 C13 1.379(4) . ? C13 N5 1.347(3) . ? C14 N6 1.339(3) . ? C14 C15 1.389(4) . ? C15 C16 1.388(4) . ? C16 C17 1.393(4) . ? C16 C8 1.477(4) 4_465 ? C17 C18 1.380(4) . ? C18 N6 1.342(3) . ? 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 O2 Zn1 O2 180.000(1) . 3_765 ? O2 Zn1 N1 90.99(8) . . ? O2 Zn1 N1 89.01(8) 3_765 . ? O2 Zn1 N1 89.01(8) . 3_765 ? O2 Zn1 N1 90.99(8) 3_765 3_765 ? N1 Zn1 N1 180.0 . 3_765 ? O2 Zn1 O1 94.45(8) . 3_765 ? O2 Zn1 O1 85.55(8) 3_765 3_765 ? N1 Zn1 O1 89.37(9) . 3_765 ? N1 Zn1 O1 90.63(9) 3_765 3_765 ? O2 Zn1 O1 85.55(8) . . ? O2 Zn1 O1 94.45(8) 3_765 . ? N1 Zn1 O1 90.63(9) . . ? N1 Zn1 O1 89.37(9) 3_765 . ? O1 Zn1 O1 180.00(17) 3_765 . ? O7 Zn2 O8 106.81(10) . . ? O7 Zn2 N5 110.76(10) . . ? O8 Zn2 N5 101.67(10) . . ? O7 Zn2 N6 105.35(10) . . ? O8 Zn2 N6 111.25(9) . . ? N5 Zn2 N6 120.40(10) . . ? O5 V1 O6 109.03(16) . . ? O5 V1 O9 109.87(14) . 4_465 ? O6 V1 O9 113.18(13) . 4_465 ? O5 V1 O4 109.96(15) . . ? O6 V1 O4 108.82(14) . . ? O9 V1 O4 105.92(12) 4_465 . ? O2 V2 O7 108.71(11) . . ? O2 V2 O4 108.91(12) . . ? O7 V2 O4 110.84(13) . . ? O2 V2 O3 111.75(11) . . ? O7 V2 O3 109.10(13) . . ? O4 V2 O3 107.54(12) . . ? O10 V3 O8 108.82(12) . . ? O10 V3 O9 110.14(15) . . ? O8 V3 O9 111.51(11) . . ? O10 V3 O3 109.42(14) . 4_566 ? O8 V3 O3 107.52(11) . 4_566 ? O9 V3 O3 109.37(13) . 4_566 ? V2 O2 Zn1 141.24(13) . . ? V2 O3 V3 134.87(14) . 4_565 ? V2 O4 V1 146.29(16) . . ? V2 O7 Zn2 161.22(16) . . ? V3 O8 Zn2 128.67(13) . . ? V3 O9 V1 134.77(15) . 4_666 ? N1 C1 C2 122.5(2) . . ? C1 C2 C3 118.7(2) . . ? C4 C3 C2 118.6(2) . . ? C4 C3 C6 120.3(2) . . ? C2 C3 C6 121.1(2) . . ? C5 C4 C3 118.9(2) . . ? N1 C5 C4 122.8(2) . . ? N2 C6 N3 124.9(2) . . ? N2 C6 C3 117.8(2) . . ? N3 C6 C3 117.3(2) . . ? N4 C7 N3 125.3(2) . . ? N4 C7 C11 118.2(2) . 3_766 ? N3 C7 C11 116.4(2) . 3_766 ? N4 C8 N2 125.1(2) . . ? N4 C8 C16 118.3(2) . 4_666 ? N2 C8 C16 116.6(2) . 4_666 ? N5 C9 C10 122.3(2) . . ? C9 C10 C11 118.5(2) . . ? C12 C11 C10 118.9(2) . . ? C12 C11 C7 119.9(2) . 3_766 ? C10 C11 C7 121.2(2) . 3_766 ? C13 C12 C11 119.4(2) . . ? N5 C13 C12 121.9(3) . . ? N6 C14 C15 122.4(2) . . ? C16 C15 C14 118.7(2) . . ? C15 C16 C17 118.8(2) . . ? C15 C16 C8 121.5(2) . 4_465 ? C17 C16 C8 119.7(2) . 