Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 186 _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name 'Brooker, Sally' 'de Geest, Duncan J.' 'Kelly, Robert J.' 'Moubaraki, Boujemaa' 'Murray, Keith S.' 'Plieger, Paul G.' _publ_contact_author_name 'Dr Sally Brooker' _publ_contact_author_address ; Chemistry University of Otago PO Box 56 Dunedin NEW ZEALAND ; _publ_contact_author_email 'SBROOKER@ALKALI.OTAGO.AC.NZ' _publ_section_title ; Exchange coupled high-spin, low-spin and spin-crossover dicobalt(II) complexes of a pyridazine-containing Schiff-base macrocycle: control of cobalt(II) spin state by choice of axial ligands ; data_codt _database_code_CSD 175886 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H36 Co2 N8 O20 S4' _chemical_formula_weight 930.65 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' '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 triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.285(3) _cell_length_b 10.959(3) _cell_length_c 11.605(4) _cell_angle_alpha 64.045(4) _cell_angle_beta 69.945(4) _cell_angle_gamma 85.962(4) _cell_volume 886.0(5) _cell_formula_units_Z 1 _cell_measurement_temperature 163(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'rectangular prism' _exptl_crystal_colour orange _exptl_crystal_size_max 0.75 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.744 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 478 _exptl_absorpt_coefficient_mu 1.262 _exptl_absorpt_correction_type 'semi-empirical(SADABS)' _exptl_absorpt_correction_T_min 0.81 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 163(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 'Bruker SMART area detector' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11375 _diffrn_reflns_av_R_equivalents 0.0212 _diffrn_reflns_av_sigmaI/netI 0.0159 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 27.41 _reflns_number_total 3716 _reflns_number_gt 3426 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution ? _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0440P)^2^+0.6165P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3716 _refine_ls_number_parameters 235 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0309 _refine_ls_R_factor_gt 0.0285 _refine_ls_wR_factor_ref 0.0776 _refine_ls_wR_factor_gt 0.0765 _refine_ls_goodness_of_fit_ref 1.055 _refine_ls_restrained_S_all 1.055 _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 Co1 Co 0.60858(3) 0.84277(2) 0.50085(2) 0.01883(9) Uani 1 1 d . . . N1 N 0.61847(19) 1.02269(15) 0.32217(15) 0.0173(3) Uani 1 1 d . . . N2 N 0.54881(19) 1.13632(15) 0.32195(15) 0.0177(3) Uani 1 1 d . . . C2 C 0.5724(2) 1.24841(18) 0.20306(18) 0.0189(4) Uani 1 1 d . . . C3 C 0.6711(2) 1.2511(2) 0.07664(19) 0.0220(4) Uani 1 1 d . . . H3 H 0.6900 1.3317 -0.0062 0.026 Uiso 1 1 calc R . . C4 C 0.7399(2) 1.1324(2) 0.07664(19) 0.0218(4) Uani 1 1 d . . . H4 H 0.8051 1.1281 -0.0064 0.026 Uiso 1 1 calc R . . C5 C 0.7105(2) 1.01889(18) 0.20304(18) 0.0184(3) Uani 1 1 d . . . N3 N 0.7689(2) 0.79950(16) 0.34325(17) 0.0240(3) Uani 1 1 d . . . C6 C 0.7864(2) 0.88693(19) 0.22100(19) 0.0211(4) Uani 1 1 d . . . H6 H 0.8453 0.8686 0.1450 0.025 Uiso 1 1 calc R . . C8 C 0.8559(3) 0.6720(2) 0.3691(2) 0.0334(5) Uani 1 1 d . . . H8A H 0.9701 0.6875 0.3725 0.040 Uiso 1 1 calc R . . H8B H 0.8754 0.6492 0.2920 0.040 Uiso 1 1 calc R . . C9 C 0.7532(3) 0.5522(2) 0.5012(2) 0.0343(5) Uani 1 1 d . . . H9A H 0.8080 0.4688 0.5015 0.041 Uiso 1 1 calc R . . H9B H 0.6364 0.5434 0.4989 0.041 Uiso 1 1 calc R . . C10 C 0.7317(3) 0.5529(2) 0.6365(2) 0.0314(5) Uani 1 1 d . . . H10A H 0.6800 0.4622 0.7120 0.038 Uiso 1 1 calc R . . H10B H 0.8468 0.5694 0.6379 0.038 Uiso 1 1 calc R . . N4 N 0.6215(2) 0.65824(16) 0.65974(16) 0.0233(3) Uani 1 1 d . . . C11 C 0.4763(2) 1.36297(19) 0.22003(19) 0.0214(4) Uani 1 1 d . . . H11 H 0.4875 1.4488 0.1440 0.026 Uiso 1 1 calc R . . O1 O 0.81379(18) 0.93432(15) 0.50888(14) 0.0263(3) Uani 1 1 d . . . H1OA H 0.8656 1.0111 0.4354 0.032 Uiso 1 1 d R . . H1OB H 0.8059 0.9465 0.5869 0.032 Uiso 1 1 d R . . O2 O 0.3927(2) 0.76462(16) 0.49736(15) 0.0349(4) Uani 1 1 d . . . H2OA H 0.3774 0.7783 0.4183 0.042 Uiso 1 1 d R . . H2OB