# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name _publ_author_address 'M. Usman Anwar' ; Department of Chemistry Memorial University of Newfoundland St. Johns, NL, A1B 3X7, Canada ; 'Andrew S. Elliott' ; Department of Chemistry Memorial University of Newfoundland St. Johns, NL, A1B 3X7, Canada ; 'Laurence K. Thompson' ; Department of Chemistry Memorial University of Newfoundland St. Johns, NL, A1B 3X7, Canada ; 'Louise N. Dawe' ; Department of chemistry Memorial University of Newfoundland St. Johns, NL, A1B 3X7, Canada ; _publ_contact_author_address ; Department of chemistry Memorial University of Newfoundland St. Johns, NL, A1B 3X7, Canada ; _publ_contact_author_email lk.thompson@mun.ca _publ_contact_author_fax 1-709-864-3702 _publ_contact_author_phone 1-709-864-8750 #TrackingRef 'Submission.cif' _publ_contact_author_name 'Prof. Laurence K. Thompson' _publ_section_title ; 'Complexes of functionally modified hydrazone ligands -- square, rectangular (M4), trigonal bi-pyramidal (M5) and pin-wheel (M6) motifs. ' ; data_1 _database_code_depnum_ccdc_archive 'CCDC 807490' _publ_section_abstract ; Please see full paper. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C28 H18 Co N8 O2 S2, B F4' _chemical_formula_sum 'C28 H18 B Co F4 N8 O2 S2' _chemical_formula_weight 708.36 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 1 2/c 1' _symmetry_space_group_name_Hall '-C 2yc' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 21.056(3) _cell_length_b 16.647(2) _cell_length_c 17.450(3) _cell_angle_alpha 90.00 _cell_angle_beta 104.873(4) _cell_angle_gamma 90.00 _cell_volume 5912.0(15) _cell_formula_units_Z 8 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 10203 _cell_measurement_theta_min 2.0551 _cell_measurement_theta_max 30.7868 _exptl_crystal_description Prism _exptl_crystal_colour Red _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.592 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2864 _exptl_absorpt_coefficient_mu 0.791 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.9537 _exptl_absorpt_correction_T_min 0.9057 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 36228 _diffrn_reflns_av_R_equivalents 0.0473 _diffrn_reflns_av_sigmaI/netI 0.0267 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.66 _diffrn_reflns_theta_max 25.50 _reflns_number_total 5498 _reflns_number_gt 5343 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Acta Cryst.2008, A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst.2008, A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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^)+(0.1255P)^2^+18.9291P] 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 5498 _refine_ls_number_parameters 461 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0854 _refine_ls_R_factor_gt 0.0836 _refine_ls_wR_factor_ref 0.2351 _refine_ls_wR_factor_gt 0.2331 _refine_ls_goodness_of_fit_ref 1.127 _refine_ls_restrained_S_all 1.127 _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 0.20597(3) 0.41440(3) 0.06732(4) 0.0464(2) Uani 1 1 d . . . S1 S 0.06863(8) 0.17225(9) 0.13940(10) 0.0727(4) Uani 1 1 d . . . S2 S 0.08991(6) 0.51077(8) -0.22859(8) 0.0569(4) Uani 1 1 d . . . B1 B 0.1785(9) 0.8181(9) 0.0908(14) 0.096(6) Uani 0.50 1 d P A 1 F1 F 0.2228(5) 0.8638(5) 0.0593(6) 0.121(3) Uani 0.50 1 d P A 1 F2 F 0.1969(3) 0.7930(4) 0.1585(4) 0.0680(17) Uani 0.50 1 d P A 1 F3 F 0.1622(6) 0.7553(5) 0.0403(5) 0.114(3) Uani 0.50 1 d P A 1 F4 F 0.1169(5) 0.8679(5) 0.0757(6) 0.105(3) Uani 0.50 1 d P A 1 B2 B -0.0677(8) 0.9309(12) 0.2984(13) 0.081(5) Uani 0.50 1 d P B 2 F5 F -0.0098(6) 0.8963(8) 0.2887(7) 0.138(4) Uani 0.50 1 d P . 2 F6 F -0.0859(11) 0.8842(11) 0.3573(19) 0.279(14) Uani 0.50 1 d P B 2 F7 F -0.0579(7) 0.9864(9) 0.3356(13) 0.184(7) Uani 0.50 1 d P B 2 F8 F -0.1069(7) 0.933(2) 0.2397(9) 0.305(16) Uani 0.50 1 d P B 2 O1 O 0.12472(16) 0.38640(19) 0.08892(19) 0.0515(8) Uani 1 1 d . . . O2 O 0.17238(16) 0.38036(19) -0.03973(19) 0.0509(8) Uani 1 1 d . . . N1 N 0.2946(2) 0.4157(2) 0.0544(2) 0.0506(9) Uani 1 1 d . . . N2 N 0.2297(2) 0.3117(2) 0.1047(2) 0.0515(9) Uani 1 1 d . . . N3 N 0.1821(2) 0.2671(2) 0.1245(2) 0.0564(10) Uani 1 1 d . . . N4 N 0.0163(2) 0.3160(3) 0.1256(3) 0.0610(11) Uani 1 1 d . . . N5 N 0.23124(19) 0.4745(2) 0.1646(2) 0.0508(9) Uani 1 1 d . . . N6 N 0.17712(18) 0.5141(2) 0.0251(2) 0.0487(9) Uani 1 1 d . . . N7 N 0.1464(2) 0.5162(2) -0.0545(3) 0.0531(10) Uani 1 1 d . . . N8 N 0.10543(18) 0.3582(3) -0.1963(2) 0.0512(9) Uani 1 1 d . . . C1 C 0.3253(3) 0.4743(3) 0.0260(3) 0.0624(13) Uani 1 1 d . . . H1 H 0.3030 0.5233 0.0090 0.075 Uiso 1 1 calc R . . C2 C 0.3899(3) 0.4640(4) 0.0212(4) 0.0778(17) Uani 1 1 d . . . H2 H 0.4112 0.5058 0.0004 0.093 Uiso 1 1 calc R . . C3 C 0.4225(3) 0.3943(4) 0.0460(4) 0.0768(17) Uani 1 1 d . . . H3 H 0.4665 0.3874 0.0427 0.092 Uiso 1 1 calc R . . C4 C 0.3912(3) 0.3339(4) 0.0758(4) 0.0675(14) Uani 1 1 d . . . H4 H 0.4135 0.2851 0.0939 0.081 Uiso 1 1 calc R . . C5 C 0.3265(2) 0.3452(3) 0.0791(3) 0.0544(12) Uani 1 1 d . . . C6 C 0.2883(2) 0.2860(3) 0.1073(3) 0.0556(12) Uani 1 1 d . . . H6 H 0.3041 0.2342 0.1256 0.067 Uiso 1 1 calc R . . C7 C 0.1290(3) 0.3116(3) 0.1132(3) 0.0536(11) Uani 1 1 d . . . C8 C 0.0696(2) 0.2747(3) 0.1256(3) 0.0543(11) Uani 1 1 d . . . C9 C -0.0314(3) 0.2616(4) 0.1359(3) 0.0675(14) Uani 1 1 d . . . C10 C -0.0948(3) 0.2841(4) 0.1390(4) 0.0835(18) Uani 1 1 d . . . H10 H -0.1089 0.3385 0.1332 0.100 Uiso 1 1 calc R . . C11 C -0.1361(4) 0.2231(5) 0.1510(5) 0.100(2) Uani 1 1 d . . . H11 H -0.1795 0.2365 0.1530 0.119 Uiso 1 1 calc R . . C12 C -0.1163(3) 0.1424(5) 0.1603(5) 0.089(2) Uani 1 1 d . . . H12 H -0.1458 0.1024 0.1694 0.107 Uiso 1 1 calc R . . C13 C -0.0545(3) 0.1216(4) 0.1562(4) 0.0800(17) Uani 1 1 d . . . H13 H -0.0407 0.0671 0.1615 0.096 Uiso 1 1 calc R . . C14 C -0.0123(3) 0.1817(3) 0.1442(3) 0.0636(13) Uani 1 1 d . . . C15 C 0.2602(3) 0.4484(4) 0.2368(3) 0.0631(13) Uani 1 1 d . . . H15 H 0.2700 0.3928 0.2445 0.076 Uiso 1 1 calc R . . C16 C 0.2767(3) 0.5000(4) 0.3017(4) 0.0750(17) Uani 1 1 d . . . H16 H 0.2973 0.4798 0.3530 0.090 Uiso 1 1 calc R . . C17 C 0.2628(3) 0.5806(4) 0.2904(4) 0.0700(16) Uani 1 1 d . . . H17 H 0.2749 0.6171 0.3335 0.084 Uiso 1 1 calc R . . C18 C 0.2312(3) 0.6078(3) 0.2160(4) 0.0646(14) Uani 1 1 d . . . H18 H 0.2199 0.6630 0.2078 0.077 Uiso 1 1 calc R . . C19 C 0.2158(2) 0.5545(3) 0.1531(3) 0.0534(11) Uani 1 1 d . . . C20 C 0.1836(3) 0.5742(3) 0.0728(4) 0.0577(12) Uani 1 1 d . . . H20 H 0.1684 0.6267 0.0562 0.069 Uiso 1 1 calc R . . C21 C 0.1467(2) 0.4431(3) -0.0815(3) 0.0499(11) Uani 1 1 d . . . C22 C 0.1149(2) 0.4300(3) -0.1660(3) 0.0486(10) Uani 1 1 d . . . C23 C 0.0751(2) 0.3653(3) -0.2766(3) 0.0517(11) Uani 1 1 d . . . C24 C 0.0572(3) 0.3007(3) -0.3295(3) 0.0603(13) Uani 1 1 d . . . H24 H 0.0649 0.2470 -0.3111 0.072 Uiso 1 1 calc R . . C25 