4_465 ? C18 C17 C16 118.9(3) . . ? N6 C18 C17 122.5(3) . . ? C5 N1 C1 118.5(2) . . ? C5 N1 Zn1 119.63(18) . . ? C1 N1 Zn1 121.89(18) . . ? C6 N2 C8 115.1(2) . . ? C7 N3 C6 115.0(2) . . ? C7 N4 C8 114.6(2) . . ? C9 N5 C13 119.0(2) . . ? C9 N5 Zn2 123.25(18) . . ? C13 N5 Zn2 117.77(19) . . ? C14 N6 C18 118.7(2) . . ? C14 N6 Zn2 123.57(18) . . ? C18 N6 Zn2 117.62(18) . . ? _diffrn_measured_fraction_theta_max 0.936 _diffrn_reflns_theta_full 33.08 _diffrn_measured_fraction_theta_full 0.936 _refine_diff_density_max 1.272 _refine_diff_density_min -1.254 _refine_diff_density_rms 0.170 data_pbcn _database_code_CSD 198639 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H17 Cu1.50 N6 O14 V4' _chemical_formula_weight 840.45 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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pbcn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 14.368(3) _cell_length_b 25.739(5) _cell_length_c 14.813(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 5478.3(17) _cell_formula_units_Z 8 _cell_measurement_temperature 90(2) _cell_measurement_reflns_used 6829 _cell_measurement_theta_min 1.58 _cell_measurement_theta_max 29.22 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.038 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3316 _exptl_absorpt_coefficient_mu 2.535 _exptl_absorpt_correction_type mulit-scan _exptl_absorpt_correction_T_min 0.6311 _exptl_absorpt_correction_T_max 0.9278 _exptl_absorpt_process_details 'SADABS SHELXL-97 (Sheldrick, 1997)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 90(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 'APEX CCD area detector' _diffrn_measurement_method 'Phi and omega scans' _diffrn_detector_area_resol_mean '512 x 512' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1% _diffrn_reflns_number 55576 _diffrn_reflns_av_R_equivalents 0.1129 _diffrn_reflns_av_sigmaI/netI 0.0640 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -34 _diffrn_reflns_limit_k_max 34 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.58 _diffrn_reflns_theta_max 29.22 _reflns_number_total 6829 _reflns_number_gt 4839 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Burker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL and CrystalMaker 5.X' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0702P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6829 _refine_ls_number_parameters 404 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0863 _refine_ls_R_factor_gt 0.0523 _refine_ls_wR_factor_ref 0.1435 _refine_ls_wR_factor_gt 0.1197 _refine_ls_goodness_of_fit_ref 1.108 _refine_ls_restrained_S_all 1.108 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu1 Cu 0.70597(4) 0.20069(2) 0.17301(4) 0.01478(14) Uani 1 1 d . . . Cu2 Cu 0.5000 0.0000 0.5000 0.0214(2) Uani 1 2 d S . . V1 V 0.59900(6) 0.20402(3) -0.03504(6) 0.01637(19) Uani 1 1 d . . . V2 V 0.79573(5) 0.18850(3) 0.38815(6) 0.01407(18) Uani 1 1 d . . . V3 V 0.63607(5) 0.18966(3) 0.55221(6) 0.01595(19) Uani 1 1 d . . . V4 V 0.58242(6) 0.08352(3) 0.66602(6) 0.0203(2) Uani 1 1 d . . . O1 O 0.6331(2) 0.27002(13) -0.0444(2) 0.0209(8) Uani 1 1 d . . . O2 O 0.6332(3) 0.17140(14) -0.1237(2) 0.0296(9) Uani 1 1 d . . . O3 O 0.6414(2) 0.17816(13) 0.0630(2) 0.0221(8) Uani 1 1 d . . . O4 O 0.7619(2) 0.21718(13) 0.2906(2) 0.0185(7) Uani 1 1 d . . . O5 O 0.8499(2) 0.13628(13) 0.3626(2) 0.0205(8) Uani 1 1 d . . . O6 O 0.6920(2) 0.16909(14) 0.4514(2) 0.0218(8) Uani 1 1 d . . . O7 O 0.5239(3) 0.20066(17) 0.5266(3) 0.0369(11) Uani 1 1 d . . . O8 O 0.6824(2) 0.24243(14) 0.5900(3) 0.0234(8) Uani 1 1 d . . . O9 O 0.6469(2) 0.14109(14) 0.6371(2) 0.0228(8) Uani 1 1 d . . . O10 O 0.5000 0.0994(2) 0.7500 0.0323(14) Uani 1 2 d S . . O11 O 0.6472(3) 0.03845(18) 0.7068(3) 0.0490(12) Uani 1 1 d . . . O12 O 0.5319(2) 0.06117(16) 0.5700(3) 0.0337(10) Uani 1 1 d . . . O96 O 0.5886(3) 0.1503(2) 0.2789(4) 0.0713(19) Uani 1 1 d . . . O97 O 0.4769(10) 0.0681(10) 0.3825(14) 0.173(11) Uani 0.50 1 d P . . O98 O 0.5000 0.2359(4) 0.7500 0.108(4) Uani 1 2 d S . . O99 O 0.5266(12) 0.0406(5) 0.2854(12) 0.112(6) Uani 0.50 1 d P . . C1 C 0.5515(3) 0.27370(18) 0.1481(3) 0.0147(9) Uani 1 1 d . . . H1 H 0.5171 0.2443 0.1332 0.018 Uiso 1 1 calc R . . C2 C 0.5135(3) 0.32185(17) 0.1322(3) 0.0138(9) Uani 1 1 d . . . H2 H 0.4547 0.3246 0.1063 0.017 Uiso 1 1 calc R . . C3 C 0.5627(3) 0.36628(17) 0.1548(3) 0.0129(9) Uani 1 1 d . . . C4 C 0.6474(3) 0.36006(18) 0.1950(3) 0.0138(9) Uani 1 1 d . . . H4 H 0.6821 0.3888 0.2126 0.017 Uiso 1 1 calc R . . C5 C 0.6807(3) 0.31060(18) 0.2091(3) 0.0155(9) Uani 1 1 d . . . H5 H 0.7378 0.3067 0.2378 0.019 Uiso 1 1 calc R . . C6 C 0.5252(3) 