# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/1990 data_global #=============================================================== # 1. SUBMISSION DETAILS _publ_contact_author # Name and address of author for correspondence ; Chen, Xiao-Ming School of Chemistry and Chemical Engineering Zhongshan University Guangzhou, 510275 P. R. China ; _publ_contact_author_phone '86-20-84112074' _publ_contact_author_fax '86 20 84112245' _publ_contact_author_email cescxm@zsu.edu.cn _publ_requested_journal 'J. Chem. Soc., Dalton Trans.' _publ_requested_coeditor_name ? _publ_contact_letter ; Dear Sir/Madam: Please consider this CIF as a supplmentary data for a manuscript submitted to J. Chem. Soc., Dalton Trans. Xiao-Ming Chen ; #=============================================================== # 2. PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_date_printers_first ? _journal_date_printers_final ? _journal_date_proofs_out ? _journal_date_proofs_in ? _journal_coeditor_name ? _journal_coeditor_code ? _journal_coeditor_notes ? _journal_techeditor_code ? _journal_techeditor_notes ? _journal_coden_ASTM ? _journal_name_full ? _journal_year ? _journal_volume ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? #=============================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Organic-inorganic hybrid materials assembled through week intermolecular interactions. Synthesis, structures and non-linear optical properties of [4,4'- bipyH~2~][M(NCS)~4~] (M = Mn^2+^, Co^2+^ and Zn^2+^; 4,4'-bipy = 4,4'- bipyridine) ; loop_ _publ_author_name _publ_author_address 'Chen Hong-Ji' ; School of Chemistry and Chemical Engineering Zhongshan University Guangzhou 510275 P. R. China ; 'Zhang, Ling-Zhi' ; School of Chemistry and Chemical Engineering Zhongshan University Guangzhou 510275 P. R. China ; 'Cai, Zhi-Gang' ; Institute of Laser & Spectroscopy Zhongshan University Guangzhou 510275 P. R. China ; 'Yang, Guang' ; School of Chemistry and Chemical Engineering Zhongshan University Guangzhou 510275 P. R. China ; 'Chen, Xiao-Ming' ; School of Chemistry and Chemical Engineering Zhongshan University Guangzhou 510275 P. R. China ; #============================================================ data_complex1 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ; {[4,4'- bpyH~2~][Mn(NCS)~4~]}~n~ ; _chemical_formula_sum 'C14 H10 Mn N6 S4' _chemical_formula_weight 445.46 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' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Mn' 'Mn' 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombicP _symmetry_space_group_name_H-M P2(1)2(1)2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' _cell_length_a 12.755(4) _cell_length_b 13.169(4) _cell_length_c 5.5100(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 925.5(4) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 26 _cell_measurement_theta_min 7 _cell_measurement_theta_max 16 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.45 _exptl_crystal_size_min 0.36 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.598 