H 0.3115 0.7058 0.5756 0.042 Uiso 1 1 d R . . O3 O 0.3550(2) 0.79844(17) 1.26300(17) 0.0401(4) Uani 1 1 d . . . H3OA H 0.3326 0.8862 1.2233 0.048 Uiso 1 1 d R . . H3OB H 0.4328 0.7829 1.2036 0.048 Uiso 1 1 d R . . O4 O 1.1212(2) 0.60988(16) 0.71714(16) 0.0372(4) Uani 1 1 d . . . H4OA H 1.1118 0.5264 0.7957 0.045 Uiso 1 1 d R . . H4OB H 1.0613 0.6581 0.7543 0.045 Uiso 1 1 d R . . S20 S 0.85593(6) 0.88286(4) 0.83327(4) 0.01906(11) Uani 1 1 d . . . S21 S 0.75895(6) 0.68720(5) 1.00404(5) 0.02341(12) Uani 1 1 d . . . O21 O 0.8804(2) 0.97085(15) 0.89137(15) 0.0305(3) Uani 1 1 d . . . O22 O 0.72581(18) 0.92526(15) 0.76794(14) 0.0287(3) Uani 1 1 d . . . O23 O 1.01583(17) 0.85619(14) 0.74624(13) 0.0243(3) Uani 1 1 d . . . O24 O 0.5920(2) 0.70873(17) 1.08472(17) 0.0427(4) Uani 1 1 d . . . O25 O 0.7499(2) 0.59863(15) 0.94266(16) 0.0356(4) Uani 1 1 d . . . O26 O 0.8865(2) 0.65722(16) 1.06992(16) 0.0376(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 Co1 0.02464(15) 0.01583(13) 0.01332(13) -0.00623(10) -0.00360(10) 0.00103(9) N1 0.0185(7) 0.0181(7) 0.0153(7) -0.0078(6) -0.0047(6) -0.0002(6) N2 0.0209(7) 0.0163(7) 0.0155(7) -0.0061(6) -0.0066(6) -0.0002(6) C2 0.0190(8) 0.0184(8) 0.0169(8) -0.0060(7) -0.0050(7) -0.0025(7) C3 0.0232(9) 0.0235(9) 0.0149(8) -0.0052(7) -0.0053(7) -0.0017(7) C4 0.0223(9) 0.0274(10) 0.0143(8) -0.0091(7) -0.0043(7) -0.0009(7) C5 0.0176(8) 0.0219(9) 0.0170(8) -0.0096(7) -0.0053(7) -0.0016(7) N3 0.0299(9) 0.0199(8) 0.0208(8) -0.0110(7) -0.0047(7) 0.0026(6) C6 0.0227(9) 0.0229(9) 0.0177(9) -0.0115(7) -0.0032(7) -0.0004(7) C8 0.0444(13) 0.0267(11) 0.0265(11) -0.0140(9) -0.0081(9) 0.0123(9) C9 0.0441(13) 0.0267(10) 0.0334(12) -0.0162(9) -0.0125(10) 0.0098(9) C10 0.0412(12) 0.0217(10) 0.0260(10) -0.0093(8) -0.0082(9) 0.0092(8) N4 0.0302(9) 0.0165(7) 0.0210(8) -0.0078(6) -0.0071(7) 0.0019(6) C11 0.0249(9) 0.0169(8) 0.0201(9) -0.0061(7) -0.0073(7) -0.0006(7) O1 0.0274(7) 0.0298(7) 0.0163(6) -0.0065(6) -0.0048(5) -0.0048(6) O2 0.0395(9) 0.0418(9) 0.0190(7) -0.0106(7) -0.0049(6) -0.0161(7) O3 0.0613(11) 0.0321(8) 0.0300(8) -0.0163(7) -0.0186(8) 0.0178(8) O4 0.0427(9) 0.0259(8) 0.0279(8) -0.0102(6) 0.0023(7) 0.0052(6) S20 0.0217(2) 0.0187(2) 0.0150(2) -0.00740(17) -0.00403(17) -0.00019(16) S21 0.0271(2) 0.0212(2) 0.0166(2) -0.00609(18) -0.00367(18) -0.00220(18) O21 0.0390(8) 0.0275(7) 0.0264(7) -0.0165(6) -0.0055(6) -0.0038(6) O22 0.0272(7) 0.0315(8) 0.0237(7) -0.0082(6) -0.0102(6) 0.0041(6) O23 0.0235(7) 0.0254(7) 0.0191(7) -0.0094(6) -0.0020(5) -0.0001(5) O24 0.0364(9) 0.0390(9) 0.0300(8) -0.0097(7) 0.0083(7) -0.0021(7) O25 0.0490(9) 0.0246(7) 0.0315(8) -0.0117(6) -0.0109(7) -0.0076(7) O26 0.0488(10) 0.0311(8) 0.0295(8) -0.0038(7) -0.0217(7) -0.0006(7) _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 O2 2.0564(16) . y Co1 O1 2.0825(15) . y Co1 N3 2.0828(17) . y Co1 N4 2.0837(17) . y Co1 N2 2.1245(16) 2_676 y Co1 N1 2.1264(16) . y N1 N2 1.334(2) . ? N1 C5 1.348(2) . ? N2 C2 1.348(2) . ? N2 Co1 2.1245(16) 2_676 ? C2 C3 1.402(3) . ? C2 C11 1.489(3) . ? C3 C4 1.383(3) . ? C4 C5 1.400(3) . ? C5 C6 1.493(3) . ? N3 C6 1.281(3) . ? N3 C8 1.484(3) . ? C8 C9 1.516(3) . ? C9 C10 1.521(3) . ? C10 N4 1.482(3) . ? N4 C11 1.275(3) 2_676 ? C11 N4 1.275(3) 2_676 ? S20 O21 1.4544(14) . ? S20 O22 1.4610(15) . ? S20 O23 1.4652(14) . ? S20 S21 2.1451(8) . ? S21 O26 1.4473(17) . ? S21 O24 1.4506(17) . ? S21 O25 1.4515(16) . ? 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 Co1 O1 174.95(6) . . y O2 Co1 N3 91.58(7) . . y O1 Co1 N3 92.61(6) . . y O2 Co1 N4 90.98(7) . . y O1 Co1 N4 91.37(6) . . y N3 Co1 N4 96.03(7) . . y O2 Co1 N2 88.89(6) . 2_676 y O1 Co1 N2 87.29(6) . 2_676 y N3 Co1 N2 173.06(6) . 2_676 y N4 Co1 N2 77.04(6) . 2_676 y O2 Co1 N1 89.89(6) . . y O1 Co1 N1 88.32(6) . . y N3 Co1 N1 76.89(7) . . y N4 Co1 N1 172.89(6) . . y N2 Co1 N1 110.03(6) 2_676 . y N2 N1 C5 120.03(15) . . ? N2 N1 Co1 124.77(11) . . ? C5 N1 Co1 115.11(12) . . ? N1 N2 C2 120.30(15) . . ? N1 N2 Co1 124.94(11) . 2_676 ? C2 N2 Co1 114.74(12) . 