0.41879(17) 0.1389(3) 0.0122(9) Uani 1 1 d . . . C7 C 0.7532(3) 0.09108(18) 0.1671(3) 0.0172(10) Uani 1 1 d . . . H7 H 0.6894 0.0873 0.1758 0.021 Uiso 1 1 calc R . . C8 C 0.8063(3) 0.04713(18) 0.1626(3) 0.0180(10) Uani 1 1 d . . . H8 H 0.7799 0.0144 0.1702 0.022 Uiso 1 1 calc R . . C9 C 0.8984(3) 0.05255(17) 0.1466(3) 0.0107(9) Uani 1 1 d . . . C10 C 0.9342(3) 0.10231(18) 0.1400(3) 0.0166(10) Uani 1 1 d . . . H10 H 0.9976 0.1072 0.1305 0.020 Uiso 1 1 calc R . . C11 C 0.8763(3) 0.14436(18) 0.1474(3) 0.0178(10) Uani 1 1 d . . . H11 H 0.9013 0.1776 0.1435 0.021 Uiso 1 1 calc R . . C12 C 0.9570(3) 0.00578(17) 0.1378(3) 0.0121(9) Uani 1 1 d . . . C13 C 1.0934(3) -0.02927(16) 0.1057(3) 0.0107(8) Uani 1 1 d . . . C14 C 0.3370(3) 0.05638(19) 0.5523(4) 0.0230(12) Uani 1 1 d . . . H14 H 0.3766 0.0847 0.5459 0.028 Uiso 1 1 calc R . . C15 C 0.2476(3) 0.06491(18) 0.5749(4) 0.0211(11) Uani 1 1 d . . . H15 H 0.2254 0.0984 0.5840 0.025 Uiso 1 1 calc R . . C16 C 0.1900(3) 0.02246(17) 0.5842(3) 0.0133(9) Uani 1 1 d . . . C17 C 0.2265(3) -0.02679(18) 0.5726(3) 0.0174(10) Uani 1 1 d . . . H17 H 0.1891 -0.0559 0.5805 0.021 Uiso 1 1 calc R . . C18 C 0.3156(3) -0.03213(19) 0.5501(4) 0.0202(11) Uani 1 1 d . . . H18 H 0.3399 -0.0653 0.5421 0.024 Uiso 1 1 calc R . . N1 N 0.6347(3) 0.26760(15) 0.1835(3) 0.0136(8) Uani 1 1 d . . . N2 N 0.4377(2) 0.42191(14) 0.1150(3) 0.0128(8) Uani 1 1 d . . . N3 N 0.7873(3) 0.13890(15) 0.1599(3) 0.0144(8) Uani 1 1 d . . . N4 N 0.9194(3) -0.04044(14) 0.1521(3) 0.0125(8) Uani 1 1 d . . . N5 N 1.0434(2) 0.01411(14) 0.1145(3) 0.0135(8) Uani 1 1 d . . . N6 N 0.3709(3) 0.00897(16) 0.5388(3) 0.0184(9) Uani 1 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 Cu1 0.0116(3) 0.0127(3) 0.0200(3) -0.0026(2) -0.0041(2) 0.0055(2) Cu2 0.0072(4) 0.0203(4) 0.0366(5) -0.0106(4) 0.0070(3) -0.0031(3) V1 0.0136(4) 0.0147(4) 0.0208(4) 0.0016(3) -0.0046(3) -0.0005(3) V2 0.0129(4) 0.0125(4) 0.0169(4) 0.0007(3) -0.0006(3) 0.0017(3) V3 0.0092(4) 0.0193(4) 0.0193(4) -0.0040(3) -0.0007(3) 0.0005(3) V4 0.0132(4) 0.0169(4) 0.0308(5) -0.0011(4) 0.0102(3) 0.0005(3) O1 0.0186(18) 0.0174(17) 0.027(2) -0.0017(15) 0.0066(15) -0.0028(14) O2 0.048(3) 0.0206(19) 0.020(2) -0.0051(16) -0.0031(17) 0.0011(18) O3 0.0229(19) 0.0190(18) 0.024(2) -0.0035(15) -0.0063(15) 0.0077(14) O4 