C 0.0285(3) 0.3158(4) -0.4075(3) 0.0640(13) Uani 1 1 d . . . H25 H 0.0173 0.2724 -0.4438 0.077 Uiso 1 1 calc R . . C26 C 0.0153(3) 0.3945(4) -0.4346(3) 0.0663(14) Uani 1 1 d . . . H26 H -0.0055 0.4034 -0.4891 0.080 Uiso 1 1 calc R . . C27 C 0.0316(3) 0.4589(4) -0.3848(3) 0.0633(14) Uani 1 1 d . . . H27 H 0.0223 0.5122 -0.4039 0.076 Uiso 1 1 calc R . . C28 C 0.0625(2) 0.4441(3) -0.3045(3) 0.0527(11) 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 0.0493(4) 0.0363(4) 0.0505(4) -0.0018(2) 0.0075(3) 0.0042(2) S1 0.0734(9) 0.0546(8) 0.0924(11) 0.0054(7) 0.0258(8) -0.0013(7) S2 0.0558(7) 0.0518(7) 0.0595(7) 0.0126(5) 0.0081(6) 0.0037(5) B1 0.097(12) 0.039(7) 0.159(19) -0.023(9) 0.044(12) -0.021(7) F1 0.124(7) 0.085(6) 0.141(8) 0.056(5) 0.011(6) -0.025(5) F2 0.064(4) 0.057(4) 0.075(4) 0.027(3) 0.003(3) 0.000(3) F3 0.193(10) 0.052(4) 0.106(6) 0.013(4) 0.054(6) -0.002(5) F4 0.119(7) 0.070(5) 0.116(7) 0.016(4) 0.013(5) -0.002(5) B2 0.055(8) 0.080(10) 0.115(14) -0.020(9) 0.034(9) -0.014(7) F5 0.103(7) 0.177(11) 0.140(10) -0.019(8) 0.042(7) 0.005(7) F6 0.25(2) 0.137(13) 0.53(4) 0.06(2) 0.24(3) 0.046(13) F7 0.146(11) 0.133(11) 0.31(2) 0.020(12) 0.123(13) 0.020(9) F8 0.091(8) 0.69(5) 0.122(10) -0.127(19) 0.002(8) 0.091(16) O1 0.0533(18) 0.0429(17) 0.0564(19) 0.0022(14) 0.0106(15) -0.0020(14) O2 0.0592(19) 0.0402(17) 0.0481(17) 0.0025(13) 0.0047(14) 0.0066(14) N1 0.054(2) 0.047(2) 0.048(2) -0.0079(16) 0.0102(18) 0.0033(17) N2 0.056(2) 0.046(2) 0.048(2) 0.0017(16) 0.0051(17) 0.0053(18) N3 0.063(3) 0.046(2) 0.056(2) 0.0043(18) 0.0100(19) 0.0050(19) N4 0.058(2) 0.067(3) 0.057(2) 0.007(2) 0.0123(19) -0.013(2) N5 0.044(2) 0.049(2) 0.059(2) -0.0084(18) 0.0121(18) 0.0012(17) N6 0.044(2) 0.037(2) 0.066(2) 0.0031(17) 0.0154(18) 0.0021(15) N7 0.051(2) 0.041(2) 0.063(2) 0.0041(17) 0.0076(19) 0.0026(16) N8 0.042(2) 0.058(2) 0.051(2) 0.0071(18) 0.0078(16) 0.0017(17) C1 0.072(3) 0.056(3) 0.058(3) -0.001(2) 0.015(3) -0.005(3) C2 0.078(4) 0.080(4) 0.084(4) -0.007(3) 0.038(3) -0.018(3) C3 0.059(3) 0.082(4) 0.095(5) -0.011(3) 0.029(3) 0.007(3) C4 0.054(3) 0.069(4) 0.077(4) -0.005(3) 0.013(3) 0.009(3) C5 0.054(3) 0.051(3) 0.055(3) -0.009(2) 0.008(2) 0.010(2) C6 0.060(3) 0.044(3) 0.059(3) -0.002(2) 0.008(2) 0.011(2) C7 0.061(3) 0.047(3) 0.051(3) 0.000(2) 0.011(2) -0.004(2) C8 0.056(3) 0.054(3) 0.050(3) 0.001(2) 0.009(2) -0.005(2) C9 0.072(3) 0.062(3) 0.069(3) -0.010(3) 0.019(3) -0.012(3) C10 0.073(4) 0.081(4) 0.098(5) -0.012(4) 0.026(4) -0.004(3) C11 0.080(5) 0.105(6) 0.125(7) -0.020(5) 0.046(5) -0.010(4) C12 0.077(4) 0.087(5) 0.110(6) -0.009(4) 0.037(4) -0.023(4) C13 0.081(4) 0.063(4) 0.097(5) -0.002(3) 0.023(4) -0.011(3) C14 0.066(3) 0.064(3) 0.060(3) -0.004(2) 0.015(3) -0.009(3) C15 0.062(3) 0.064(3) 0.061(3) -0.013(3) 0.011(2) 0.004(3) C16 0.069(4) 0.087(4) 0.068(4) -0.026(3) 0.015(3) 0.000(3) C17 0.060(3) 0.074(4) 0.079(4) -0.036(3) 0.024(3) -0.012(3) C18 0.060(3) 0.051(3) 0.091(4) -0.024(3) 0.034(3) -0.012(2) C19 0.050(3) 0.042(2) 0.073(3) -0.014(2) 0.023(2) -0.005(2) C20 0.057(3) 0.036(2) 0.082(4) -0.004(2) 0.021(3) 0.002(2) C21 0.040(2) 0.052(3) 0.055(3) 0.009(2) 0.008(2) 0.0032(19) C22 0.041(2) 0.048(3) 0.055(3) 0.009(2) 0.009(2) 0.0012(19) C23 0.043(2) 0.058(3) 0.055(3) 0.009(2) 0.013(2) -0.002(2) C24 0.055(3) 0.059(3) 0.066(3) 0.007(2) 0.015(2) 0.001(2) C25 0.055(3) 0.078(4) 0.056(3) -0.001(3) 0.011(2) -0.009(3) C26 0.057(3) 0.084(4) 0.054(3) 0.007(3) 0.007(2) -0.008(3) C27 0.055(3) 0.072(4) 0.058(3) 0.019(3) 0.006(2) 0.002(3) C28 0.042(2) 0.059(3) 0.055(3) 0.010(2) 0.010(2) 0.000(2) _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 N2 1.852(4) . ? Co1 N6 1.854(4) . ? Co1 O1 1.902(3) . ? Co1 O2 1.906(3) . ? Co1 N5 1.924(4) . ? Co1 N1 1.936(4) . ? S1 C8 1.724(5) . ? S1 C14 1.734(6) . ? S2 C28 1.711(5) . ? S2 C22 1.727(5) . ? B1 F2 1.22(2) . ? B1 F3 1.354(18) . ? B1 F1 1.42(2) . ? B1 F4 1.50(2) . ? B2 F7 1.12(2) . ? B2 F8 1.14(2) . ? B2 F5 1.397(19) . ? B2 F6 1.42(3) . ? F5 F5 1.51(2) 2 ? O1 C7 1.311(6) . ? O2 C21 1.309(6) . ? N1 C1 1.333(7) . ? N1 C5 1.368(6) . ? N2 C6 1.295(6) . ? N2 N3 1.362(6) . ? N3 C7 1.312(6) . ? N4 C8 1.316(7) . ? N4 C9 1.399(7) . ? N5 C15 1.324(7) . ? N5 C19 1.374(6) . ? N6 C20 1.285(6) . ? N6 N7 1.375(6) . ? N7 C21 1.305(6) . ? N8 C22 1.302(6) . ? N8 C23 1.387(6) . ? C1 C2 1.396(8) . ? C1 H1 0.9500 . ? C2 C3 1.361(9) . ? C2 H2 0.9500 . ? C3 C4 1.375(9) . ? C3 H3 0.9500 . ? C4 C5 1.392(7) . ? C4 H4 0.9500 . ? C5 C6 1.436(7) . ? C6 H6 0.9500 . ? C7 C8 1.459(7) . ? C9 C14 1.388(8) . ? C9 C10 1.401(9) . ? C10 C11 1.387(10) . ? C10 H10 0.9500 . ? C11 C12 1.404(11) . ? C11 H11 0.9500 . ? C12 C13 1.365(9) . ? C12 H12 0.9500 . ? C13 C14 1.390(8) . ? C13 H13 0.9500 . ? C15 C16 1.392(8) . ? C15 H15 0.9500 . ? C16 C17 1.378(9) . ? C16 H16 0.9500 . ? C17 C18 1.375(9) . ? C17 H17 0.9500 . ? C18 C19 1.383(7) . ? C18 H18 0.9500 . ? C19 C20 1.429(8) . ? C20 H20 0.9500 . ? C21 C22 1.471(7) . ? C23 C28 1.400(7) . ? C23 C24 1.405(8) . ? C24 C25 1.365(7) . ? C24 H24 0.9500 . ? C25 C26 1.395(8) . ? C25 H25 0.9500 . ? C26 C27 1.368(8) . ? C26 H26 0.9500 . ? C27 C28 1.408(7) . ? C27 H27 0.9500 . ? 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 N2 Co1 N6 176.05(18) . . ? N2 Co1 O1 83.07(16) . . ? N6 Co1 O1 94.50(15) . . ? N2 Co1 O2 93.98(15) . . ? N6 Co1 O2 82.87(16) . . ? O1 Co1 O2 89.71(14) . . ? N2 Co1 N5 100.41(18) . . ? N6 Co1 N5 82.69(18) . . ? O1 Co1 N5 90.67(15) . . ? O2 Co1 N5 165.54(16) . . ? N2 Co1 N1 82.56(17) . . ? N6 Co1 N1 99.82(16) . . ? O1 Co1 N1 165.63(15) . . ? O2 Co1 N1 90.88(15) . . ? N5 Co1 N1 92.32(16) . . ? C8 S1 C14 87.9(3) . . ? C28 S2 C22 88.4(2) . . ? F2 B1 F3 109.3(13) . . ? F2 B1 F1 118.8(16) . . ? F3 B1 F1 104.1(15) . . ? F2 B1 F4 113.8(15) . . ? F3 B1 F4 104.4(15) . . ? F1 B1 F4 105.0(14) . . ? F7 B2 F8 119(3) . . ? F7 B2 F5 111.9(15) . . ? F8 B2 F5 111.0(17) . . ? F7 B2 F6 94.4(19) . . ? F8 B2 F6 114(2) . . ? F5 B2 F6 105.6(17) . . ? B2 F5 F5 123.7(15) . 