2_676 ? N2 C2 C3 121.95(17) . . ? N2 C2 C11 113.53(16) . . ? C3 C2 C11 124.43(17) . . ? C4 C3 C2 117.75(17) . . ? C3 C4 C5 117.83(17) . . ? N1 C5 C4 122.10(17) . . ? N1 C5 C6 113.42(16) . . ? C4 C5 C6 124.34(16) . . ? C6 N3 C8 120.61(16) . . ? C6 N3 Co1 116.95(13) . . ? C8 N3 Co1 122.42(13) . . ? N3 C6 C5 117.15(16) . . ? N3 C8 C9 113.02(18) . . ? C8 C9 C10 118.91(19) . . ? N4 C10 C9 112.62(18) . . ? C11 N4 C10 120.67(17) 2_676 . ? C11 N4 Co1 116.53(13) 2_676 . ? C10 N4 Co1 122.75(13) . . ? N4 C11 C2 117.64(17) 2_676 . ? O21 S20 O22 113.06(9) . . ? O21 S20 O23 114.54(9) . . ? O22 S20 O23 112.30(9) . . ? O21 S20 S21 105.30(7) . . ? O22 S20 S21 106.79(7) . . ? O23 S20 S21 103.81(6) . . ? O26 S21 O24 113.95(11) . . ? O26 S21 O25 114.63(10) . . ? O24 S21 O25 114.02(11) . . ? O26 S21 S20 103.69(7) . . ? O24 S21 S20 104.60(7) . . ? O25 S21 S20 104.27(7) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 Co1 N1 N2 94.34(14) . . . . ? O1 Co1 N1 N2 -80.94(14) . . . . ? N3 Co1 N1 N2 -174.01(15) . . . . ? N4 Co1 N1 N2 -168.6(4) . . . . ? N2 Co1 N1 N2 5.56(17) 2_676 . . . ? O2 Co1 N1 C5 -89.07(13) . . . . ? O1 Co1 N1 C5 95.65(13) . . . . ? N3 Co1 N1 C5 2.58(12) . . . . ? N4 Co1 N1 C5 8.0(5) . . . . ? N2 Co1 N1 C5 -177.85(12) 2_676 . . . ? C5 N1 N2 C2 -1.1(2) . . . . ? Co1 N1 N2 C2 175.33(12) . . . . ? C5 N1 N2 Co1 177.19(12) . . . 2_676 ? Co1 N1 N2 Co1 -6.38(19) . . . 2_676 ? N1 N2 C2 C3 -0.8(3) . . . . ? Co1 N2 C2 C3 -179.23(13) 2_676 . . . ? N1 N2 C2 C11 175.97(15) . . . . ? Co1 N2 C2 C11 -2.48(19) 2_676 . . . ? N2 C2 C3 C4 2.2(3) . . . . ? C11 C2 C3 C4 -174.16(17) . . . . ? C2 C3 C4 C5 -1.8(3) . . . . ? N2 N1 C5 C4 1.5(3) . . . . ? Co1 N1 C5 C4 -175.28(13) . . . . ? N2 N1 C5 C6 177.31(15) . . . . ? Co1 N1 C5 C6 0.55(19) . . . . ? C3 C4 C5 N1 0.0(3) . . . . ? C3 C4 C5 C6 -175.35(17) . . . . ? O2 Co1 N3 C6 83.57(15) . . . . ? O1 Co1 N3 C6 -93.62(15) . . . . ? N4 Co1 N3 C6 174.72(15) . . . . ? N2 Co1 N3 C6 177.4(4) 2_676 . . . ? N1 Co1 N3 C6 -5.95(14) . . . . ? O2 Co1 N3 C8 -94.68(17) . . . . ? O1 Co1 N3 C8 88.14(17) . . . . ? N4 Co1 N3 C8 -3.52(17) . . . . ? N2 Co1 N3 C8 -0.9(6) 2_676 . . . ? N1 Co1 N3 C8 175.80(17) . . . . ? C8 N3 C6 C5 -173.53(18) . . . . ? Co1 N3 C6 C5 8.2(2) . . . . ? N1 C5 C6 N3 -5.7(2) . . . . ? C4 C5 C6 N3 169.98(18) . . . . ? C6 N3 C8 C9 -147.16(19) . . . . ? Co1 N3 C8 C9 31.0(3) . . . . ? N3 C8 C9 C10 -68.5(3) . . . . ? C8 C9 C10 N4 68.5(3) . . . . ? C9 C10 N4 C11 146.1(2) . . . 2_676 ? C9 C10 N4 Co1 -31.1(2) . . . . ? O2 Co1 N4 C11 -82.00(15) . . . 2_676 ? O1 Co1 N4 C11 93.54(15) . . . 2_676 ? N3 Co1 N4 C11 -173.69(14) . . . 2_676 ? N2 Co1 N4 C11 6.64(14) 2_676 . . 2_676 ? N1 Co1 N4 C11 -179.0(4) . . . 2_676 ? O2 Co1 N4 C10 95.39(16) . . . . ? O1 Co1 N4 C10 -89.08(16) . . . . ? N3 Co1 N4 C10 3.69(17) . . . . ? N2 Co1 N4 C10 -175.98(17) 2_676 . . . ? N1 Co1 N4 C10 -1.6(6) . . . . ? N2 C2 C11 N4 -3.2(2) . . . 2_676 ? C3 C2 C11 N4 173.41(18) . . . 2_676 ? O21 S20 S21 O26 -54.90(10) . . . . ? O22 S20 S21 O26 -175.35(10) . . . . ? O23 S20 S21 O26 65.81(10) . . . . ? O21 S20 S21 O24 64.78(11) . . . . ? O22 S20 S21 O24 -55.67(11) . . . . ? O23 S20 S21 O24 -174.51(10) . . . . ? O21 S20 S21 O25 -175.20(10) . . . . ? O22 S20 S21 O25 64.35(10) . . . . ? O23 S20 S21 O25 -54.49(10) . . . . ? _diffrn_measured_fraction_theta_max 0.920 _diffrn_reflns_theta_full 27.41 _diffrn_measured_fraction_theta_full 0.920 _refine_diff_density_max 0.778 _refine_diff_density_min -0.581 _refine_diff_density_rms 0.068 data_cowr _database_code_CSD 175887 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H38 Cl4 Co2 N10 O22' _chemical_formula_weight 1054.28 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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Co' 'Co' 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.8623(16) _cell_length_b 10.5945(19) _cell_length_c 11.653(2) _cell_angle_alpha 69.380(2) _cell_angle_beta 85.619(2) _cell_angle_gamma 86.172(2) _cell_volume 1020.1(3) _cell_formula_units_Z 1 _cell_measurement_temperature 158(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour orange-red _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.716 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 538 _exptl_absorpt_coefficient_mu 1.168 _exptl_absorpt_correction_type 'semi-empirical (SADABS)' _exptl_absorpt_correction_T_min 0.77 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 