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 450 _exptl_absorpt_coefficient_mu 1.174 _exptl_absorpt_correction_type PSI-SCAN _exptl_absorpt_correction_T_min 0.489 _exptl_absorpt_correction_T_max 0.787 _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 R3m' _diffrn_measurement_method '\W scan' _diffrn_standards_number 2 _diffrn_standards_interval_count 120 _diffrn_standards_decay_% NONE _diffrn_reflns_number 1079 _diffrn_reflns_av_R_equivalents 0.0286 _diffrn_reflns_av_sigmaI/netI 0.0196 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -1 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 2.22 _diffrn_reflns_theta_max 27.98 _reflns_number_total 1047 _reflns_number_gt 931 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SHELXTL-Plus (Sheldrick, 1990)' _computing_cell_refinement 'SHELXTL-Plus (Sheldrick, 1990)' _computing_data_reduction 'SHELXTL-Plus (Sheldrick, 1990)' _computing_structure_solution 'SHELXS-90 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL v. 5 (Sheldrick, 1997)' _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^+0.6422P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.049(4) _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 0.00(6) _refine_ls_number_reflns 1047 _refine_ls_number_parameters 115 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0458 _refine_ls_R_factor_gt 0.0387 _refine_ls_wR_factor_ref 0.1093 _refine_ls_wR_factor_gt 0.1011 _refine_ls_goodness_of_fit_ref 1.133 _refine_ls_restrained_S_all 1.133 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.5000 1.0000 0.66531(18) 0.0444(4) Uani 1 d S . . S1 S 0.62874(13) 1.26126(10) 0.1296(3) 0.0588(5) Uani 1 d . . . S2 S 0.74644(14) 0.93192(9) 1.3026(3) 0.0497(4) Uani 1 d . . . N1 N 0.5507(4) 1.1209(3) 0.4588(9) 0.0533(15) Uani 1 d . . . C1 C 0.5828(4) 1.1787(3) 0.3182(9) 0.0379(13) Uani 1 d . . . N2 N 0.6137(4) 0.9466(4) 0.9027(9) 0.0538(14) Uani 1 d . . . C2 C 0.6681(5) 0.9399(4) 1.0697(10) 0.0398(14) Uani 1 d . . . N3 N 0.8293(5) 1.2029(4) 0.5722(13) 0.0677(17) Uani 1 d . . . H3A H 0.7861 1.2569 0.5754 0.080 Uiso 1 d R . . C3 C 0.8983(5) 1.1959(4) 0.3896(13) 0.0560(19) Uani 1 d . . . H3 H 0.8877 1.2508 0.2663 0.080 Uiso 1 d R . . C4 C 0.9671(4) 1.1162(3) 0.3812(10) 0.0434(17) Uani 1 d . . . H4 H 1.0071 1.1049 0.1906 0.080 Uiso 1 d R . . C5 C 0.9619(4) 1.0431(3) 0.5627(9) 0.0327(14) Uani 1 d . . . C6 C 0.8894(4) 1.0519(4) 0.7472(10) 0.0421(15) Uani 1 d . . . H6 H 0.8757 1.0001 0.9207 0.080 Uiso 1 d R . . C7 C 0.8213(5) 1.1334(4) 0.7466(13) 0.0578(18) Uani 1 d . . . H7 H 0.7672 1.1316 0.8825 0.080 Uiso 1 d R . . 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 Mn1 0.0522(10) 0.0448(5) 0.0360(5) 0.000 0.000 0.0008(6) S1 0.0596(14) 0.0554(6) 0.0612(9) 0.0149(7) 0.0200(9) 0.0117(7) S2 0.0483(12) 0.0504(6) 0.0504(7) -0.0034(6) -0.0117(8) -0.0056(7) N1 0.053(4) 0.052(2) 0.055(3) 0.007(2) 0.011(3) 0.008(2) C1 0.025(4) 0.047(2) 0.042(2) -0.003(2) 0.001(3) 0.010(2) N2 0.048(4) 0.069(3) 0.044(2) 0.000(2) -0.006(3) 0.001(3) C2 0.035(4) 0.040(2) 0.045(3) -0.001(2) 0.009(3) -0.001(2) N3 