2 ? C7 O1 Co1 107.8(3) . . ? C21 O2 Co1 107.8(3) . . ? C1 N1 C5 119.9(5) . . ? C1 N1 Co1 128.7(4) . . ? C5 N1 Co1 111.4(3) . . ? C6 N2 N3 124.6(4) . . ? C6 N2 Co1 119.1(4) . . ? N3 N2 Co1 116.3(3) . . ? C7 N3 N2 108.0(4) . . ? C8 N4 C9 107.6(5) . . ? C15 N5 C19 119.5(4) . . ? C15 N5 Co1 128.6(4) . . ? C19 N5 Co1 111.9(3) . . ? C20 N6 N7 125.4(4) . . ? C20 N6 Co1 118.0(4) . . ? N7 N6 Co1 116.4(3) . . ? C21 N7 N6 107.3(4) . . ? C22 N8 C23 108.3(4) . . ? N1 C1 C2 120.4(6) . . ? N1 C1 H1 119.8 . . ? C2 C1 H1 119.8 . . ? C3 C2 C1 120.4(6) . . ? C3 C2 H2 119.8 . . ? C1 C2 H2 119.8 . . ? C2 C3 C4 119.5(6) . . ? C2 C3 H3 120.2 . . ? C4 C3 H3 120.2 . . ? C3 C4 C5 119.0(6) . . ? C3 C4 H4 120.5 . . ? C5 C4 H4 120.5 . . ? N1 C5 C4 120.7(5) . . ? N1 C5 C6 115.1(4) . . ? C4 C5 C6 124.2(5) . . ? N2 C6 C5 111.9(4) . . ? N2 C6 H6 124.0 . . ? C5 C6 H6 124.0 . . ? O1 C7 N3 124.8(5) . . ? O1 C7 C8 117.2(4) . . ? N3 C7 C8 118.0(4) . . ? N4 C8 C7 123.0(5) . . ? N4 C8 S1 118.4(4) . . ? C7 C8 S1 118.6(4) . . ? C14 C9 N4 115.8(5) . . ? C14 C9 C10 120.4(6) . . ? N4 C9 C10 123.8(6) . . ? C11 C10 C9 116.8(7) . . ? C11 C10 H10 121.6 . . ? C9 C10 H10 121.6 . . ? C10 C11 C12 122.6(7) . . ? C10 C11 H11 118.7 . . ? C12 C11 H11 118.7 . . ? C13 C12 C11 119.6(6) . . ? C13 C12 H12 120.2 . . ? C11 C12 H12 120.2 . . ? C12 C13 C14 118.8(6) . . ? C12 C13 H13 120.6 . . ? C14 C13 H13 120.6 . . ? C9 C14 C13 121.7(6) . . ? C9 C14 S1 110.2(4) . . ? C13 C14 S1 128.1(5) . . ? N5 C15 C16 121.9(6) . . ? N5 C15 H15 119.0 . . ? C16 C15 H15 119.0 . . ? C17 C16 C15 119.0(6) . . ? C17 C16 H16 120.5 . . ? C15 C16 H16 120.5 . . ? C18 C17 C16 119.3(5) . . ? C18 C17 H17 120.3 . . ? C16 C17 H17 120.3 . . ? C17 C18 C19 119.8(5) . . ? C17 C18 H18 120.1 . . ? C19 C18 H18 120.1 . . ? N5 C19 C18 120.5(5) . . ? N5 C19 C20 113.6(4) . . ? C18 C19 C20 125.9(5) . . ? N6 C20 C19 113.6(4) . . ? N6 C20 H20 123.2 . . ? C19 C20 H20 123.2 . . ? N7 C21 O2 125.6(5) . . ? N7 C21 C22 117.2(4) . . ? O2 C21 C22 117.2(4) . . ? N8 C22 C21 121.8(4) . . ? N8 C22 S2 117.9(4) . . ? C21 C22 S2 120.3(4) . . ? N8 C23 C28 115.4(4) . . ? N8 C23 C24 125.0(5) . . ? C28 C23 C24 119.6(5) . . ? C25 C24 C23 119.3(5) . . ? C25 C24 H24 120.3 . . ? C23 C24 H24 120.3 . . ? C24 C25 C26 120.7(6) . . ? C24 C25 H25 119.7 . . ? C26 C25 H25 119.7 . . ? C27 C26 C25 121.7(5) . . ? C27 C26 H26 119.2 . . ? C25 C26 H26 119.2 . . ? C26 C27 C28 118.1(5) . . ? C26 C27 H27 120.9 . . ? C28 C27 H27 120.9 . . ? C23 C28 C27 120.6(5) . . ? C23 C28 S2 110.0(4) . . ? C27 C28 S2 129.4(4) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.50 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.864 _refine_diff_density_min -0.621 _refine_diff_density_rms 0.092 data_2 _database_code_depnum_ccdc_archive 'CCDC 807491' #TrackingRef 'Submission.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C84 H60 Co5 N30 O6 S6, 2(B F4), F6 Si, 10(H2 O)' _chemical_formula_sum 'C84 H80 B2 Co5 F14 N30 O16 S6 Si' _chemical_formula_weight 2568.46 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' B B 0.0013 0.0007 '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' F F 0.0171 0.0103 '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' Si Si 0.0817 0.0704 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 13.1328(12) _cell_length_b 29.758(3) _cell_length_c 27.266(3) _cell_angle_alpha 90.00 _cell_angle_beta 104.666(2) _cell_angle_gamma 90.00 _cell_volume 10308.7(17) _cell_formula_units_Z 4 _cell_measurement_temperature 158(2) _cell_measurement_reflns_used 33675 _cell_measurement_theta_min 1.9473 _cell_measurement_theta_max 30.7426 _exptl_crystal_description Prism _exptl_crystal_colour Brown _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.655 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5212 _exptl_absorpt_coefficient_mu 1.025 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.9715 _exptl_absorpt_correction_T_min 0.8781 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 158(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 132880 _diffrn_reflns_av_R_equivalents 0.0947 _diffrn_reflns_av_sigmaI/netI 0.0610 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 37 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 34 _diffrn_reflns_theta_min 2.55 _diffrn_reflns_theta_max 26.50 _reflns_number_total 21346 _reflns_number_gt 17835 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Acta Cryst. 2008. A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst. 2008. A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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. Similarity restraints (SIMU) were applied to the disordered BF4- anion. F12-F14 and F15-F17 were treated as two disordered PARTs; their occupancies were refined and convergence was achieved. ; _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^)+(0.0723P)^2^+40.5557P] 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 21346 _refine_ls_number_parameters 1361 _refine_ls_number_restraints 42 _refine_ls_R_factor_all 0.1152 _refine_ls_R_factor_gt 0.0965 _refine_ls_wR_factor_ref 0.2244 _refine_ls_wR_factor_gt 0.2134 _refine_ls_goodness_of_fit_ref 1.142 _refine_ls_restrained_S_all 1.141 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.877 0.204 -0.028 49 9 '\~1 H2O ' 2 0.500 0.500 0.000 720 179 '\~18 H2O ' 3 0.123 0.796 0.028 49 9 '\~1 H2O ' 4 0.500 1.000 0.500 720 179 '\~18 H2O ' 5 0.877 0.296 0.472 49 9 '\~1 H2O ' 6 0.123 0.704 0.528 49 9 '\~1 H2O ' _platon_squeeze_details ; The Platon Squeeze procedure was applied to recover 394 electrons per unit cell in six voids (total volume 1636 ^A^3); that is 98.5 electrons per formula unit (with Z=4). Disordered lattice solvent water molecules (approximately 10) were present prior to the application of Squeeze, however, a good point atom model could not be achieved. The application of Squeeze gave a good improvement in the data statistics and allowed for a full anisotropic refinement of the core structure. PLATON Reference : Spek, A.L. (2003), J.Appl.Cryst. 36, 7-13 ; 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 0.47370(6) 0.59234(3) 0.33323(3) 0.03425(19) Uani 1 1 d . . . Co2 Co 0.21435(6) 0.66684(3) 0.31881(3) 0.0368(2) Uani 1 1 d . . . Co3 Co 0.34740(7) 0.55820(3) 0.19186(3) 0.0382(2) Uani 1 1 d . . . Co4 Co 0.29553(7) 0.68894(3) 0.19119(3) 0.0377(2) Uani 1 1 d . . . Co5 Co 0.58753(6) 0.69840(3) 0.27596(3) 0.0363(2) Uani 1 1 d . . . S1 S 0.61232(13) 0.69488(6) 0.45361(6) 0.0433(4) Uani 1 1 d . . . S2 S 0.21339(14) 0.50424(6) 0.36255(7) 0.0493(4) Uani 1 1 d . . . S3 S 0.71164(13) 0.51889(6) 0.26739(7) 0.0449(4) Uani 1 1 d . . . S4 S 0.26055(13) 0.82169(6) 0.26722(7) 0.0466(4) Uani 1 1 d . . . S5 S 0.50699(15) 0.68628(7) 0.08346(8) 0.0558(5) Uani 1 1 d . . . S6 S -0.01816(17) 0.62459(8) 0.12307(8) 0.0681(6) Uani 1 1 d . . . Si1 Si 0.18893(17) 0.92430(7) 0.37174(8) 0.0533(5) Uani 1 1 d . . . F1 F 0.1903(4) 0.88201(15) 0.41184(18) 0.0709(13) Uani 1 1 d . . . F2 F 0.1151(4) 0.95582(17) 0.40024(17) 0.0709(13) Uani 1 1 d . . . F3 F 0.1912(4) 0.96670(16) 0.3304(2) 0.0812(15) Uani 1 1 d . . . F4 F 0.2979(4) 0.94681(17) 0.4104(2) 0.0773(14) Uani 1 1 d . . . F5 F 0.2626(5) 0.89319(17) 0.3439(2) 0.0877(16) Uani 1 1 d . . . F6 F 0.0805(4) 0.90489(17) 0.3325(2) 0.0825(15) Uani 1 1 d . . . F7 F 0.7881(6) 0.6848(2) 0.0758(2) 0.110(2) Uani 1 1 d . . . F8 F 0.7231(9) 0.7519(3) 0.0435(3) 0.191(5) Uani 1 1 d . . . F9 F 0.8652(10) 0.7327(3) 0.0320(3) 0.174(4) Uani 1 1 d . . . F10 F 0.7375(6) 0.6907(3) -0.0075(2) 0.128(3) Uani 1 1 d . . . F11 F 0.0129(6) 0.4789(2) 0.4338(3) 0.150(4) Uani 1 1 d U A . F12 F -0.1176(9) 0.5077(4) 0.3750(4) 0.091(4) Uani 0.596(17) 1 d PU A 1 F13 F -0.1316(14) 0.4406(6) 0.4167(5) 0.130(7) Uani 0.596(17) 1 d PU A 1 F14 F -0.0525(12) 0.4439(5) 0.3575(5) 