158 _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 'CCD area detector' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11856 _diffrn_reflns_av_R_equivalents 0.0366 _diffrn_reflns_av_sigmaI/netI 0.0353 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 6 _diffrn_reflns_theta_min 2.89 _diffrn_reflns_theta_max 26.44 _reflns_number_total 3947 _reflns_number_gt 3277 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SMART' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0642P)^2^+5.4788P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3947 _refine_ls_number_parameters 271 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0806 _refine_ls_R_factor_gt 0.0675 _refine_ls_wR_factor_ref 0.1787 _refine_ls_wR_factor_gt 0.1717 _refine_ls_goodness_of_fit_ref 1.082 _refine_ls_restrained_S_all 1.082 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Co1 Co 0.12891(8) 0.34499(7) 0.04860(6) 0.0274(2) Uani 1 1 d . . . N1 N 0.0857(5) 0.4626(4) -0.1366(4) 0.0268(9) Uani 1 1 d . . . N2 N -0.0047(5) 0.5732(4) -0.1714(4) 0.0281(9) Uani 1 1 d . . . C2 C -0.0225(6) 0.6409(6) -0.2906(5) 0.0332(12) Uani 1 1 d . . . C3 C 0.0523(7) 0.6018(6) -0.3833(5) 0.0378(13) Uani 1 1 d . . . H3 H 0.0391 0.6521 -0.4675 0.045 Uiso 1 1 calc R . . C4 C 0.1464(6) 0.4872(6) -0.3476(5) 0.0350(12) Uani 1 1 d . . . H4 H 0.2001 0.4555 -0.4066 0.042 Uiso 1 1 calc R . . C5 C 0.1601(6) 0.4191(5) -0.2213(5) 0.0297(11) Uani 1 1 d . . . C6 C 0.2579(6) 0.2973(5) -0.1680(5) 0.0310(11) Uani 1 1 d . . . H6 H 0.3177 0.2583 -0.2191 0.037 Uiso 1 1 calc R . . N3 N 0.2602(5) 0.2458(4) -0.0518(4) 0.0323(10) Uani 1 1 d . . . C8 C 0.3542(7) 0.1229(6) 0.0075(6) 0.0399(13) Uani 1 1 d . . . H8A H 0.4417 0.1176 -0.0490 0.048 Uiso 1 1 calc R . . H8B H 0.2938 0.0426 0.0237 0.048 Uiso 1 1 calc R . . C9 C 0.4122(8) 0.1215(7) 0.1287(6) 0.0475(15) Uani 1 1 d . . . H9A H 0.4567 0.2095 0.1141 0.057 Uiso 1 1 calc R . . H9B H 0.4945 0.0510 0.1532 0.057 Uiso 1 1 calc R . . C10 C 0.2923(8) 0.0955(6) 0.2364(6) 0.0473(16) Uani 1 1 d . . . H10A H 0.2333 0.0172 0.2419 0.057 Uiso 1 1 calc R . . H10B H 0.3436 0.0730 0.3141 0.057 Uiso 1 1 calc R . . N4 N 0.1889(6) 0.2138(5) 0.2210(4) 0.0356(11) Uani 1 1 d . . . C11 C 0.1299(7) 0.2395(6) 0.3125(5) 0.0395(13) Uani 1 1 d . . . H11 H 0.1533 0.1841 0.3936 0.047 Uiso 1 1 calc R . . O1 O -0.0635(5) 0.2443(4) 0.0498(4) 0.0391(9) Uani 1 1 d . . . H1W1 H -0.0784 0.2211 -0.0111 0.047 Uiso 1 1 d . . . H2W1 H -0.0983 0.1821 0.1130 0.047 Uiso 1 1 d . . . O2 O 0.3030(5) 0.4727(4) 0.0349(4) 0.0390(9) Uani 1 1 d . . . H1W2 H 0.3257 0.4924 0.0959 0.047 Uiso 1 1 d . . . H2W2 H 0.3378 0.5332 -0.0296 0.047 Uiso 1 1 d . . . O3 O -0.0813(7) 0.1360(6) -0.1225(5) 0.0678(15) Uani 1 1 d . . . H1W3 H 0.0021 0.1019 -0.1417 0.081 Uiso 1 1 d . . . H2W3 H -0.1114 0.1984 -0.1865 0.081 Uiso 1 1 d . . . Cl1 Cl -0.19772(19) -0.04534(15) 0.33165(14) 0.0450(4) Uani 1 1 d . . . O11 O -0.1900(8) -0.0097(6) 0.2020(5) 0.0781(18) Uani 1 1 d . . . O12 O -0.3518(8) -0.0401(7) 0.3738(8) 0.113(3) Uani 1 1 d . . . O13 O -0.1242(11) 0.0481(10) 0.3617(10) 0.136(3) Uani 1 1 d . . . O14 O -0.1410(10) -0.1808(6) 0.3838(6) 0.102(3) Uani 1 1 d . . . Cl2 Cl 0.3360(2) 0.6016(2) 0.30391(18) 0.0624(5) Uani 1 1 d . . . O21 O 0.3541(10) 0.6416(10) 0.1762(6) 0.122(3) Uani 1 1 d . . . O22 O 0.2234(9) 0.6797(8) 0.3432(6) 0.096(2) Uani 1 1 d . . . O23 O 0.4763(7) 0.5968(7) 0.3564(6) 0.0804(18) Uani 1 1 d . . . O24 O 0.2894(9) 0.4656(9) 0.3522(12) 0.150(4) Uani 1 1 d . . . N30 N 0.3695(7) 0.6503(6) -0.2064(5) 0.0542(15) Uani 1 1 d . . . C30 C 0.3969(8) 0.6986(7) -0.3086(6) 0.0502(16) Uani 1 1 d . . . C31 C 0.4304(11) 0.7615(8) -0.4413(7) 0.071(2) Uani 1 1 d . . . H31A H 0.3355 0.7931 -0.4825 0.085 Uiso 1 1 calc R . . H31B H 0.4832 0.6951 -0.4728 0.085 Uiso 1 1 calc R . . H31C H 0.4947 0.8382 -0.4571 0.085 Uiso 1 1 calc 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 0.0299(4) 0.0240(4) 0.0251(4) -0.0063(3) 0.0030(3) 0.0027(3) N1 0.026(2) 0.025(2) 0.029(2) -0.0085(17) 0.0037(17) -0.0023(17) N2 0.027(2) 0.028(2) 0.027(2) -0.0078(18) 0.0022(17) 0.0002(17) C2 0.038(3) 0.033(3) 0.026(3) -0.008(2) 0.000(2) 0.001(2) C3 0.043(3) 0.043(3) 