0.0193(17) 0.0148(16) 0.0213(18) 0.0006(14) -0.0025(14) 0.0051(13) O5 0.0161(17) 0.0141(16) 0.031(2) 0.0011(15) -0.0027(15) 0.0028(14) O6 0.0206(18) 0.0257(19) 0.0190(19) -0.0054(15) 0.0066(14) -0.0070(15) O7 0.0135(18) 0.044(3) 0.053(3) -0.012(2) -0.0101(17) 0.0032(17) O8 0.0206(18) 0.0201(18) 0.029(2) -0.0037(16) -0.0051(15) 0.0004(15) O9 0.0152(17) 0.032(2) 0.0213(19) 0.0046(16) -0.0004(14) -0.0100(15) O10 0.027(3) 0.027(3) 0.042(4) 0.000 0.023(3) 0.000 O11 0.045(3) 0.036(3) 0.065(3) 0.009(2) 0.010(2) 0.024(2) O12 0.0100(17) 0.034(2) 0.057(3) -0.025(2) 0.0074(17) -0.0071(15) O96 0.042(3) 0.079(4) 0.093(4) -0.048(3) -0.034(3) 0.028(3) O97 0.054(9) 0.29(3) 0.178(18) 0.179(19) 0.040(10) 0.072(12) O98 0.128(10) 0.106(9) 0.089(8) 0.000 -0.025(7) 0.000 O99 0.129(14) 0.046(7) 0.160(16) -0.026(8) -0.096(11) 0.007(8) C1 0.011(2) 0.013(2) 0.020(3) -0.0051(19) -0.0021(18) -0.0005(17) C2 0.0051(19) 0.015(2) 0.021(2) -0.0006(19) -0.0049(17) 0.0004(16) C3 0.012(2) 0.011(2) 0.015(2) -0.0004(18) 0.0028(17) 0.0025(17) C4 0.007(2) 0.015(2) 0.020(2) -0.0006(19) 0.0006(17) -0.0003(16) C5 0.010(2) 0.019(2) 0.018(2) -0.002(2) -0.0018(18) 0.0013(17) C6 0.009(2) 0.013(2) 0.015(2) 0.0014(18) 0.0011(17) -0.0011(17) C7 0.007(2) 0.018(2) 0.026(3) -0.005(2) 0.0013(18) 0.0031(17) C8 0.011(2) 0.012(2) 0.031(3) 0.000(2) 0.0036(19) -0.0009(17) C9 0.0069(19) 0.013(2) 0.013(2) -0.0010(17) -0.0005(16) 0.0008(16) C10 0.009(2) 0.014(2) 0.027(3) 0.001(2) 0.0024(19) -0.0020(17) C11 0.015(2) 0.009(2) 0.029(3) 0.0025(19) 0.002(2) 0.0002(17) C12 0.0079(19) 0.014(2) 0.014(2) 0.0008(18) 0.0013(16) 0.0004(17) C13 0.0088(19) 0.010(2) 0.013(2) 0.0018(17) 0.0018(16) 0.0000(16) C14 0.012(2) 0.013(2) 0.044(3) -0.001(2) 0.006(2) -0.0044(18) C15 0.012(2) 0.011(2) 0.040(3) -0.007(2) 0.005(2) -0.0005(18) C16 0.008(2) 0.012(2) 0.020(2) 0.0022(18) 0.0010(17) 0.0007(16) C17 0.011(2) 0.011(2) 0.030(3) 0.002(2) 0.0061(19) -0.0007(17) C18 0.012(2) 0.016(2) 0.032(3) -0.003(2) 0.005(2) 0.0025(18) N1 0.0086(17) 0.0141(19) 0.018(2) -0.0001(16) -0.0012(15) 0.0020(14) N2 0.0073(17) 0.0098(17) 0.021(2) 0.0009(16) -0.0022(15) -0.0013(14) N3 0.0087(17) 0.0140(19) 0.020(2) -0.0011(16) -0.0011(15) 0.0042(14) N4 0.0091(17) 0.0089(17) 0.020(2) 0.0010(15) 0.0009(15) -0.0018(14) N5 0.0082(17) 0.0121(18) 0.020(2) 0.0005(16) 