0.136(6) Uani 0.596(17) 1 d PU A 1 F15 F -0.0699(11) 0.4845(5) 0.3548(5) 0.069(5) Uani 0.404(17) 1 d PU A 2 F16 F -0.1618(18) 0.4813(10) 0.4117(8) 0.146(9) Uani 0.404(17) 1 d PU A 2 F17 F -0.0906(15) 0.4201(5) 0.3973(8) 0.098(8) Uani 0.404(17) 1 d PU A 2 O1 O 0.3792(3) 0.64753(14) 0.34287(15) 0.0361(9) Uani 1 1 d . . . O2 O 0.3613(3) 0.56655(14) 0.27136(15) 0.0372(9) Uani 1 1 d . . . O3 O 0.5596(3) 0.62888(13) 0.29127(16) 0.0383(9) Uani 1 1 d . . . O4 O 0.4211(3) 0.71289(14) 0.24927(15) 0.0374(9) Uani 1 1 d . . . O5 O 0.3725(3) 0.62904(14) 0.18216(15) 0.0383(9) Uani 1 1 d . . . O6 O 0.2113(3) 0.66145(15) 0.24008(15) 0.0403(10) Uani 1 1 d . . . N1 N 0.5759(4) 0.62418(17) 0.39688(18) 0.0364(11) Uani 1 1 d . . . N2 N 0.3928(4) 0.71287(17) 0.39075(19) 0.0379(11) Uani 1 1 d . . . N3 N 0.2892(4) 0.71888(17) 0.36165(19) 0.0381(11) Uani 1 1 d . . . N4 N 0.2835(5) 0.78909(19) 0.3992(2) 0.0555(16) Uani 1 1 d . . . H4A H 0.3491 0.7871 0.4173 0.067 Uiso 1 1 calc R . . H4B H 0.2461 0.8131 0.4016 0.067 Uiso 1 1 calc R . . N5 N 0.0977(4) 0.72249(17) 0.30773(19) 0.0400(12) Uani 1 1 d . . . N6 N 0.3796(4) 0.55343(16) 0.37098(18) 0.0349(11) Uani 1 1 d . . . N7 N 0.2042(4) 0.52557(19) 0.25251(19) 0.0433(12) Uani 1 1 d . . . N8 N 0.2098(4) 0.53602(18) 0.20298(19) 0.0427(12) Uani 1 1 d . . . N9 N 0.0455(4) 0.5037(2) 0.1726(2) 0.0545(15) Uani 1 1 d . . . H9A H 0.0375 0.4989 0.2033 0.065 Uiso 1 1 calc R . . H9B H -0.0043 0.4956 0.1459 0.065 Uiso 1 1 calc R . . N10 N 0.2401(4) 0.55195(19) 0.11554(19) 0.0434(12) Uani 1 1 d . . . N11 N 0.5756(4) 0.54053(16) 0.31720(18) 0.0355(11) Uani 1 1 d . . . N12 N 0.6848(4) 0.61709(17) 0.24460(19) 0.0384(11) Uani 1 1 d . . . N13 N 0.6653(4) 0.66269(16) 0.23414(18) 0.0353(11) Uani 1 1 d . . . N14 N 0.7681(5) 0.6574(2) 0.1765(2) 0.0523(15) Uani 1 1 d . . . H14A H 0.7820 0.6288 0.1832 0.063 Uiso 1 1 calc R . . H14B H 0.7944 0.6712 0.1539 0.063 Uiso 1 1 calc R . . N15 N 0.6283(4) 0.74623(17) 0.2213(2) 0.0424(12) Uani 1 1 d . . . N16 N 0.2348(4) 0.75269(18) 0.2072(2) 0.0405(12) Uani 1 1 d . . . N17 N 0.4664(4) 0.77380(17) 0.3052(2) 0.0403(12) Uani 1 1 d . . . N18 N 0.5614(4) 0.74980(17) 0.31910(19) 0.0383(11) Uani 1 1 d . . . N19 N 0.6194(5) 0.8019(2) 0.3845(2) 0.0616(18) Uani 1 1 d . . . H19A H 0.5588 0.8162 0.3776 0.074 Uiso 1 1 calc R . . H19B H 0.6716 0.8111 0.4096 0.074 Uiso 1 1 calc R . . N20 N 0.7340(4) 0.70492(17) 0.3394(2) 0.0416(12) Uani 1 1 d . . . N21 N 0.3823(4) 0.70984(18) 0.13867(19) 0.0411(12) Uani 1 1 d . . . N22 N 0.4952(4) 0.60136(18) 0.1414(2) 0.0445(13) Uani 1 1 d . . . N23 N 0.4749(4) 0.56146(18) 0.1635(2) 0.0432(12) Uani 1 1 d . . . N24 N 0.5994(5) 0.5259(2) 0.1290(2) 0.0524(14) Uani 1 1 d . . . H24A H 0.6169 0.5512 0.1165 0.063 Uiso 1 1 calc R . . H24B H 0.6305 0.5006 0.1245 0.063 Uiso 1 1 calc R . . N25 N 0.4102(4) 0.48917(18) 0.1966(2) 0.0431(12) Uani 1 1 d . . . N26 N 0.1586(4) 0.66526(17) 0.13777(18) 0.0384(11) Uani 1 1 d . . . N27 N 0.0612(4) 0.61867(19) 0.23699(19) 0.0439(13) Uani 1 1 d . . . N28 N 0.1003(4) 0.62101(18) 0.28960(19) 0.0400(12) Uani 1 1 d . . . N29 N -0.0329(4) 0.5731(2) 0.3001(2) 0.0520(15) Uani 1 1 d . . . H29A H -0.0599 0.5703 0.2672 0.062 Uiso 1 1 calc R . . H29B H -0.0618 0.5589 0.3215 0.062 Uiso 1 1 calc R . . N30 N 0.1734(4) 0.63512(19) 0.3845(2) 0.0449(13) Uani 1 1 d . . . C1 C 0.7077(5) 0.6540(2) 0.4626(2) 0.0393(14) Uani 1 1 d . . . C2 C 0.8062(5) 0.6527(3) 0.4983(3) 0.0523(17) Uani 1 1 d . . . H2 H 0.8291 0.6768 0.5213 0.063 Uiso 1 1 calc R . . C3 C 0.8684(5) 0.6151(2) 0.4986(3) 0.0494(16) Uani 1 1 d . . . H3 H 0.9341 0.6131 0.5231 0.059 Uiso 1 1 calc R . . C4 C 0.8375(5) 0.5805(2) 0.4641(3) 0.0480(16) Uani 1 1 d . . . H4 H 0.8830 0.5556 0.4649 0.058 Uiso 1 1 calc R . . C5 C 0.7421(5) 0.5816(2) 0.4289(2) 0.0407(14) Uani 1 1 d . . . H5 H 0.7211 0.5578 0.4053 0.049 Uiso 1 1 calc R . . C6 C 0.6773(5) 0.6183(2) 0.4286(2) 0.0365(13) Uani 1 1 d . . . C7 C 0.5347(4) 0.66308(19) 0.4062(2) 0.0331(12) Uani 1 1 d . . . C8 C 0.4289(4) 0.6754(2) 0.3779(2) 0.0333(12) Uani 1 1 d . . . C9 C 0.2412(5) 0.7561(2) 0.3684(3) 0.0433(15) Uani 1 1 d . . . C10 C 0.1300(5) 0.7586(2) 0.3376(2) 0.0400(14) Uani 1 1 d . . . C11 C 0.0669(5) 0.7952(2) 0.3388(3) 0.0529(17) Uani 1 1 d . . . H11 H 0.0925 0.8201 0.3600 0.063 Uiso 1 1 calc R . . C12 C -0.0355(6) 0.7948(3) 0.3080(3) 0.064(2) Uani 1 1 d . . . H12 H -0.0813 0.8195 0.3083 0.077 Uiso 1 1 calc R . . C13 C -0.0695(6) 0.7583(3) 0.2773(3) 0.062(2) Uani 1 1 d . . . H13 H -0.1390 0.7574 0.2560 0.074 Uiso 1 1 calc R . . C14 C 0.0000(6) 0.7227(3) 0.2783(3) 0.0534(17) Uani 1 1 d . . . H14 H -0.0234 0.6975 0.2570 0.064 Uiso 1 1 calc R . . C15 C 0.2893(5) 0.5172(2) 0.4234(2) 0.0470(16) Uani 1 1 d . . . C16 C 0.2700(6) 0.5053(3) 0.4701(3) 0.0563(18) Uani 1 1 d . . . H16 H 0.2117 0.4870 0.4719 0.068 Uiso 1 1 calc R . . C17 C 0.3394(6) 0.5212(3) 0.5132(3) 0.0545(18) Uani 1 1 d . . . H17 H 0.3284 0.5141 0.5454 0.065 Uiso 1 1 calc R . . C18 C 0.4252(6) 0.5475(2) 0.5105(3) 0.0497(16) Uani 1 1 d . . . H18 H 0.4722 0.5574 0.5411 0.060 Uiso 1 1 calc R . . C19 C 0.4446(5) 0.5598(2) 0.4648(2) 0.0459(15) Uani 1 1 d . . . H19 H 0.5029 0.5782 0.4635 0.055 Uiso 1 1 calc R . . C20 C 0.3744(5) 0.5440(2) 0.4204(2) 0.0397(14) Uani 1 1 d . . . C21 C 0.2996(5) 0.5355(2) 0.3380(2) 0.0382(13) Uani 1 1 d . . . C22 C 0.2868(5) 0.5429(2) 0.2836(2) 0.0388(13) Uani 1 1 d . . . C23 C 0.1330(5) 0.5231(2) 0.1666(2) 0.0451(15) Uani 1 1 d . . . C24 C 0.1460(6) 0.5342(2) 0.1155(2) 0.0484(16) Uani 1 1 d . . . C25 C 0.0685(7) 0.5295(3) 0.0710(3) 0.068(2) Uani 1 1 d . . . H25 H 0.0022 0.5170 0.0716 0.082 Uiso 1 1 calc R . . C26 C 0.0874(7) 0.5429(3) 0.0256(3) 0.070(2) Uani 1 1 d . . . H26 H 0.0348 0.5398 -0.0053 0.084 Uiso 1 1 calc R . . C27 C 0.1834(7) 0.5607(3) 0.0262(3) 0.064(2) Uani 1 1 d . . . H27 H 0.1980 0.5707 -0.0044 0.077 Uiso 1 1 calc R . . C28 C 0.2589(6) 0.5642(3) 0.0713(3) 0.0539(18) Uani 1 1 d . . . H28 H 0.3263 0.5757 0.0711 0.065 Uiso 1 1 calc R . . C29 C 0.6626(5) 0.4766(2) 0.2988(2) 0.0419(14) Uani 1 1 d . . . C30 C 0.6836(6) 0.4310(2) 0.3002(3) 0.0522(17) Uani 1 1 d . . . H30 H 0.7319 0.4191 0.2828 0.063 Uiso 1 1 calc R . . C31 C 0.6337(6) 0.4028(2) 0.3270(3) 0.0580(19) Uani 1 1 d . . . H31 H 0.6490 0.3716 0.3293 0.070 Uiso 1 1 calc R . . C32 C 0.5602(6) 0.4211(2) 0.3508(3) 0.0498(16) Uani 1 1 d . . . H32 H 0.5245 0.4015 0.3683 0.060 Uiso 1 1 calc R . . C33 C 0.5382(5) 0.4656(2) 0.3496(2) 0.0425(14) Uani 1 1 d . . . H33 H 0.4887 0.4770 0.3665 0.051 Uiso 1 1 calc R . . C34 C 0.5897(5) 0.4946(2) 0.3230(2) 0.0379(13) Uani 1 1 d . . . C35 C 0.6328(5) 0.5561(2) 0.2884(2) 0.0361(13) Uani 1 1 d . . . C36 C 0.6254(4) 0.6043(2) 0.2741(2) 0.0342(12) Uani 1 1 d . . . C37 C 0.7072(5) 0.6799(2) 0.2006(2) 0.0399(14) Uani 1 1 d . . . C38 C 0.6851(5) 0.7287(2) 0.1913(3) 0.0446(15) Uani 1 1 d . . . C39 C 0.7185(6) 0.7537(2) 0.1558(3) 