0.026(3) -0.011(2) -0.003(2) 0.003(3) C4 0.036(3) 0.044(3) 0.028(3) -0.016(2) 0.002(2) -0.001(2) C5 0.027(3) 0.033(3) 0.031(3) -0.014(2) 0.004(2) -0.005(2) C6 0.029(3) 0.031(3) 0.037(3) -0.018(2) 0.005(2) 0.001(2) N3 0.034(2) 0.029(2) 0.035(3) -0.0137(19) 0.0019(19) 0.0035(18) C8 0.045(3) 0.029(3) 0.044(3) -0.013(3) -0.002(3) 0.011(2) C9 0.050(4) 0.045(4) 0.048(4) -0.018(3) -0.010(3) 0.013(3) C10 0.061(4) 0.037(3) 0.039(3) -0.010(3) -0.010(3) 0.020(3) N4 0.041(3) 0.031(2) 0.031(2) -0.0074(19) -0.005(2) 0.008(2) C11 0.044(3) 0.043(3) 0.025(3) -0.006(2) -0.005(2) 0.009(3) O1 0.042(2) 0.040(2) 0.034(2) -0.0107(17) 0.0078(17) -0.0146(18) O2 0.044(2) 0.041(2) 0.032(2) -0.0104(17) 0.0010(17) -0.0089(18) O3 0.082(4) 0.072(4) 0.059(3) -0.035(3) 0.000(3) -0.006(3) Cl1 0.0543(9) 0.0393(8) 0.0371(8) -0.0088(6) 0.0008(6) -0.0011(7) O11 0.120(5) 0.057(3) 0.044(3) -0.007(2) 0.003(3) 0.018(3) O12 0.081(5) 0.090(5) 0.139(7) -0.013(5) 0.051(4) -0.020(4) O13 0.126(7) 0.136(7) 0.190(10) -0.104(7) -0.038(7) -0.024(6) O14 0.173(7) 0.061(4) 0.058(4) -0.009(3) -0.025(4) 0.048(4) Cl2 0.0547(10) 0.0910(14) 0.0584(11) -0.0469(10) 0.0122(8) -0.0209(10) O21 0.153(8) 0.166(8) 0.058(4) -0.061(5) -0.022(4) 0.042(6) O22 0.111(5) 0.115(6) 0.064(4) -0.042(4) 0.013(4) 0.012(4) O23 0.064(4) 0.113(5) 0.079(4) -0.050(4) 0.000(3) -0.017(3) O24 0.079(5) 0.106(6) 0.281(13) -0.087(8) 0.020(6) -0.043(5) N30 0.061(4) 0.060(4) 0.041(3) -0.015(3) 0.007(3) -0.027(3) C30 0.062(4) 0.045(4) 0.045(4) -0.017(3) 0.006(3) -0.016(3) C31 0.114(7) 0.056(4) 0.040(4) -0.015(3) 0.025(4) -0.016(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 Co1 O1 2.068(4) . Y Co1 O2 2.079(4) . Y Co1 N3 2.080(4) . Y Co1 N4 2.085(5) . Y Co1 N2 2.125(4) 2_565 Y Co1 N1 2.127(4) . Y N1 N2 1.330(6) . ? N1 C5 1.342(7) . ? N2 C2 1.336(7) . ? N2 Co1 2.125(4) 2_565 ? C2 C3 1.395(8) . ? C2 C11 1.492(8) 2_565 ? C3 C4 1.380(8) . ? C4 C5 1.403(8) . ? C5 C6 1.474(7) . ? C6 N3 1.270(7) . ? N3 C8 1.475(7) . ? C8 C9 1.534(9) . ? C9 C10 1.541(9) . ? C10 N4 1.468(7) . ? N4 C11 1.259(7) . ? C11 C2 1.492(8) 2_565 ? Cl1 O13 1.375(7) . ? Cl1 O11 1.420(5) . ? Cl1 O14 1.420(6) . ? Cl1 O12 1.420(7) . ? Cl2 O21 1.395(7) . ? Cl2 O22 1.406(7) . ? Cl2 O23 1.418(6) . ? Cl2 O24 1.428(8) . ? N30 C30 1.133(8) . ? C30 C31 1.467(9) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Co1 O2 171.37(16) . . Y O1 Co1 N3 93.38(17) . . Y O2 Co1 N3 91.24(17) . . Y O1 Co1 N4 93.95(18) . . Y O2 Co1 N4 92.80(18) . . Y N3 Co1 N4 96.04(18) . . Y O1 Co1 N2 87.00(16) . 2_565 Y O2 Co1 N2 89.33(16) . 2_565 Y N3 Co1 N2 172.73(18) . 2_565 Y N4 Co1 N2 76.70(18) . 2_565 Y O1 Co1 N1 86.38(16) . . Y O2 Co1 N1 87.60(16) . . Y N3 Co1 N1 76.64(17) . . Y N4 Co1 N1 172.68(17) . . Y N2 Co1 N1 110.62(16) 2_565 . Y N2 N1 C5 120.0(4) . . ? N2 N1 Co1 124.9(3) . . Y C5 N1 Co1 115.0(3) . . ? N1 N2 C2 120.2(4) . . ? N1 N2 Co1 124.4(3) . 2_565 Y C2 N2 Co1 115.4(3) . 2_565 ? N2 C2 C3 122.7(5) . . ? N2 C2 C11 112.9(5) . 2_565 ? C3 C2 C11 124.4(5) . 2_565 ? C4 C3 C2 117.3(5) . . ? C3 C4 C5 117.7(5) . . ? N1 C5 C4 122.0(5) . . ? N1 C5 C6 113.3(5) . . ? C4 C5 C6 124.7(5) . . ? N3 C6 C5 118.3(5) . . ? C6 N3 C8 121.0(5) . . ? C6 N3 Co1 116.7(4) . . Y C8 N3 Co1 122.2(4) . . ? N3 C8 C9 111.9(5) . . ? C8 C9 C10 115.4(6) . . ? N4 C10 C9 111.5(5) . . ? C11 N4 C10 121.0(5) . . ? C11 N4 Co1 116.7(4) . . Y C10 N4 Co1 122.3(4) . . ? N4 C11 C2 118.4(5) . 2_565 ? O13 Cl1 O11 109.2(6) . . ? O13 Cl1 O14 115.2(6) . . ? O11 Cl1 O14 108.2(4) . . ? O13 Cl1 O12 107.4(6) . . ? O11 Cl1 O12 108.9(5) . . ? O14 Cl1 O12 107.8(5) . . ? O21 Cl2 O22 112.7(5) . . ? O21 Cl2 O23 111.1(5) . . ? O22 Cl2 O23 112.5(4) . . ? O21 Cl2 O24 109.0(7) . . ? O22 Cl2 O24 106.7(5) . . ? O23 Cl2 O24 104.3(5) . . ? N30 C30 C31 179.3(8) . . ? _diffrn_measured_fraction_theta_max 0.940 _diffrn_reflns_theta_full 26.44 _diffrn_measured_fraction_theta_full 0.940 _refine_diff_density_max 1.491 _refine_diff_density_min -0.763 _refine_diff_density_rms 0.111 data_c2uponm _database_code_CSD 179659 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C21 H20 Cl Co2 N11 O7' _chemical_formula_weight 691.79 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Co' 'Co' 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/m 