0.052(4) 0.049(2) 0.102(4) -0.024(3) -0.023(4) 0.019(2) C3 0.047(5) 0.039(2) 0.082(4) -0.001(3) -0.032(4) 0.007(3) C4 0.039(5) 0.043(2) 0.048(3) 0.004(2) -0.009(3) -0.010(2) C5 0.019(4) 0.040(2) 0.039(2) -0.0045(19) -0.004(2) -0.0044(19) C6 0.025(5) 0.053(2) 0.049(3) -0.007(2) 0.004(3) 0.000(3) C7 0.046(5) 0.059(3) 0.069(4) -0.017(3) -0.003(4) 0.008(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 Mn1 N1 2.061(5) 2_675 ? Mn1 N1 2.061(5) . yes Mn1 N2 2.075(5) . yes Mn1 N2 2.075(5) 2_675 ? S1 C1 1.614(5) . yes S2 C2 1.630(6) . yes N1 C1 1.161(6) . yes N2 C2 1.156(7) . yes N3 C7 1.332(9) . ? N3 C3 1.340(9) . ? C3 C4 1.369(8) . ? C4 C5 1.390(7) . ? C5 C6 1.380(7) . ? C5 C5 1.494(9) 2_775 ? C6 C7 1.381(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 N1 Mn1 N1 113.0(3) 2_675 . yes N1 Mn1 N2 107.79(19) 2_675 . yes N1 Mn1 N2 113.0(2) . . yes N1 Mn1 N2 113.0(2) 2_675 2_675 yes N1 Mn1 N2 107.79(19) . 2_675 yes N2 Mn1 N2 101.9(3) . 2_675 yes C1 N1 Mn1 170.3(4) . . yes N1 C1 S1 178.3(5) . . yes C2 N2 Mn1 161.3(5) . . yes N2 C2 S2 178.9(5) . . yes C7 N3 C3 123.1(5) . . ? N3 C3 C4 119.9(6) . . ? C3 C4 C5 118.4(6) . . ? C6 C5 C4 120.3(4) . . ? C6 C5 C5 120.0(4) . 2_775 ? C4 C5 C5 119.7(4) . 2_775 ? C5 C6 C7 119.1(5) . . ? N3 C7 C6 119.2(6) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N3 H3A S2 0.90 2.44 3.241(5) 149.0 3_657 N3 H3A S1 0.90 3.17 3.617(6) 112.7 . _diffrn_measured_fraction_theta_max 0.694 _diffrn_reflns_theta_full 27.98 _diffrn_measured_fraction_theta_full 0.694 _refine_diff_density_max 0.292 _refine_diff_density_min -0.250 _refine_diff_density_rms 0.063 data_complex2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety {[4,4'-bipyH~2~][Co(NCS)~4~]}~n~ _chemical_formula_sum 'C14 H10 Co N6 S4' _chemical_formula_weight 449.45 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' 'S' 'S' 0.1246 0.1234 '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 OrthorhombicP _symmetry_space_group_name_H-M P2(1)2(1)2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' _cell_length_a 12.858(4) _cell_length_b 13.019(2) _cell_length_c 5.452(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 912.7(5) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 6.5 _cell_measurement_theta_max 15.0 _exptl_crystal_description prism _exptl_crystal_colour blue _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.42 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.636 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 454 _exptl_absorpt_coefficient_mu 1.408 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.599 _exptl_absorpt_correction_T_max 0.733 _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 R3m' _diffrn_measurement_method '\w scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count 120 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2 _diffrn_reflns_number 1293 _diffrn_reflns_av_R_equivalents 0.0257 _diffrn_reflns_av_sigmaI/netI 0.0172 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -2 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 2.23 _diffrn_reflns_theta_max 