0.0535(18) Uani 1 1 d . . . H39 H 0.7581 0.7403 0.1349 0.064 Uiso 1 1 calc R . . C40 C 0.6931(6) 0.7988(3) 0.1515(3) 0.059(2) Uani 1 1 d . . . H40 H 0.7147 0.8168 0.1271 0.071 Uiso 1 1 calc R . . C41 C 0.6376(6) 0.8175(3) 0.1816(3) 0.059(2) Uani 1 1 d . . . H41 H 0.6212 0.8487 0.1791 0.071 Uiso 1 1 calc R . . C42 C 0.6044(6) 0.7906(2) 0.2167(3) 0.0528(17) Uani 1 1 d . . . H42 H 0.5644 0.8036 0.2376 0.063 Uiso 1 1 calc R . . C43 C 0.1435(5) 0.8172(2) 0.2199(3) 0.0473(16) Uani 1 1 d . . . C44 C 0.0576(6) 0.8464(3) 0.2107(3) 0.063(2) Uani 1 1 d . . . H44 H 0.0574 0.8723 0.2311 0.076 Uiso 1 1 calc R . . C45 C -0.0270(6) 0.8362(3) 0.1707(4) 0.074(3) Uani 1 1 d . . . H45 H -0.0862 0.8556 0.1634 0.088 Uiso 1 1 calc R . . C46 C -0.0281(6) 0.7980(3) 0.1407(3) 0.063(2) Uani 1 1 d . . . H46 H -0.0870 0.7925 0.1130 0.075 Uiso 1 1 calc R . . C47 C 0.0557(6) 0.7680(3) 0.1510(3) 0.0552(18) Uani 1 1 d . . . H47 H 0.0543 0.7415 0.1314 0.066 Uiso 1 1 calc R . . C48 C 0.1425(5) 0.7782(2) 0.1914(3) 0.0468(16) Uani 1 1 d . . . C49 C 0.3003(5) 0.77221(19) 0.2460(2) 0.0361(13) Uani 1 1 d . . . C50 C 0.4031(5) 0.75130(19) 0.2688(2) 0.0361(13) Uani 1 1 d . . . C51 C 0.6323(5) 0.7664(2) 0.3568(2) 0.0419(14) Uani 1 1 d . . . C52 C 0.7334(5) 0.7412(2) 0.3689(2) 0.0428(15) Uani 1 1 d . . . C53 C 0.8212(5) 0.7535(3) 0.4072(3) 0.0498(17) Uani 1 1 d . . . H53 H 0.8197 0.7797 0.4269 0.060 Uiso 1 1 calc R . . C54 C 0.9104(6) 0.7270(3) 0.4160(3) 0.0577(19) Uani 1 1 d . . . H54 H 0.9709 0.7346 0.4421 0.069 Uiso 1 1 calc R . . C55 C 0.9102(6) 0.6893(3) 0.3862(3) 0.0549(18) Uani 1 1 d . . . H55 H 0.9702 0.6703 0.3915 0.066 Uiso 1 1 calc R . . C56 C 0.8205(6) 0.6799(2) 0.3484(3) 0.0496(16) Uani 1 1 d . . . H56 H 0.8208 0.6542 0.3278 0.060 Uiso 1 1 calc R . . C57 C 0.4582(6) 0.7411(3) 0.0776(3) 0.0527(17) Uani 1 1 d . . . C58 C 0.4735(7) 0.7748(3) 0.0456(3) 0.069(2) Uani 1 1 d . . . H58 H 0.5159 0.7700 0.0225 0.083 Uiso 1 1 calc R . . C59 C 0.4265(7) 0.8152(3) 0.0478(3) 0.069(2) Uani 1 1 d . . . H59 H 0.4389 0.8391 0.0270 0.082 Uiso 1 1 calc R . . C60 C 0.3602(7) 0.8224(3) 0.0800(3) 0.063(2) Uani 1 1 d . . . H60 H 0.3277 0.8509 0.0805 0.075 Uiso 1 1 calc R . . C61 C 0.3419(6) 0.7884(2) 0.1109(3) 0.0529(18) Uani 1 1 d . . . H61 H 0.2959 0.7930 0.1323 0.063 Uiso 1 1 calc R . . C62 C 0.3912(5) 0.7479(2) 0.1102(3) 0.0469(16) Uani 1 1 d . . . C63 C 0.4387(5) 0.6769(2) 0.1285(2) 0.0442(15) Uani 1 1 d . . . C64 C 0.4359(5) 0.6328(2) 0.1528(2) 0.0421(14) Uani 1 1 d . . . C65 C 0.5249(5) 0.5259(2) 0.1550(3) 0.0474(16) Uani 1 1 d . . . C66 C 0.4914(5) 0.4839(2) 0.1752(2) 0.0459(16) Uani 1 1 d . . . C67 C 0.5360(7) 0.4419(3) 0.1712(3) 0.063(2) Uani 1 1 d . . . H67 H 0.5927 0.4387 0.1556 0.076 Uiso 1 1 calc R . . C68 C 0.4947(7) 0.4053(3) 0.1906(3) 0.063(2) Uani 1 1 d . . . H68 H 0.5232 0.3762 0.1884 0.076 Uiso 1 1 calc R . . C69 C 0.4141(7) 0.4105(3) 0.2125(3) 0.063(2) Uani 1 1 d . . . H69 H 0.3859 0.3853 0.2261 0.076 Uiso 1 1 calc R . . C70 C 0.3734(6) 0.4529(2) 0.2148(3) 0.0509(17) Uani 1 1 d . . . H70 H 0.3164 0.4564 0.2301 0.061 Uiso 1 1 calc R . . C71 C 0.0182(6) 0.6423(3) 0.0705(3) 0.068(2) Uani 1 1 d . . . C72 C -0.0345(8) 0.6386(4) 0.0185(3) 0.087(3) Uani 1 1 d . . . H72 H -0.1015 0.6245 0.0086 0.105 Uiso 1 1 calc R . . C73 C 0.0112(8) 0.6553(4) -0.0174(3) 0.087(3) Uani 1 1 d . . . H73 H -0.0236 0.6524 -0.0523 0.105 Uiso 1 1 calc R . . C74 C 0.1145(8) 0.6778(4) -0.0020(3) 0.087(3) Uani 1 1 d . . . H74 H 0.1451 0.6897 -0.0273 0.105 Uiso 1 1 calc R . . C75 C 0.1655(6) 0.6819(3) 0.0466(3) 0.0579(19) Uani 1 1 d . . . H75 H 0.2323 0.6962 0.0562 0.069 Uiso 1 1 calc R . . C76 C 0.1168(7) 0.6640(3) 0.0843(3) 0.063(2) Uani 1 1 d . . . C77 C 0.0959(5) 0.6444(2) 0.1603(2) 0.0412(14) Uani 1 1 d . . . C78 C 0.1255(5) 0.6407(2) 0.2163(2) 0.0378(13) Uani 1 1 d . . . C79 C 0.0509(5) 0.5985(2) 0.3173(2) 0.0436(15) Uani 1 1 d . . . C80 C 0.0948(5) 0.6048(2) 0.3727(2) 0.0422(14) Uani 1 1 d . . . C81 C 0.0599(5) 0.5822(2) 0.4088(3) 0.0483(16) Uani 1 1 d . . . H81 H 0.0051 0.5606 0.3992 0.058 Uiso 1 1 calc R . . C82 C 0.1049(6) 0.5909(3) 0.4596(3) 0.0565(19) Uani 1 1 d . . . H82 H 0.0815 0.5754 0.4852 0.068 Uiso 1 1 calc R . . C83 C 0.1835(6) 0.6222(3) 0.4722(3) 0.062(2) Uani 1 1 d . . . H83 H 0.2149 0.6293 0.5067 0.074 Uiso 1 1 calc R . . C84 C 0.2164(6) 0.6434(3) 0.4334(3) 0.0534(18) Uani 1 1 d . . . H84 H 0.2720 0.6647 0.4421 0.064 Uiso 1 1 calc R . . B1 B 0.7713(16) 0.7138(7) 0.0361(5) 0.115(6) Uani 1 1 d . . . B2 B -0.0662(12) 0.4658(4) 0.3975(4) 0.083(3) Uani 1 1 d U . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Co1 0.0331(4) 0.0346(4) 0.0355(4) -0.0016(3) 0.0095(3) -0.0021(3) Co2 0.0325(4) 0.0405(5) 0.0369(4) -0.0017(3) 0.0080(3) -0.0014(3) Co3 0.0370(4) 0.0400(5) 0.0381(4) -0.0030(4) 0.0107(4) -0.0049(4) Co4 0.0358(4) 0.0399(5) 0.0365(4) -0.0007(4) 0.0073(3) -0.0015(3) Co5 0.0335(4) 0.0350(4) 0.0404(4) 0.0000(3) 0.0093(3) 0.0000(3) S1 0.0369(8) 0.0458(9) 0.0445(9) -0.0093(7) 0.0050(7) 0.0011(7) S2 0.0447(9) 0.0581(11) 0.0460(9) 0.0032(8) 0.0131(7) -0.0123(8) S3 0.0440(9) 0.0387(8) 0.0572(10) 0.0009(7) 0.0222(8) 0.0042(7) S4 0.0385(8) 0.0411(9) 0.0582(10) -0.0039(8) 0.0087(7) 0.0026(7) S5 0.0527(10) 0.0619(11) 0.0596(11) 0.0153(9) 0.0269(9) 0.0059(9) S6 0.0561(12) 0.0882(16) 0.0598(12) -0.0057(11) 0.0143(10) -0.0179(11) Si1 0.0520(12) 0.0493(11) 0.0619(13) 0.0027(10) 0.0208(10) 0.0016(9) F1 0.076(3) 0.057(3) 0.077(3) 0.020(2) 0.014(3) 0.004(2) F2 0.059(3) 0.091(3) 0.066(3) 0.009(2) 0.022(2) 0.028(2) F3 0.103(4) 0.059(3) 0.088(4) 0.011(3) 0.036(3) -0.002(3) F4 0.054(3) 0.071(3) 0.106(4) -0.004(3) 0.020(3) -0.005(2) F5 0.098(4) 0.065(3) 0.117(4) -0.017(3) 0.057(4) 0.001(3) F6 0.082(4) 0.071(3) 0.080(3) 0.004(3) -0.004(3) 0.000(3) F7 0.151(6) 0.122(5) 0.074(3) 0.051(3) 0.061(4) 0.065(4) F8 0.271(12) 0.192(9) 0.109(6) 0.082(6) 0.045(7) 0.138(9) F9 0.258(12) 0.120(6) 0.130(7) 0.018(5) 0.024(7) -0.063(7) F10 0.141(6) 0.144(6) 0.076(4) 0.037(4) -0.017(4) -0.047(5) F11 0.149(6) 0.109(5) 0.135(6) 0.056(4) -0.071(5) -0.046(5) F12 0.078(7) 0.074(6) 0.100(8) -0.001(6) -0.016(6) -0.011(5) F13 0.164(15) 0.121(14) 0.097(9) 0.040(10) 0.018(9) -0.070(12) F14 0.217(15) 0.107(11) 0.121(10) -0.017(8) 0.109(10) 0.003(9) F15 0.073(8) 0.061(10) 0.075(8) 0.030(7) 0.022(7) -0.002(7) F16 0.156(18) 0.19(2) 0.114(14) -0.032(16) 0.085(13) -0.023(17) F17 0.096(12) 0.063(9) 0.114(16) -0.023(9) -0.012(10) 0.001(8) O1 0.031(2) 0.039(2) 0.038(2) -0.0070(18) 0.0077(17) -0.0021(17) O2 0.039(2) 0.041(2) 0.031(2) -0.0031(17) 0.0078(17) -0.0047(18) O3 0.038(2) 0.034(2) 0.045(2) 0.0001(18) 0.0143(19) 0.0036(18) O4 0.029(2) 0.041(2) 0.041(2) -0.0006(19) 0.0074(17) -0.0013(17) O5 0.036(2) 0.042(2) 0.040(2) 0.0005(18) 0.0158(18) -0.0056(18) O6 0.035(2) 0.048(3) 0.038(2) 0.0000(19) 0.0093(18) -0.0052(19) N1 0.029(2) 0.045(3) 0.036(3) 0.005(2) 0.009(2) 0.002(2) N2 0.032(3) 0.043(3) 