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' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z' _cell_length_a 10.225(2) _cell_length_b 22.337(5) _cell_length_c 11.066(2) _cell_angle_alpha 90.00 _cell_angle_beta 98.84(3) _cell_angle_gamma 90.00 _cell_volume 2497.4(9) _cell_formula_units_Z 4 _cell_measurement_temperature 158(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.840 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1400 _exptl_absorpt_coefficient_mu 1.505 _exptl_absorpt_correction_type 'Semi-empirical(SADABS)' _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 158(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 'Bruker SMART area detector' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1880 _diffrn_reflns_av_R_equivalents 0.0779 _diffrn_reflns_av_sigmaI/netI 0.0519 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -5 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min -3 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.09 _diffrn_reflns_theta_max 26.55 _reflns_number_total 1619 _reflns_number_gt 1469 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; The structure was solved in C2 and refined to R1=0.16 (observed data). At this point high correlation among parameters and a mirror plane relating one half of the structure to the other were apparent. Refinement continued in space group C2/m to R1=0.16. A large number of weakly observed reflections had Fo>Fc. About 20 reflections with especially poor agreement between Fo and Fc, with respect to the esd of Fo, were eliminated. Refinement then converged at R1=0.148. All atoms have chemically sensible anisotropic displacement parameters, with no restraints imposed. The structure could also be solved and refined to R1=0.21 in space group P2(1)/c. The molecular structure is identical to that in space group C2/m. There are many significant violations of the class of systematic absences arising form the assumption of C centering. There are also a reasonable fraction of reflections arising from the c glide in space goup P2(1)/c that are significantly observed. While the crystal quality was not good, data processing statistics would indicate that refinement should have converged at values for R1 of ca. 0.08 or better. Various twinning models were tried, but there is no support for any twinning, at least within the monoclinic crystal system. Intrinsic monoclinicity is inferred from the lack of violations of the class of systematic absence arising from a 2(1) screw axis. Inspection of the structure reveals that the NCO ligands are all tilted away from a pseudo-mirror plane that passes through the Co-Co vector. We suspect, but are not at this stage in a position to confirm, that this structure is either modulated (leading to intensity at positions where zero intensity from systematic absences are expected) or is a composite of structures in space groups C2/m and P2(1)/c -- perhaps due to a phase transition near the data collection temperature. In any event, the average molecular structure of the dicobalt complex incarcerated in this this crystal is unequivocally established, and reliance can be placed on metrical parameters derived from this structure, noting that esds are quite large. 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^)+(0.0918P)^2^+156.2998P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1619 _refine_ls_number_parameters 195 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1545 _refine_ls_R_factor_gt 0.1474 _refine_ls_wR_factor_ref 0.3329 _refine_ls_wR_factor_gt 0.3281 _refine_ls_goodness_of_fit_ref 1.128 _refine_ls_restrained_S_all 1.128 _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 Co2 Co 0.4165(2) 0.91940(10) 0.2690(2) 0.0410(9) Uani 1 1 d . . . Cl2 Cl 1.0000 0.8810(3) 0.0000 0.058(2) Uani 1 2 d S . . O21 O 1.0907(13) 0.9186(6) 0.0769(13) 0.066(5) Uani 1 1 d . . . O22 O 0.9276(19) 0.8445(12) 0.072(3) 0.149(12) Uani 1 1 d . . . N7 N 0.3742(12) 0.9702(6) 0.1000(15) 0.039(4) Uani 1 1 d . . . N121 N 0.5085(19) 1.0000 0.3404(18) 0.041(6) Uani 1 2 d S . . C122 C 0.629(2) 1.0000 0.378(2) 0.040(6) Uani 1 2 d S . . O123 O 0.7442(17) 1.0000 0.4182(18) 