0.0022(15) 0.0005(14) N6 0.0078(17) 0.021(2) 0.027(2) -0.0037(18) 0.0059(16) -0.0020(15) _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 O3 1.963(3) . ? Cu1 O4 1.965(3) . ? Cu1 N3 1.983(4) . ? Cu1 N1 2.010(4) . ? Cu1 O8 2.496(4) 2_654 ? Cu1 O96 2.644(7) . ? Cu2 O12 1.940(4) 5_656 ? Cu2 O12 1.940(4) . ? Cu2 N6 1.956(4) . ? Cu2 N6 1.956(4) 5_656 ? Cu2 O97 2.492(14) 5_656 ? Cu2 O97 2.492(14) . ? V1 O2 1.635(4) . ? V1 O3 1.710(4) . ? V1 O7 1.772(4) 3_655 ? V1 O1 1.773(3) . ? V2 O5 1.599(3) . ? V2 O4 1.693(3) . ? V2 O1 1.785(3) 2_655 ? V2 O6 1.829(3) . ? V3 O8 1.613(4) . ? V3 O7 1.680(4) . ? V3 O6 1.777(3) . ? V3 O9 1.780(4) . ? V4 O11 1.606(4) . ? V4 O12 1.697(4) . ? V4 O10 1.7652(15) . ? V4 O9 1.799(4) . ? O1 V2 1.785(3) 2_654 ? O7 V1 1.772(4) 3_655 ? O8 Cu1 2.496(4) 2_655 ? O10 V4 1.7652(15) 3_656 ? O99 O99 1.30(2) 3_655 ? C1 N1 1.314(6) . ? C1 C2 1.375(6) . ? C2 C3 1.386(6) . ? C3 C4 1.365(6) . ? C3 C6 1.474(6) . ? C4 C5 1.376(6) . ? C5 N1 1.344(6) . ? C6 N2 1.308(5) . ? C6 N4 1.332(6) 8_765 ? C7 N3 1.329(6) . ? C7 C8 1.366(6) . ? C8 C9 1.352(6) . ? C9 C10 1.383(6) . ? C9 C12 1.474(6) . ? C10 C11 1.370(6) . ? C11 N3 1.300(6) . ? C12 N5 1.307(5) . ? C12 N4 1.323(6) . ? C13 N5 1.334(5) . ? C13 N2 1.341(5) 8_755 ? C13 C16 1.434(6) 7_655 ? C14 N6 1.329(6) . ? C14 C15 1.345(7) . ? C15 C16 1.378(6) . ? C16 C17 1.383(6) . ? C16 C13 1.434(6) 7_456 ? C17 C18 1.330(6) . ? C18 N6 1.333(6) . ? N2 C13 1.341(5) 8_765 ? N4 C6 1.332(6) 8_755 ? 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 O3 Cu1 O4 173.34(15) . . ? O3 Cu1 N3 87.70(15) . . ? O4 Cu1 N3 91.10(15) . . ? O3 Cu1 N1 94.38(15) . . ? O4 Cu1 N1 87.43(15) . . ? N3 Cu1 N1 174.35(16) . . ? O3 Cu1 O8 93.88(14) . 2_654 ? O4 Cu1 O8 92.72(14) . 2_654 ? N3 Cu1 O8 92.50(14) . 2_654 ? N1 Cu1 O8 82.12(14) . 2_654 ? O3 Cu1 O96 92.65(15) . . ? O4 Cu1 O96 80.85(15) . . ? N3 Cu1 O96 92.31(16) . . ? N1 Cu1 O96 92.85(15) . . ? O8 Cu1 O96 172.04(14) 2_654 . ? O12 Cu2 O12 180.00(14) 5_656 . ? O12 Cu2 N6 91.67(16) 5_656 . ? O12 Cu2 N6 88.33(16) . . ? O12 Cu2 N6 88.33(16) 5_656 5_656 ? O12 Cu2 N6 91.67(16) . 5_656 ? N6 Cu2 N6 180.0(2) . 5_656 ? O12 Cu2 O97 80.4(7) 5_656 5_656 ? O12 Cu2 O97 99.6(7) . 5_656 ? N6 Cu2 O97 90.2(3) . 