0.037(3) 0.000(2) 0.006(2) 0.000(2) N3 0.024(2) 0.044(3) 0.045(3) 0.004(2) 0.008(2) 0.002(2) N4 0.039(3) 0.046(3) 0.074(4) -0.015(3) 0.000(3) 0.008(3) N5 0.036(3) 0.040(3) 0.043(3) 0.002(2) 0.008(2) -0.001(2) N6 0.036(3) 0.033(3) 0.037(3) 0.000(2) 0.013(2) 0.001(2) N7 0.041(3) 0.050(3) 0.039(3) -0.006(2) 0.009(2) -0.009(2) N8 0.048(3) 0.048(3) 0.032(3) -0.004(2) 0.010(2) -0.009(2) N9 0.044(3) 0.076(4) 0.042(3) -0.012(3) 0.008(3) -0.020(3) N10 0.042(3) 0.052(3) 0.038(3) -0.006(2) 0.013(2) -0.008(2) N11 0.036(3) 0.035(3) 0.036(3) 0.003(2) 0.011(2) -0.003(2) N12 0.038(3) 0.040(3) 0.040(3) 0.002(2) 0.014(2) 0.000(2) N13 0.042(3) 0.030(2) 0.036(3) 0.007(2) 0.014(2) 0.006(2) N14 0.054(4) 0.050(3) 0.063(4) 0.014(3) 0.032(3) 0.007(3) N15 0.037(3) 0.037(3) 0.052(3) 0.005(2) 0.009(2) -0.001(2) N16 0.036(3) 0.044(3) 0.042(3) 0.010(2) 0.010(2) 0.005(2) N17 0.032(3) 0.041(3) 0.046(3) 0.003(2) 0.007(2) 0.005(2) N18 0.035(3) 0.040(3) 0.042(3) -0.005(2) 0.012(2) 0.006(2) N19 0.049(4) 0.058(4) 0.066(4) -0.030(3) -0.007(3) 0.010(3) N20 0.039(3) 0.040(3) 0.044(3) 0.000(2) 0.005(2) -0.002(2) N21 0.041(3) 0.042(3) 0.041(3) 0.004(2) 0.010(2) 0.000(2) N22 0.047(3) 0.040(3) 0.045(3) -0.001(2) 0.010(3) -0.002(2) N23 0.043(3) 0.041(3) 0.047(3) 0.000(2) 0.012(2) -0.005(2) N24 0.051(3) 0.048(3) 0.065(4) 0.001(3) 0.028(3) 0.004(3) N25 0.046(3) 0.038(3) 0.045(3) -0.001(2) 0.013(2) -0.003(2) N26 0.036(3) 0.044(3) 0.033(3) -0.007(2) 0.003(2) 0.000(2) N27 0.038(3) 0.057(3) 0.034(3) -0.008(2) 0.005(2) -0.005(2) N28 0.037(3) 0.045(3) 0.038(3) -0.002(2) 0.008(2) -0.002(2) N29 0.042(3) 0.071(4) 0.041(3) -0.009(3) 0.008(2) -0.024(3) N30 0.040(3) 0.055(3) 0.041(3) 0.004(3) 0.014(2) -0.001(3) C1 0.028(3) 0.046(3) 0.042(3) -0.006(3) 0.007(3) 0.001(3) C2 0.040(4) 0.066(5) 0.047(4) -0.003(3) 0.004(3) -0.003(3) C3 0.033(3) 0.059(4) 0.051(4) 0.011(3) 0.002(3) 0.004(3) C4 0.045(4) 0.051(4) 0.047(4) 0.017(3) 0.010(3) 0.008(3) C5 0.035(3) 0.045(4) 0.041(3) -0.001(3) 0.007(3) 0.002(3) C6 0.031(3) 0.041(3) 0.037(3) 0.006(3) 0.008(2) 0.002(2) C7 0.033(3) 0.037(3) 0.031(3) -0.003(2) 0.009(2) -0.004(2) C8 0.026(3) 0.037(3) 0.038(3) 0.001(3) 0.010(2) 0.001(2) C9 0.040(3) 0.036(3) 0.048(4) 0.001(3) 0.001(3) 0.003(3) C10 0.032(3) 0.042(3) 0.048(4) 0.004(3) 0.012(3) -0.001(3) C11 0.040(4) 0.049(4) 0.069(5) 0.001(4) 0.012(3) 0.008(3) C12 0.045(4) 0.060(5) 0.085(6) 0.011(4) 0.013(4) 0.008(4) C13 0.040(4) 0.074(5) 0.067(5) 0.012(4) 0.004(4) -0.002(4) C14 0.043(4) 0.057(4) 0.057(4) -0.004(4) 0.007(3) -0.001(3) C15 0.043(4) 0.057(4) 0.041(4) 0.002(3) 0.010(3) 0.005(3) C16 0.053(4) 0.066(5) 0.051(4) 0.011(4) 0.014(3) -0.001(4) C17 0.062(5) 0.062(5) 0.040(4) 0.009(3) 0.015(3) -0.006(4) C18 0.057(4) 0.056(4) 0.036(3) 0.006(3) 0.013(3) 0.001(3) C19 0.046(4) 0.055(4) 0.036(3) 0.003(3) 0.009(3) -0.002(3) C20 0.039(3) 0.038(3) 0.047(4) 0.004(3) 0.018(3) 0.004(3) C21 0.033(3) 0.040(3) 0.042(3) -0.004(3) 0.011(3) -0.006(3) C22 0.038(3) 0.042(3) 0.039(3) -0.004(3) 0.015(3) 0.002(3) C23 0.043(4) 0.049(4) 0.043(4) -0.012(3) 0.011(3) -0.006(3) C24 0.052(4) 0.060(4) 0.032(3) -0.003(3) 0.009(3) -0.013(3) C25 0.069(5) 0.095(6) 0.043(4) -0.025(4) 0.018(4) -0.021(5) C26 0.067(5) 0.098(7) 0.039(4) -0.018(4) 0.001(4) -0.021(5) C27 0.069(5) 0.086(6) 0.035(4) -0.005(4) 0.010(4) -0.013(4) C28 0.046(4) 0.065(5) 0.051(4) -0.003(4) 0.013(3) -0.010(3) C29 0.040(3) 0.039(3) 0.046(4) -0.002(3) 0.010(3) -0.006(3) C30 0.055(4) 0.040(4) 0.066(5) -0.002(3) 0.023(4) 0.010(3) C31 0.067(5) 0.027(3) 0.083(5) 0.000(3) 0.025(4) 0.002(3) C32 0.061(4) 0.035(3) 0.057(4) 0.002(3) 0.022(3) -0.003(3) C33 0.047(4) 0.041(3) 0.040(3) -0.002(3) 0.012(3) -0.011(3) C34 0.038(3) 0.034(3) 0.038(3) -0.007(3) 0.002(3) -0.002(3) C35 0.032(3) 0.037(3) 0.040(3) -0.005(3) 0.009(2) 0.001(2) C36 0.026(3) 0.039(3) 0.037(3) 0.004(3) 0.008(2) -0.004(2) C37 0.036(3) 0.043(3) 0.041(3) 0.004(3) 0.010(3) 0.004(3) C38 0.037(3) 0.046(4) 0.048(4) 0.001(3) 0.006(3) 0.000(3) C39 0.059(4) 0.046(4) 0.060(4) 0.014(3) 0.024(4) -0.003(3) C40 0.061(5) 0.056(4) 0.069(5) 0.015(4) 0.031(4) 0.000(4) C41 0.054(4) 0.049(4) 0.077(5) 0.015(4) 0.018(4) 0.011(3) C42 0.051(4) 0.047(4) 0.062(4) 0.009(3) 0.018(3) 0.006(3) C43 0.044(4) 0.041(4) 0.056(4) 0.003(3) 0.010(3) 0.001(3) C44 0.048(4) 0.059(5) 0.080(6) -0.007(4) 0.010(4) 0.008(4) C45 0.045(4) 0.066(5) 0.101(7) 0.006(5) 0.001(4) 0.017(4) C46 0.051(4) 0.068(5) 0.059(5) 0.004(4) -0.003(4) 0.009(4) C47 0.042(4) 0.062(5) 0.055(4) -0.001(4) -0.001(3) 0.000(3) C48 0.043(4) 0.048(4) 0.050(4) 0.005(3) 0.013(3) 0.001(3) C49 0.035(3) 0.029(3) 0.044(3) 0.005(3) 0.010(3) -0.001(2) C50 0.035(3) 0.032(3) 0.041(3) 0.004(3) 0.009(3) 0.003(2) C51 0.039(3) 0.044(4) 0.042(3) -0.003(3) 0.009(3) -0.002(3) C52 0.041(3) 0.045(4) 0.045(4) -0.001(3) 0.017(3) -0.001(3) C53 0.031(3) 0.060(4) 0.052(4) -0.007(3) 0.000(3) -0.003(3) C54 0.039(4) 0.071(5) 0.056(4) -0.005(4) -0.003(3) 0.000(3) C55 0.044(4) 0.058(4) 0.063(5) 0.003(4) 0.013(3) 0.004(3) C56 0.048(4) 0.050(4) 0.049(4) 0.002(3) 0.009(3) 0.009(3) C57 0.047(4) 0.061(4) 0.051(4) 0.014(3) 0.014(3) -0.004(3) C58 0.064(5) 0.082(6) 0.068(5) 0.031(5) 0.029(4) -0.004(4) C59 0.069(5) 0.051(5) 0.075(6) 0.026(4) -0.003(4) -0.003(4) C60 0.062(5) 0.064(5) 0.059(5) 0.003(4) 0.010(4) 0.004(4) C61 0.064(5) 0.043(4) 0.048(4) 0.011(3) 0.007(3) -0.008(3) C62 0.039(3) 0.055(4) 0.044(4) 0.010(3) 0.005(3) -0.002(3) C63 0.046(4) 0.054(4) 0.030(3) 0.002(3) 0.005(3) -0.007(3) C64 0.048(4) 0.038(3) 0.039(3) 0.005(3) 0.010(3) -0.002(3) C65 0.040(4) 0.056(4) 0.047(4) -0.001(3) 0.012(3) -0.011(3) C66 0.047(4) 0.041(4) 0.041(4) -0.004(3) -0.004(3) 0.003(3) C67 0.061(5) 0.050(4) 0.079(6) -0.001(4) 0.018(4) 0.000(4) C68 0.065(5) 0.046(4) 0.083(6) 0.002(4) 0.025(4) 0.012(4) C69 0.076(6) 0.046(4) 0.066(5) 0.004(4) 0.013(4) -0.011(4) C70 0.050(4) 0.042(4) 0.063(4) -0.003(3) 0.017(3) -0.001(3) C71 0.051(4) 0.098(7) 0.049(4) -0.023(4) 0.003(3) 0.013(4) C72 0.075(6) 0.124(9) 0.059(5) -0.004(6) 0.012(5) 0.001(6) C73 0.082(7) 0.129(9) 0.048(5) 0.012(5) 0.010(5) 0.008(6) C74 0.084(7) 0.124(9) 0.051(5) 0.002(5) 0.013(5) 0.003(6) C75 0.049(4) 0.074(5) 0.051(4) -0.002(4) 0.013(3) -0.010(4) C76 0.058(5) 0.080(6) 0.054(4) -0.003(4) 0.017(4) -0.005(4) C77 0.034(3) 0.044(4) 0.046(4) -0.002(3) 0.012(3) 0.002(3) C78 0.038(3) 0.039(3) 0.035(3) -0.011(3) 0.007(3) 0.000(3) C79 0.047(4) 0.041(3) 0.046(4) -0.008(3) 0.017(3) 0.000(3) C80 0.033(3) 0.045(4) 0.047(4) 0.001(3) 0.008(3) -0.008(3) C81 0.036(3) 0.054(4) 0.055(4) 0.002(3) 0.013(3) -0.003(3) C82 0.043(4) 0.075(5) 0.055(4) 0.016(4) 0.020(3) 0.009(4) C83 0.039(4) 0.099(6) 0.047(4) 0.005(4) 0.009(3) -0.010(4) C84 0.047(4) 0.063(5) 0.043(4) 0.007(3) -0.002(3) -0.005(3) B1 0.142(14) 0.144(14) 0.071(8) 0.048(9) 0.046(9) 0.069(12) B2 0.121(9) 0.065(6) 0.060(6) -0.004(5) 0.017(6) -0.026(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 Co1 O2 