0.054(6) Uani 1 2 d S . . N131 N 0.5826(14) 0.8726(6) 0.3278(14) 0.043(4) Uani 1 1 d . . . C132 C 0.6952(18) 0.8650(9) 0.3605(19) 0.056(6) Uani 1 1 d . . . O133 O 0.8149(12) 0.8551(6) 0.3891(13) 0.057(4) Uani 1 1 d . . . N1 N 0.2808(16) 0.8570(7) 0.3300(16) 0.059(6) Uani 1 1 d . . . N2 N 0.2479(14) 0.9699(6) 0.3064(16) 0.048(4) Uani 1 1 d . . . N8 N 0.3850(13) 0.8554(7) 0.1197(15) 0.046(5) Uani 1 1 d . . . C1 C 0.166(2) 0.8753(9) 0.3412(18) 0.053(6) Uani 1 1 d . . . H1A H 0.0972 0.8484 0.3532 0.063 Uiso 1 1 calc R . . C2 C 0.1444(16) 0.9427(9) 0.3342(18) 0.049(5) Uani 1 1 d . . . C3 C 0.0313(17) 0.9715(9) 0.353(2) 0.052(6) Uani 1 1 d . . . H3A H -0.0452 0.9496 0.3654 0.062 Uiso 1 1 calc R . . C10 C 0.2893(16) 0.9696(8) -0.110(2) 0.052(6) Uani 1 1 d . . . H10A H 0.2575 0.9476 -0.1819 0.062 Uiso 1 1 calc R . . C11 C 0.3361(16) 0.9415(9) -0.0037(19) 0.052(6) Uani 1 1 d . . . C12 C 0.3443(15) 0.8778(7) 0.0138(17) 0.038(4) Uani 1 1 d . . . H12 H 0.3193 0.8518 -0.0539 0.045 Uiso 1 1 calc R . . C13 C 0.3963(18) 0.7905(8) 0.137(2) 0.051(6) Uani 1 1 d . . . H13A H 0.3867 0.7706 0.0561 0.061 Uiso 1 1 calc R . . H13B H 0.4851 0.7807 0.1817 0.061 Uiso 1 1 calc R . . C14 C 0.295(2) 0.7680(7) 0.2052(17) 0.048(5) Uani 1 1 d . . . H14A H 0.3014 0.7238 0.2093 0.057 Uiso 1 1 calc R . . H14B H 0.2068 0.7783 0.1597 0.057 Uiso 1 1 calc R . . C15 C 0.3051(19) 0.7926(8) 0.3362(19) 0.050(5) Uani 1 1 d . . . H15A H 0.2389 0.7728 0.3792 0.060 Uiso 1 1 calc R . . H15B H 0.3942 0.7845 0.3821 0.060 Uiso 1 1 calc 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 Co2 0.0236(13) 0.0575(15) 0.0411(15) 0.0003(10) 0.0026(12) -0.0021(10) Cl2 0.030(4) 0.049(4) 0.088(6) 0.000 -0.010(4) 0.000 O21 0.048(8) 0.088(10) 0.056(10) -0.023(7) -0.011(8) -0.019(7) O22 0.051(11) 0.18(2) 0.22(3) 0.10(2) 0.044(16) -0.024(13) N7 0.012(6) 0.038(6) 0.067(11) -0.003(6) 0.005(8) 0.011(5) N121 0.027(11) 0.070(14) 0.027(12) 0.000 0.003(10) 0.000 C122 0.024(13) 0.066(16) 0.034(15) 0.000 0.017(13) 0.000 O123 0.026(9) 0.086(13) 0.049(13) 0.000 0.000(10) 0.000 N131 0.032(8) 0.041(8) 0.056(10) -0.005(6) 0.009(8) 0.007(6) C132 0.032(10) 0.077(13) 0.057(14) -0.014(10) -0.004(11) 0.016(10) O133 0.025(7) 0.084(10) 0.062(10) -0.010(7) 0.008(8) 0.004(6) N1 0.045(10) 0.063(10) 0.062(12) 0.011(8) -0.013(10) -0.010(8) N2 0.031(8) 0.060(8) 0.053(11) -0.006(7) 0.006(8) 0.001(7) N8 0.013(7) 0.060(9) 0.063(11) -0.002(7) -0.001(8) -0.001(6) C1 0.040(12) 0.070(12) 0.047(12) 0.004(9) 0.002(11) -0.005(10) C2 0.014(8) 0.087(14) 0.047(13) -0.001(9) 0.010(10) -0.021(9) C3 0.015(8) 0.097(14) 0.048(14) -0.006(9) 0.021(10) 0.002(8) C10 0.026(9) 0.049(9) 0.075(15) 0.004(9) -0.013(11) -0.012(8) C11 0.019(9) 0.086(14) 0.051(13) -0.023(10) 0.002(10) -0.019(9) C12 0.021(9) 0.037(9) 0.057(12) 0.006(7) 0.013(9) -0.007(7) C13 0.034(10) 0.050(10) 0.070(14) -0.002(8) 0.009(11) 0.014(8) C14 0.058(12) 0.032(9) 0.051(12) -0.011(7) 0.004(11) -0.011(8) C15 0.036(11) 0.050(11) 0.063(13) 0.010(8) 0.007(11) 0.004(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 Co2 N131 2.015(13) . ? Co2 N121 2.127(9) . ? Co2 N1 2.147(18) . ? Co2 N2 2.154(17) . ? Co2 N8 2.170(16) . ? Co2 N7 2.173(15) . ? Cl2 O22 1.42(2) 2_755 ? Cl2 O22 1.42(2) . ? Cl2 O21 1.430(11) . ? Cl2 O21 1.430(11) 2_755 ? N7 C11 1.32(2) . ? N7 N7 1.33(3) 6_575 ? N121 C122 1.23(3) . ? N121 Co2 2.127(9) 6_575 ? C122 O123 1.20(3) . ? N131 C132 1.17(2) . ? C132 O133 1.235(19) . ? N1 C1 1.27(3) . ? N1 C15 1.46(2) . ? N2 C2 1.30(3) . ? N2 N2 1.34(3) 6_575 ? N8 C12 1.28(2) . ? N8 C13 1.46(2) . ? C1 C2 1.52(3) . ? C2 C3 1.37(3) . ? C3 C3 1.27(4) 6_575 ? C10 C11 1.35(3) . ? C10 C10 1.36(3) 6_575 ? C11 C12 1.44(3) . ? C13 C14 1.46(3) . ? C14 C15 1.54(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 N131 Co2 N121 90.9(6) . . ? N131 Co2 N1 96.6(6) . . ? N121 Co2 N1 134.6(8) . . ? N131 Co2 N2 150.4(6) . . ? N121 Co2 N2 78.8(7) . . ? N1 Co2 N2 72.8(7) . . ? N131 Co2 N8 85.6(5) . . ? N121 Co2 N8 147.8(8) . . ? N1 Co2 N8 77.6(7) . . ? N2 Co2 N8 117.5(5) . . ? N131 Co2 N7 126.5(6) . . ? N121 Co2 N7 84.0(6) . . ? N1 Co2 N7 123.8(5) . . ? N2 Co2 N7 80.3(6) . . ? N8 Co2 N7 72.7(6) . . ? O22 Cl2 O22 110(3) 2_755 . ? O22 Cl2 O21 108.8(10) 2_755 . ? O22 Cl2 O21 110.5(14) . . ? O22 Cl2 O21 110.5(14) 2_755 2_755 ? O22 Cl2 O21 108.8(10) . 