5_656 ? N6 Cu2 O97 89.8(3) 5_656 5_656 ? O12 Cu2 O97 99.6(7) 5_656 . ? O12 Cu2 O97 80.4(7) . . ? N6 Cu2 O97 89.8(3) . . ? N6 Cu2 O97 90.2(3) 5_656 . ? O97 Cu2 O97 180.000(1) 5_656 . ? O2 V1 O3 112.03(18) . . ? O2 V1 O7 109.4(2) . 3_655 ? O3 V1 O7 106.03(19) . 3_655 ? O2 V1 O1 110.25(18) . . ? O3 V1 O1 109.93(17) . . ? O7 V1 O1 109.11(18) 3_655 . ? O5 V2 O4 107.71(18) . . ? O5 V2 O1 110.89(17) . 2_655 ? O4 V2 O1 112.41(17) . 2_655 ? O5 V2 O6 106.75(17) . . ? O4 V2 O6 108.80(17) . . ? O1 V2 O6 110.08(17) 2_655 . ? O8 V3 O7 109.4(2) . . ? O8 V3 O6 110.83(18) . . ? O7 V3 O6 107.1(2) . . ? O8 V3 O9 108.09(18) . . ? O7 V3 O9 111.2(2) . . ? O6 V3 O9 110.18(17) . . ? O11 V4 O12 108.6(2) . . ? O11 V4 O10 106.9(2) . . ? O12 V4 O10 112.44(14) . . ? O11 V4 O9 112.7(2) . . ? O12 V4 O9 107.46(19) . . ? O10 V4 O9 108.8(2) . . ? V1 O1 V2 140.8(2) . 2_654 ? V1 O3 Cu1 139.3(2) . . ? V2 O4 Cu1 141.2(2) . . ? V3 O6 V2 135.9(2) . . ? V3 O7 V1 161.5(3) . 3_655 ? V3 O8 Cu1 158.5(2) . 2_655 ? V3 O9 V4 134.6(2) . . ? V4 O10 V4 153.3(3) 3_656 . ? V4 O12 Cu2 145.5(3) . . ? N1 C1 C2 122.5(4) . . ? C1 C2 C3 120.0(4) . . ? C4 C3 C2 117.6(4) . . ? C4 C3 C6 120.2(4) . . ? C2 C3 C6 122.1(4) . . ? C3 C4 C5 119.0(4) . . ? N1 C5 C4 123.2(4) . . ? N2 C6 N4 124.5(4) . 8_765 ? N2 C6 C3 116.8(4) . . ? N4 C6 C3 118.7(4) 8_765 . ? N3 C7 C8 123.9(4) . . ? C9 C8 C7 118.0(4) . . ? C8 C9 C10 118.1(4) . . ? C8 C9 C12 119.3(4) . . ? C10 C9 C12 122.5(4) . . ? C11 C10 C9 120.0(4) . . ? N3 C11 C10 121.6(4) . . ? N5 C12 N4 125.3(4) . . ? N5 C12 C9 115.6(4) . . ? N4 C12 C9 119.2(4) . . ? N5 C13 N2 126.5(4) . 8_755 ? N5 C13 C16 116.1(4) . 7_655 ? N2 C13 C16 117.4(4) 8_755 7_655 ? N6 C14 C15 122.5(4) . . ? C14 C15 C16 118.0(4) . . ? C15 C16 C17 119.1(4) . . ? C15 C16 C13 120.4(4) . 7_456 ? C17 C16 C13 120.4(4) . 7_456 ? C18 C17 C16 119.4(4) . . ? C17 C18 N6 121.5(4) . . ? C1 N1 C5 117.5(4) . . ? C1 N1 Cu1 122.4(3) . . ? C5 N1 Cu1 118.5(3) . . ? C6 N2 C13 113.9(4) . 8_765 ? C11 N3 C7 118.3(4) . . ? C11 N3 Cu1 120.4(3) . . ? C7 N3 Cu1 121.2(3) . . ? C12 N4 C6 116.2(4) . 8_755 ? C12 N5 C13 113.6(4) . . ? C14 N6 C18 119.4(4) . . ? C14 N6 Cu2 120.0(3) . . ? C18 N6 Cu2 120.5(3) . . ? _diffrn_measured_fraction_theta_max 0.916 _diffrn_reflns_theta_full 29.22 _diffrn_measured_fraction_theta_full 0.916 _refine_diff_density_max 1.433 _refine_diff_density_min -0.963 _refine_diff_density_rms 0.166