2.086(4) . ? Co1 O3 2.102(4) . ? Co1 O1 2.114(4) . ? Co1 N1 2.129(5) . ? Co1 N6 2.138(5) . ? Co1 N11 2.157(5) . ? Co2 N28 2.033(5) . ? Co2 N3 2.036(5) . ? Co2 O6 2.143(4) . ? Co2 O1 2.175(4) . ? Co2 N30 2.209(5) . ? Co2 N5 2.224(5) . ? Co3 N23 2.016(6) . ? Co3 N8 2.018(5) . ? Co3 O2 2.143(4) . ? Co3 O5 2.161(4) . ? Co3 N25 2.205(5) . ? Co3 N10 2.206(5) . ? Co4 O5 2.094(4) . ? Co4 O4 2.101(4) . ? Co4 O6 2.101(4) . ? Co4 N26 2.127(5) . ? Co4 N21 2.136(5) . ? Co4 N16 2.145(5) . ? Co5 N18 2.011(5) . ? Co5 N13 2.015(5) . ? Co5 O3 2.160(4) . ? Co5 O4 2.165(4) . ? Co5 N15 2.223(5) . ? Co5 N20 2.246(5) . ? S1 C7 1.714(6) . ? S1 C1 1.719(6) . ? S2 C21 1.727(6) . ? S2 C15 1.749(7) . ? S3 C35 1.712(6) . ? S3 C29 1.735(7) . ? S4 C49 1.711(6) . ? S4 C43 1.744(7) . ? S5 C63 1.717(7) . ? S5 C57 1.746(8) . ? S6 C77 1.689(7) . ? S6 C71 1.706(9) . ? Si1 F6 1.654(5) . ? Si1 F5 1.655(5) . ? Si1 F1 1.664(5) . ? Si1 F2 1.675(5) . ? Si1 F4 1.686(5) . ? Si1 F3 1.698(5) . ? F7 B1 1.360(14) . ? F8 B1 1.338(17) . ? F9 B1 1.38(2) . ? F10 B1 1.347(19) . ? F11 B2 1.301(13) . ? F12 B2 1.475(16) . ? F13 B2 1.342(18) . ? F14 B2 1.320(15) . ? F15 B2 1.281(16) . ? F16 B2 1.48(2) . ? F17 B2 1.40(2) . ? O1 C8 1.309(7) . ? O2 C22 1.314(7) . ? O3 C36 1.306(7) . ? O4 C50 1.308(7) . ? O5 C64 1.299(7) . ? O6 C78 1.306(7) . ? N1 C7 1.330(7) . ? N1 C6 1.403(7) . ? N2 C8 1.292(8) . ? N2 N3 1.403(7) . ? N3 C9 1.309(8) . ? N4 C9 1.320(8) . ? N4 H4A 0.8800 . ? N4 H4B 0.8800 . ? N5 C14 1.331(8) . ? N5 C10 1.349(8) . ? N6 C21 1.310(8) . ? N6 C20 1.396(8) . ? N7 C22 1.303(8) . ? N7 N8 1.406(7) . ? N8 C23 1.281(8) . ? N9 C23 1.333(8) . ? N9 H9A 0.8800 . ? N9 H9B 0.8800 . ? N10 C28 1.343(9) . ? N10 C24 1.343(8) . ? N11 C35 1.301(7) . ? N11 C34 1.383(8) . ? N12 C36 1.313(7) . ? N12 N13 1.397(7) . ? N13 C37 1.288(8) . ? N14 C37 1.336(8) . ? N14 H14A 0.8800 . ? N14 H14B 0.8800 . ? N15 C38 1.343(9) . ? N15 C42 1.355(8) . ? N16 C49 1.318(8) . ? N16 C48 1.402(8) . ? N17 C50 1.305(8) . ? N17 N18 1.404(7) . ? N18 C51 1.298(8) . ? N19 C51 1.336(8) . ? N19 H19A 0.8800 . ? N19 H19B 0.8800 . ? N20 C56 1.328(8) . ? N20 C52 1.347(8) . ? N21 C63 1.301(9) . ? N21 C62 1.394(8) . ? N22 C64 1.304(8) . ? N22 N23 1.388(7) . ? N23 C65 1.297(9) . ? N24 C65 1.345(8) . ? N24 H24A 0.8800 . ? N24 H24B 0.8800 . ? N25 C70 1.330(9) . ? N25 C66 1.348(9) . ? N26 C77 1.301(8) . ? N26 C76 1.422(9) . ? N27 C78 1.305(8) . ? N27 N28 1.398(7) . ? N28 C79 1.300(8) . ? N29 C79 1.320(8) . ? N29 H29A 0.8800 . ? N29 H29B 0.8800 . ? N30 C84 1.331(9) . ? N30 C80 1.346(8) . ? C1 C6 1.400(9) . ? C1 C2 1.409(9) . ? C2 C3 1.383(10) . ? C2 H2 0.9500 . ? C3 C4 1.384(10) . ? C3 H3 0.9500 . ? C4 C5 1.373(9) . ? C4 H4 0.9500 . ? C5 C6 1.381(8) . ? C5 H5 0.9500 . ? C7 C8 1.456(8) . ? C9 C10 1.491(8) . ? C10 C11 1.374(9) . ? C11 C12 1.393(10) . ? C11 H11 0.9500 . ? C12 C13 1.375(12) . ? C12 H12 0.9500 . ? C13 C14 1.395(11) . ? C13 H13 0.9500 . ? C14 H14 0.9500 . ? C15 C20 1.393(9) . ? C15 C16 1.404(10) . ? C16 C17 1.376(10) . ? C16 H16 0.9500 . ? C17 C18 1.389(10) . ? C17 H17 0.9500 . ? C18 C19 1.382(9) . ? C18 H18 0.9500 . ? C19 C20 1.403(9) . ? C19 H19 0.9500 . ? C21 C22 1.466(9) . ? C23 C24 1.486(9) . ? C24 C25 1.378(10) . ? C25 C26 1.382(11) . ? C25 H25 0.9500 . ? C26 C27 1.364(11) . ? C26 H26 0.9500 . ? C27 C28 1.373(10) . ? C27 H27 0.9500 . ? C28 H28 0.9500 . ? C29 C30 1.385(9) . ? C29 C34 1.398(9) . ? C30 C31 1.382(10) . ? C30 H30 0.9500 . ? C31 C32 1.401(10) . ? C31 H31 0.9500 . ? C32 C33 1.354(9) . ? C32 H32 0.9500 . ? C33 C34 1.407(9) . ? C33 H33 0.9500 . ? C35 C36 1.481(8) . ? C37 C38 1.489(9) . ? C38 C39 1.377(9) . ? C39 C40 1.382(10) . ? C39 H39 0.9500 . ? C40 C41 1.349(11) . ? C40 H40 0.9500 . ? C41 C42 1.399(10) . ? C41 H41 0.9500 . ? C42 H42 0.9500 . ? C43 C44 1.395(10) . ? C43 C48 1.397(10) . ? C44 C45 1.379(11) . ? C44 H44 0.9500 . ? C45 C46 1.397(12) . ? C45 H45 0.9500 . ? C46 C47 1.390(10) . ? C46 H46 0.9500 . ? C47 C48 1.403(10) . ? C47 H47 0.9500 . ? C49 C50 1.474(8) . ? C51 C52 1.487(9) . ? C52 C53 1.395(9) . ? C53 C54 1.381(10) . ? C53 H53 0.9500 . ? C54 C55 1.387(11) . ? C54 H54 0.9500 . ? C55 C56 1.382(10) . ? C55 H55 0.9500 . ? C56 H56 0.9500 . ? C57 C58 1.378(10) . ? C57 C62 1.415(10) . ? C58 C59 1.359(12) . ? C58 H58 0.9500 . ? C59 C60 1.400(12) . ? C59 H59 0.9500 . ? C60 C61 1.376(10) . ? C60 H60 0.9500 . ? C61 C62 1.371(10) . ? C61 H61 0.9500 . ? C63 C64 1.474(9) . ? C65 C66 1.477(10) . ? C66 C67 1.396(10) . ? C67 C68 1.382(11) . ? C67 H67 0.9500 . ? C68 C69 1.351(11) . ? C68 H68 0.9500 . ? C69 C70 1.378(10) . ? C69 H69 0.9500 . ? C70 H70 0.9500 . ? C71 C76 1.411(11) . ? C71 C72 1.415(12) . ? C72 C73 1.365(13) . ? C72 H72 0.9500 . ? C73 C74 1.476(14) . ? C73 H73 0.9500 . ? C74 C75 1.329(11) . ? C74 H74 0.9500 . ? C75 C76 1.444(11) . ? C75 H75 0.9500 . ? C77 C78 1.481(9) . ? C79 C80 1.486(9) . ? C80 C81 1.365(9) . ? C81 C82 1.385(10) . ? C81 H81 0.9500 . ? C82 C83 1.369(11) . ? C82 H82 0.9500 . ? C83 C84 1.392(10) . ? C83 H83 0.9500 . ? C84 H84 0.9500 . ? 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 O3 96.77(16) . . ? O2 Co1 O1 93.94(16) . . ? O3 Co1 O1 94.50(16) . . ? O2 Co1 N1 173.66(18) . . ? O3 Co1 N1 84.19(18) . . ? O1 Co1 N1 79.73(17) . . ? O2 Co1 N6 79.22(17) . . ? O3 Co1 N6 175.98(18) . . ? O1 Co1 N6 86.09(17) . . ? N1 Co1 N6 99.83(19) . . ? O2 Co1 N11 85.51(18) . . ? O3 Co1 N11 79.25(17) . . ? O1 Co1 N11 173.61(17) . . ? N1 Co1 N11 100.82(19) . . ? N6 Co1 N11 100.04(18) . . ? N28 Co2 N3 159.3(2) . . ? N28 Co2 O6 74.48(18) . . ? N3 Co2 O6 121.02(18) . . ? N28 Co2 O1 121.28(19) . . ? N3 Co2 O1 74.28(17) . . ? O6 Co2 O1 92.68(16) . . ? N28 Co2 N30 74.0(2) . . ? N3 Co2 N30 92.4(2) . . ? O6 Co2 N30 146.51(19) . . ? O1 Co2 N30 94.06(18) . . ? N28 Co2 N5 91.9(2) . . ? N3 Co2 N5 74.18(19) . . ? O6 Co2 N5 94.72(18) . . ? O1 Co2 N5 146.80(17) . . ? N30 Co2 N5 97.3(2) . . ? N23 Co3 N8 159.3(2) . . ? N23 Co3 O2 121.06(19) . . ? N8 Co3 O2 74.69(18) . . ? N23 Co3 O5 74.86(19) . . ? N8 Co3 O5 120.5(2) . . ? O2 Co3 O5 91.95(16) . . ? N23 Co3 N25 74.5(2) . . ? N8 Co3 N25 91.3(2) . . ? O2 Co3 N25 96.56(18) . . ? O5 Co3 N25 148.20(18) . . ? N23 Co3 N10 92.1(2) . . ? N8 Co3 N10 74.4(2) . . ? O2 Co3 N10 146.55(18) . . ? O5 Co3 N10 92.72(18) . . ? N25 Co3 N10 96.7(2) . . ? O5 Co4 O4 93.86(16) . . ? O5 Co4 O6 95.18(16) . . ? O4 Co4 O6 95.31(16) . . ? O5 Co4 N26 89.25(18) . . ? O4 Co4 N26 174.10(18) . . ? O6 Co4 N26 79.41(18) . . ? O5 Co4 N21 79.27(18) . . ? O4 Co4 N21 87.51(18) . . ? O6 Co4 N21 173.96(19) . . ? N26 Co4 N21 98.0(2) . . ? O5 Co4 N16 172.77(19) . . ? O4 Co4 N16 78.93(18) . . ? O6 Co4 N16 86.17(18) . . ? N26 Co4 N16 98.0(2) . . ? N21 Co4 N16 99.6(2) . . ? N18 Co5 N13 156.6(2) . . ? N18 Co5 O3 123.55(19) . . ? N13 Co5 O3 74.90(17) . . ? N18 Co5 O4 74.80(18) . . ? N13 Co5 O4 121.86(18) . . ? O3 Co5 O4 92.83(16) . . ? N18 Co5 N15 90.7(2) . . ? N13 Co5 N15 