2_755 ? O21 Cl2 O21 108.2(12) . 2_755 ? C11 N7 N7 119.1(11) . 6_575 ? C11 N7 Co2 119.2(13) . . ? N7 N7 Co2 121.5(4) 6_575 . ? C122 N121 Co2 119.0(7) . . ? C122 N121 Co2 119.0(7) . 6_575 ? Co2 N121 Co2 115.7(7) . 6_575 ? O123 C122 N121 178(3) . . ? C132 N131 Co2 156.9(15) . . ? N131 C132 O133 176(2) . . ? C1 N1 C15 117.8(18) . . ? C1 N1 Co2 118.4(14) . . ? C15 N1 Co2 122.7(15) . . ? C2 N2 N2 118.0(12) . 6_575 ? C2 N2 Co2 120.3(13) . . ? N2 N2 Co2 121.6(4) 6_575 . ? C12 N8 C13 120.8(16) . . ? C12 N8 Co2 115.4(12) . . ? C13 N8 Co2 123.6(13) . . ? N1 C1 C2 116.3(18) . . ? N2 C2 C3 124(2) . . ? N2 C2 C1 111.0(18) . . ? C3 C2 C1 125.3(19) . . ? C3 C3 C2 118.1(12) 6_575 . ? C11 C10 C10 117.7(11) . 6_575 ? N7 C11 C10 123.2(19) . . ? N7 C11 C12 111.1(17) . . ? C10 C11 C12 125.6(16) . . ? N8 C12 C11 120.8(16) . . ? C14 C13 N8 111.1(16) . . ? C13 C14 C15 114.4(15) . . ? N1 C15 C14 108.8(15) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N131 Co2 N7 C11 78.5(14) . . . . ? N121 Co2 N7 C11 165.2(15) . . . . ? N1 Co2 N7 C11 -53.5(16) . . . . ? N2 Co2 N7 C11 -115.1(14) . . . . ? N8 Co2 N7 C11 7.8(13) . . . . ? N131 Co2 N7 N7 -107.7(6) . . . 6_575 ? N121 Co2 N7 N7 -20.9(6) . . . 6_575 ? N1 Co2 N7 N7 120.4(7) . . . 6_575 ? N2 Co2 N7 N7 58.7(4) . . . 6_575 ? N8 Co2 N7 N7 -178.4(5) . . . 6_575 ? N131 Co2 N121 C122 10(2) . . . . ? N1 Co2 N121 C122 110(2) . . . . ? N2 Co2 N121 C122 162(2) . . . . ? N8 Co2 N121 C122 -74(2) . . . . ? N7 Co2 N121 C122 -117(2) . . . . ? N131 Co2 N121 Co2 161.5(11) . . . 6_575 ? N1 Co2 N121 Co2 -98.2(11) . . . 6_575 ? N2 Co2 N121 Co2 -46.4(11) . . . 6_575 ? N8 Co2 N121 Co2 78.3(15) . . . 6_575 ? N7 Co2 N121 Co2 34.9(11) . . . 6_575 ? Co2 N121 C122 O123 -104.5(15) . . . . ? Co2 N121 C122 O123 104.5(15) 6_575 . . . ? N121 Co2 N131 C132 -21(4) . . . . ? N1 Co2 N131 C132 -156(4) . . . . ? N2 Co2 N131 C132 -90(5) . . . . ? N8 Co2 N131 C132 127(4) . . . . ? N7 Co2 N131 C132 62(4) . . . . ? Co2 N131 C132 O133 -112(42) . . . . ? N131 Co2 N1 C1 161.4(15) . . . . ? N121 Co2 N1 C1 63.5(17) . . . . ? N2 Co2 N1 C1 9.7(15) . . . . ? N8 Co2 N1 C1 -114.5(15) . . . . ? N7 Co2 N1 C1 -55.5(18) . . . . ? N131 Co2 N1 C15 -30.9(14) . . . . ? N121 Co2 N1 C15 -128.8(14) . . . . ? N2 Co2 N1 C15 177.4(15) . . . . ? N8 Co2 N1 C15 53.1(13) . . . . ? N7 Co2 N1 C15 112.2(13) . . . . ? N131 Co2 N2 C2 -78.9(18) . . . . ? N121 Co2 N2 C2 -150.6(16) . . . . ? N1 Co2 N2 C2 -6.4(14) . . . . ? N8 Co2 N2 C2 59.1(17) . . . . ? N7 Co2 N2 C2 123.7(15) . . . . ? N131 Co2 N2 N2 98.6(11) . . . 6_575 ? N121 Co2 N2 N2 26.9(6) . . . 6_575 ? N1 Co2 N2 N2 171.1(6) . . . 6_575 ? N8 Co2 N2 N2 -123.4(5) . . . 6_575 ? N7 Co2 N2 N2 -58.9(4) . . . 6_575 ? N131 Co2 N8 C12 -137.9(14) . . . . ? N121 Co2 N8 C12 -53.1(17) . . . . ? N1 Co2 N8 C12 124.3(14) . . . . ? N2 Co2 N8 C12 61.5(15) . . . . ? N7 Co2 N8 C12 -7.4(13) . . . . ? N131 Co2 N8 C13 47.7(14) . . . . ? N121 Co2 N8 C13 132.5(15) . . . . ? N1 Co2 N8 C13 -50.1(14) . . . . ? N2 Co2 N8 C13 -113.0(14) . . . . ? N7 Co2 N8 C13 178.2(15) . . . . ? C15 N1 C1 C2 -179.9(16) . . . . ? Co2 N1 C1 C2 -12(2) . . . . ? N2 N2 C2 C3 6(2) 6_575 . . . ? Co2 N2 C2 C3 -176.5(15) . . . . ? N2 N2 C2 C1 -174.8(10) 6_575 . . . ? Co2 N2 C2 C1 3(2) . . . . ? N1 C1 C2 N2 6(3) . . . . ? N1 C1 C2 C3 -175(2) . . . . ? N2 C2 C3 C3 -6(2) . . . 6_575 ? C1 C2 C3 C3 174.9(13) . . . 6_575 ? N7 N7 C11 C10 -4(2) 6_575 . . . ? Co2 N7 C11 C10 170.0(15) . . . . ? N7 N7 C11 C12 179.2(10) 6_575 . . . ? Co2 N7 C11 C12 -7(2) . . . . ? C10 C10 C11 N7 4(2) 6_575 . . . ? C10 C10 C11 C12 -179.8(15) 6_575 . . . ? C13 N8 C12 C11 -178.5(17) . . . . ? Co2 N8 C12 C11 7(2) . . . . ? N7 C11 C12 N8 0(3) . . . . ? C10 C11 C12 N8 -176.9(19) . . . . ? C12 N8 C13 C14 -109(2) . . . . ? Co2 N8 C13 C14 64.7(17) . . . . ? N8 C13 C14 C15 -63(2) . . . . ? C1 N1 C15 C14 99(2) . . . . ? Co2 N1 C15 C14 -69.0(17) . . . . ? C13 C14 C15 N1 65(2) . . . . ? _diffrn_measured_fraction_theta_max 0.604 _diffrn_reflns_theta_full 26.55 _diffrn_measured_fraction_theta_full 0.604 _refine_diff_density_max 0.932 _refine_diff_density_min -1.191 _refine_diff_density_rms 0.181