27.51 _reflns_number_total 1287 _reflns_number_gt 1210 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SHELXTL-Plus (Sheldrick, 1990)' _computing_cell_refinement 'SHELXTL-Plus (Sheldrick, 1990)' _computing_data_reduction 'SHELXTL-Plus (Sheldrick, 1990)' _computing_structure_solution 'SHELXS-90 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL v. 5 (Sheldrick, 1997)' _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^)+(0.0365P)^2^+0.3966P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.03(3) _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.03(3) _refine_ls_number_reflns 1287 _refine_ls_number_parameters 115 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0327 _refine_ls_R_factor_gt 0.0291 _refine_ls_wR_factor_ref 0.0787 _refine_ls_wR_factor_gt 0.0769 _refine_ls_goodness_of_fit_ref 1.175 _refine_ls_restrained_S_all 1.175 _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 Co1 Co 0.5000 0.0000 0.32079(11) 0.03545(18) Uani 1 d S . . S1 S 0.37322(8) -0.25609(8) 0.8588(2) 0.0502(3) Uani 1 d . . . S2 S 0.24960(7) 0.06873(7) -0.28729(17) 0.0423(2) Uani 1 d . . . N1 N 0.4517(2) -0.1130(2) 0.5280(6) 0.0448(8) Uani 1 d . . . C1 C 0.4198(3) -0.1713(3) 0.6664(7) 0.0378(7) Uani 1 d . . . N2 N 0.3888(2) 0.0486(3) 0.0994(6) 0.0446(7) Uani 1 d . . . C2 C 0.3318(2) 0.0586(2) -0.0610(6) 0.0334(7) Uani 1 d . . . N3 N 0.1690(3) -0.2045(3) 0.4357(8) 0.0581(10) Uani 1 d . . . H3N H 0.2065 -0.2640 0.4394 0.073(15) Uiso 1 d R . . C3 C 0.1001(3) -0.1992(3) 0.6169(9) 0.0520(11) Uani 1 d . . . H3 H 0.0977 -0.2531 0.7367 0.080 Uiso 1 d R . . C4 C 0.0320(3) -0.1175(3) 0.6276(7) 0.0397(8) Uani 1 d . . . H4 H -0.0176 -0.1130 0.7588 0.080 Uiso 1 d R . . C5 C 0.0362(2) -0.0435(2) 0.4453(6) 0.0301(6) Uani 1 d . . . C6 C 0.1108(3) -0.0517(3) 0.2599(7) 0.0415(8) Uani 1 d . . . H6 H 0.1129 -0.0023 0.1294 0.080 Uiso 1 d R . . C7 C 0.1778(3) -0.1337(4) 0.2614(9) 0.0544(11) Uani 1 d . . . H7 H 0.2317 -0.1394 0.1404 0.080 Uiso 1 d R . . 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 0.0407(3) 0.0364(3) 0.0293(3) 0.000 0.000 0.0015(3) S1 0.0537(5) 0.0468(5) 0.0501(6) 0.0139(5) 0.0158(5) 0.0101(4) S2 0.0406(4) 0.0443(4) 0.0422(5) -0.0007(4) -0.0097(4) -0.0059(4) N1 0.0497(17) 0.0418(16) 0.0428(18) 0.0046(16) 0.0083(15) 0.0044(14) C1 0.0378(16) 0.0405(17) 0.0351(17) -0.0034(18) 0.0029(16) 0.0092(14) N2 0.0452(16) 0.0524(17) 0.0362(15) 0.0006(15) -0.0054(14) 0.0012(15) C2 0.0326(15) 0.0301(15) 0.0375(16) -0.0009(15) 0.0050(14) -0.0024(13) N3 0.0460(17) 0.0413(17) 0.087(3) -0.017(2) -0.021(2) 0.0165(15) C3 0.049(2) 0.0361(17) 0.070(3) 0.002(2) -0.022(2) 0.0000(16) C4 0.0408(17) 0.0362(16) 0.0421(19) 0.0027(17) -0.0065(15) -0.0043(14) C5 0.0256(13) 0.0316(14) 0.0331(15) -0.0016(14) -0.0034(12) -0.0049(12) C6 0.0399(17) 0.0455(19) 0.0391(18) -0.0051(16) 0.0042(15) -0.0014(16) C7 0.0437(19) 0.060(2) 0.059(3) -0.016(2) 0.0034(19) 0.0120(19) _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 N1 1.956(3) 2_655 ? Co1 N1 1.956(3) . yes Co1 N2 1.975(3) . yes Co1 N2 1.975(3) 2_655 ? S1 C1 1.636(4) . yes S2 C2 1.630(3) . yes N1 C1 1.146(4) . yes N2 C2 1.149(4) . yes N3 C3 1.329(6) . ? N3 C7 1.329(6) . ? C3 C4 1.378(5) . ? C4 C5 1.385(5) . ? C5 C6 1.397(4) . ? C5 C5 1.467(6) 2 ? C6 C7 1.371(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 N1 Co1 N1 109.4(2) 2_655 . yes N1 Co1 N2 109.99(13) 2_655 . yes N1 Co1 N2 111.36(13) . . yes N1 Co1 N2 111.36(13) 2_655 2_655 yes N1 Co1 N2 109.99(13) . 2_655 yes N2 Co1 N2 104.64(19) . 2_655 yes C1 N1 Co1 172.7(3) . . yes N1 C1 S1 178.7(3) . . yes C2 N2 Co1 164.5(3) . . yes N2 C2 S2 178.0(3) . . yes C3 N3 C7 123.5(3) . . ? N3 C3 C4 119.7(4) . . ? C3 C4 C5 118.7(4) . . ? C4 C5 C6 119.6(3) . . ? C4 C5 C5 120.8(3) . 2 ? C6 C5 C5 119.6(3) . 2 ? C7 C6 C5 119.1(4) . . ? N3 C7 C6 119.4(4) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.243 _refine_diff_density_min -0.228 _refine_diff_density_rms 0.053 data_complex_3 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety {[4,4'-bipyH~2~][Zn(NCS)~4~]}~n~ _chemical_formula_sum 'C14 H10 N6 S4 Zn' _chemical_formula_weight 455.89 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' 'S' 'S' 0.1246 0.1234 '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 P2(1)2(1)2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' _cell_length_a 12.895(7) _cell_length_b 13.008(4) _cell_length_c 5.458(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 915.5(7) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 6.5 _cell_measurement_theta_max 15.0 _exptl_crystal_description prism _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.42 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.654 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 460 _exptl_absorpt_coefficient_mu 1.807 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.479 _exptl_absorpt_correction_T_max 0.896 _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 R3m' _diffrn_measurement_method '\w scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count 120 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2 _diffrn_reflns_number 1343 _diffrn_reflns_av_R_equivalents 0.0849 _diffrn_reflns_av_sigmaI/netI 0.0300 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -1 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 2.22 _diffrn_reflns_theta_max 27.49 _reflns_number_total 1320 _reflns_number_gt 1135 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SHELXTL-Plus (Sheldrick, 1990)' _computing_cell_refinement 'SHELXTL-Plus (Sheldrick, 1990)' _computing_data_reduction 'SHELXTL-Plus (Sheldrick, 1990)' _computing_structure_solution 'SHELXS-90 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL v. 5 (Sheldrick, 1997)' _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^)+(0.0318P)^2^+4.3249P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.050(4) _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 0.05(5) _refine_ls_number_reflns 1320 _refine_ls_number_parameters 116 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0629 _refine_ls_R_factor_gt 0.0514 _refine_ls_wR_factor_ref 0.1425 _refine_ls_wR_factor_gt 0.1378 _refine_ls_goodness_of_fit_ref 1.243 _refine_ls_restrained_S_all 1.243 _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 Zn1 Zn 0.5000 0.0000 0.3180(2) 0.0341(3) Uani 1 d S . . S1 S 0.3735(2) -0.25485(19) 0.8565(5) 0.0511(6) Uani 1 d . . . S2 S 0.24869(17) 0.06866(17) -0.2832(4) 0.0425(5) Uani 1 d . . . N1 N 0.4509(6) -0.1135(6) 0.5214(15) 0.0454(19) Uani 1 d . . . C1 C 0.4200(6) -0.1703(7) 0.6637(17) 0.0372(19) Uani 1 d . . . N2 N 0.3896(6) 0.0505(6) 0.1011(13) 0.0467(19) Uani 1 d . . . C2 C 0.3317(6) 0.0592(6) -0.0569(16) 0.0334(18) Uani 1 d . . . N3 N 0.1692(6) -0.2051(7) 0.4373(19) 0.056(2) Uani 1 d . . . H3N H 0.2067 -0.2646 0.4411 0.21(10) Uiso 1 d R . . C3 C 0.1014(8) -0.1992(7) 0.624(2) 0.055(3) Uani 1 d . . . H3 H 0.0990 -0.2532 0.7435 0.080 Uiso 1 d R . . C4 C 0.0326(6) -0.1183(6) 0.6267(17) 0.038(2) Uani 1 d . . . H4 H -0.0170 -0.1137 0.7579 0.080 Uiso 1 d R . . C5 C 0.0363(5) -0.0437(6) 0.4456(14) 0.0306(17) Uani 1 d . . . C6 C 0.1099(6) -0.0513(7) 0.2629(16) 0.043(2) Uani 1 d . . . H6 H 0.1120 -0.0018 0.1323 0.080 Uiso 1 d R . . C7 C 0.1780(7) -0.1334(8) 0.267(2) 0.055(3) Uani 1 d . . . H7 H 0.2319 -0.1392 0.1462 0.080 Uiso 1 d R . . 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 0.0392(6) 0.0372(6) 0.0260(6) 0.000 0.000 0.0015(7) S1 0.0544(13) 0.0465(11) 0.0524(15) 0.0145(12) 0.0175(13) 0.0098(11) S2 0.0404(10) 0.0450(11) 0.0421(12) 0.0001(11) -0.0079(11) -0.0063(10) N1 0.053(4) 0.042(4) 0.041(4) 0.007(4) 0.006(4) 0.003(4) C1 0.035(4) 0.044(4) 0.033(4) 0.001(5) 0.010(4) 0.009(4) N2 0.045(4) 0.058(4) 0.037(4) 0.002(4) -0.012(4) 0.004(4) C2 0.032(4) 0.029(4) 0.039(4) -0.001(4) 0.005(4) -0.001(3) N3 0.037(4) 0.048(5) 0.083(7) -0.013(5) -0.018(5) 0.011(4) C3 0.055(6) 0.041(5) 0.070(7) 0.000(5) -0.027(6) -0.003(4) C4 0.035(4) 0.033(4) 0.045(5) 0.001(4) -0.008(4) -0.002(3) C5 0.025(3) 0.035(4) 0.032(4) -0.008(4) -0.001(3) -0.003(3) C6 0.040(4) 0.052(5) 0.037(4) -0.005(4) 0.008(4) 0.003(4) C7 0.045(5) 0.054(6) 0.066(7) -0.016(6) -0.004(5) 0.010(5) _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 N1 1.953(8) 2_655 ? Zn1 N1 1.953(8) . yes Zn1 N2 1.965(7) . yes Zn1 N2 1.965(7) 2_655 ? S1 C1 1.636(9) . yes S2 C2 1.638(9) . yes N1 C1 1.144(11) . yes N2 C2 1.146(10) . yes N3 C7 1.321(13) . ? N3 C3 1.344(14) . ? C3 C4 1.377(12) . ? C4 C5 1.385(11) . ? C5 C6 1.381(11) . ? C5 C5 1.474(15) . ? C6 C7 1.382(13) . ? 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 Zn1 N1 110.7(5) 2_655 . yes N1 Zn1 N2 109.0(3) 2_655 . yes N1 Zn1 N2 111.1(3) . . yes N1 Zn1 N2 111.1(3) 2_655 2_655 yes N1 Zn1 N2 109.0(3) . 2_655 yes N2 Zn1 N2 105.9(5) . 2_655 yes C1 N1 Zn1 171.0(7) . . yes N1 C1 S1 177.3(9) . . yes C2 N2 Zn1 163.4(8) . . yes N2 C2 S2 178.6(8) . . yes C7 N3 C3 123.2(9) . . ? N3 C3 C4 118.2(10) . . ? C3 C4 C5 120.3(9) . . ? C6 C5 C4 119.3(7) . . ? C6 C5 C5 119.5(7) . 2 ? C4 C5 C5 121.2(6) . 2 ? C5 C6 C7 118.6(9) . . ? N3 C7 C6 120.2(9) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.558 _refine_diff_density_min -0.396 _refine_diff_density_rms 0.103 #_eof #End of Crystallographic Information File