73.46(19) . . ? O3 Co5 N15 145.53(18) . . ? O4 Co5 N15 92.37(18) . . ? N18 Co5 N20 74.0(2) . . ? N13 Co5 N20 91.3(2) . . ? O3 Co5 N20 95.05(18) . . ? O4 Co5 N20 146.77(18) . . ? N15 Co5 N20 99.0(2) . . ? C7 S1 C1 89.4(3) . . ? C21 S2 C15 88.7(3) . . ? C35 S3 C29 88.4(3) . . ? C49 S4 C43 88.4(3) . . ? C63 S5 C57 88.4(3) . . ? C77 S6 C71 90.1(4) . . ? F6 Si1 F5 90.9(3) . . ? F6 Si1 F1 91.5(3) . . ? F5 Si1 F1 88.2(3) . . ? F6 Si1 F2 89.5(3) . . ? F5 Si1 F2 179.6(4) . . ? F1 Si1 F2 91.7(3) . . ? F6 Si1 F4 177.0(3) . . ? F5 Si1 F4 90.4(3) . . ? F1 Si1 F4 91.3(3) . . ? F2 Si1 F4 89.2(3) . . ? F6 Si1 F3 89.3(3) . . ? F5 Si1 F3 90.0(3) . . ? F1 Si1 F3 178.1(3) . . ? F2 Si1 F3 90.1(3) . . ? F4 Si1 F3 88.0(3) . . ? C8 O1 Co1 112.6(3) . . ? C8 O1 Co2 109.0(3) . . ? Co1 O1 Co2 137.60(19) . . ? C22 O2 Co1 114.3(4) . . ? C22 O2 Co3 108.4(3) . . ? Co1 O2 Co3 136.2(2) . . ? C36 O3 Co1 113.5(3) . . ? C36 O3 Co5 108.0(3) . . ? Co1 O3 Co5 137.9(2) . . ? C50 O4 Co4 114.6(4) . . ? C50 O4 Co5 107.9(4) . . ? Co4 O4 Co5 136.0(2) . . ? C64 O5 Co4 113.8(4) . . ? C64 O5 Co3 107.5(4) . . ? Co4 O5 Co3 136.3(2) . . ? C78 O6 Co4 113.3(4) . . ? C78 O6 Co2 109.2(4) . . ? Co4 O6 Co2 136.6(2) . . ? C7 N1 C6 111.2(5) . . ? C7 N1 Co1 109.9(4) . . ? C6 N1 Co1 138.6(4) . . ? C8 N2 N3 109.0(5) . . ? C9 N3 N2 117.4(5) . . ? C9 N3 Co2 123.0(4) . . ? N2 N3 Co2 119.1(4) . . ? C9 N4 H4A 120.0 . . ? C9 N4 H4B 120.0 . . ? H4A N4 H4B 120.0 . . ? C14 N5 C10 118.0(6) . . ? C14 N5 Co2 127.6(5) . . ? C10 N5 Co2 114.2(4) . . ? C21 N6 C20 110.8(5) . . ? C21 N6 Co1 110.5(4) . . ? C20 N6 Co1 138.6(4) . . ? C22 N7 N8 107.4(5) . . ? C23 N8 N7 117.0(5) . . ? C23 N8 Co3 122.8(4) . . ? N7 N8 Co3 118.9(4) . . ? C23 N9 H9A 120.0 . . ? C23 N9 H9B 120.0 . . ? H9A N9 H9B 120.0 . . ? C28 N10 C24 118.9(6) . . ? C28 N10 Co3 127.4(5) . . ? C24 N10 Co3 113.7(4) . . ? C35 N11 C34 109.9(5) . . ? C35 N11 Co1 110.4(4) . . ? C34 N11 Co1 139.1(4) . . ? C36 N12 N13 107.5(5) . . ? C37 N13 N12 116.3(5) . . ? C37 N13 Co5 124.1(4) . . ? N12 N13 Co5 119.3(4) . . ? C37 N14 H14A 120.0 . . ? C37 N14 H14B 120.0 . . ? H14A N14 H14B 120.0 . . ? C38 N15 C42 118.3(6) . . ? C38 N15 Co5 115.1(4) . . ? C42 N15 Co5 126.6(5) . . ? C49 N16 C48 110.2(5) . . ? C49 N16 Co4 110.6(4) . . ? C48 N16 Co4 138.9(5) . . ? C50 N17 N18 107.2(5) . . ? C51 N18 N17 115.6(5) . . ? C51 N18 Co5 123.9(4) . . ? N17 N18 Co5 120.0(4) . . ? C51 N19 H19A 120.0 . . ? C51 N19 H19B 120.0 . . ? H19A N19 H19B 120.0 . . ? C56 N20 C52 118.2(6) . . ? C56 N20 Co5 128.3(5) . . ? C52 N20 Co5 113.3(4) . . ? C63 N21 C62 111.2(6) . . ? C63 N21 Co4 110.6(4) . . ? C62 N21 Co4 138.0(5) . . ? C64 N22 N23 108.5(5) . . ? C65 N23 N22 117.2(5) . . ? C65 N23 Co3 122.5(4) . . ? N22 N23 Co3 118.6(4) . . ? C65 N24 H24A 120.0 . . ? C65 N24 H24B 120.0 . . ? H24A N24 H24B 120.0 . . ? C70 N25 C66 118.0(6) . . ? C70 N25 Co3 127.8(5) . . ? C66 N25 Co3 114.1(4) . . ? C77 N26 C76 110.1(6) . . ? C77 N26 Co4 111.1(4) . . ? C76 N26 Co4 138.7(5) . . ? C78 N27 N28 108.0(5) . . ? C79 N28 N27 117.6(5) . . ? C79 N28 Co2 123.0(4) . . ? N27 N28 Co2 118.6(4) . . ? C79 N29 H29A 120.0 . . ? C79 N29 H29B 120.0 . . ? H29A N29 H29B 120.0 . . ? C84 N30 C80 118.0(6) . . ? C84 N30 Co2 127.1(5) . . ? C80 N30 Co2 114.9(4) . . ? C6 C1 C2 119.7(6) . . ? C6 C1 S1 111.6(4) . . ? C2 C1 S1 128.7(5) . . ? C3 C2 C1 117.6(7) . . ? C3 C2 H2 121.2 . . ? C1 C2 H2 121.2 . . ? C2 C3 C4 121.7(6) . . ? C2 C3 H3 119.2 . . ? C4 C3 H3 119.2 . . ? C5 C4 C3 121.1(6) . . ? C5 C4 H4 119.4 . . ? C3 C4 H4 119.4 . . ? C4 C5 C6 118.3(6) . . ? C4 C5 H5 120.9 . . ? C6 C5 H5 120.9 . . ? C5 C6 C1 121.6(6) . . ? C5 C6 N1 126.1(6) . . ? C1 C6 N1 112.3(5) . . ? N1 C7 C8 120.0(5) . . ? N1 C7 S1 115.6(4) . . ? C8 C7 S1 124.4(4) . . ? N2 C8 O1 126.6(5) . . ? N2 C8 C7 116.2(5) . . ? O1 C8 C7 117.3(5) . . ? N3 C9 N4 125.4(6) . . ? N3 C9 C10 113.6(5) . . ? N4 C9 C10 121.0(6) . . ? N5 C10 C11 123.1(6) . . ? N5 C10 C9 114.4(5) . . ? C11 C10 C9 122.5(6) . . ? C10 C11 C12 118.4(7) . . ? C10 C11 H11 120.8 . . ? C12 C11 H11 120.8 . . ? C13 C12 C11 119.2(7) . . ? C13 C12 H12 120.4 . . ? C11 C12 H12 120.4 . . ? C12 C13 C14 118.6(7) . . ? C12 C13 H13 120.7 . . ? C14 C13 H13 120.7 . . ? N5 C14 C13 122.7(7) . . ? N5 C14 H14 118.7 . . ? C13 C14 H14 118.7 . . ? C20 C15 C16 122.0(6) . . ? C20 C15 S2 110.1(5) . . ? C16 C15 S2 127.9(6) . . ? C17 C16 C15 117.0(7) . . ? C17 C16 H16 121.5 . . ? C15 C16 H16 121.5 . . ? C16 C17 C18 121.4(7) . . ? C16 C17 H17 119.3 . . ? C18 C17 H17 119.3 . . ? C19 C18 C17 122.2(7) . . ? C19 C18 H18 118.9 . . ? C17 C18 H18 118.9 . . ? C18 C19 C20 117.3(6) . . ? C18 C19 H19 121.4 . . ? C20 C19 H19 121.4 . . ? C15 C20 N6 114.1(6) . . ? C15 C20 C19 120.2(6) . . ? N6 C20 C19 125.7(6) . . ? N6 C21 C22 120.0(5) . . ? N6 C21 S2 116.3(5) . . ? C22 C21 S2 123.7(5) . . ? N7 C22 O2 126.7(6) . . ? N7 C22 C21 117.5(5) . . ? O2 C22 C21 115.8(5) . . ? N8 C23 N9 124.7(6) . . ? N8 C23 C24 113.8(6) . . ? N9 C23 C24 121.3(6) . . ? N10 C24 C25 121.1(6) . . ? N10 C24 C23 114.3(6) . . ? C25 C24 C23 124.6(7) . . ? C24 C25 C26 119.8(8) . . ? C24 C25 H25 120.1 . . ? C26 C25 H25 120.1 . . ? C27 C26 C25 118.5(7) . . ? C27 C26 H26 120.8 . . ? C25 C26 H26 120.8 . . ? C26 C27 C28 119.8(7) . . ? C26 C27 H27 120.1 . . ? C28 C27 H27 120.1 . . ? N10 C28 C27 121.9(7) . . ? N10 C28 H28 119.1 . . ? C27 C28 H28 119.1 . . ? C30 C29 C34 121.3(6) . . ? C30 C29 S3 128.9(5) . . ? C34 C29 S3 109.8(5) . . ? C31 C30 C29 119.3(7) . . ? C31 C30 H30 120.3 . . ? C29 C30 H30 120.3 . . ? C30 C31 C32 119.0(6) . . ? C30 C31 H31 120.5 . . ? C32 C31 H31 120.5 . . ? C33 C32 C31 122.4(7) . . ? C33 C32 H32 118.8 . . ? C31 C32 H32 118.8 . . ? C32 C33 C34 119.0(6) . . ? C32 C33 H33 120.5 . . ? C34 C33 H33 120.5 . . ? N11 C34 C29 114.4(6) . . ? N11 C34 C33 126.6(6) . . ? C29 C34 C33 118.9(6) . . ? N11 C35 C36 119.6(5) . . ? N11 C35 S3 117.5(5) . . ? C36 C35 S3 122.9(4) . . ? O3 C36 N12 127.3(5) . . ? O3 C36 C35 117.0(5) . . ? N12 C36 C35 115.7(5) . . ? N13 C37 N14 124.5(6) . . ? N13 C37 C38 114.1(6) . . ? N14 C37 C38 121.4(6) . . ? N15 C38 C39 122.8(6) . . ? N15 C38 C37 112.9(6) . . ? C39 C38 C37 124.2(6) . . ? C38 C39 C40 118.2(7) . . ? C38 C39 H39 120.9 . . ? C40 C39 H39 120.9 . . ? C41 C40 C39 120.3(7) . . ? C41 C40 H40 119.8 . . ? C39 C40 H40 119.8 . . ? C40 C41 C42 119.3(7) . . ? C40 C41 H41 120.3 . . ? C42 C41 H41 120.3 . . ? N15 C42 C41 121.1(7) . . ? N15 C42 H42 119.5 . . ? C41 C42 H42 119.5 . . ? C44 C43 C48 121.7(7) . . ? C44 C43 S4 127.3(6) . . ? C48 C43 S4 110.9(5) . . ? C45 C44 C43 117.1(8) . . ? C45 C44 H44 121.4 . . ? C43 C44 H44 121.4 . . ? C44 C45 C46 122.0(7) . . ? C44 C45 H45 119.0 . . ? C46 C45 H45 119.0 . . ? C47 C46 C45 120.9(7) . . ? C47 C46 H46 119.5 . . ? C45 C46 H46 119.5 . . ? C46 C47 C48 117.6(7) . . ? C46 C47 H47 121.2 . . ? C48 C47 H47 121.2 . . ? C43 C48 N16 113.2(6) . . ? C43 C48 C47 120.5(7) . . ? N16 C48 C47 126.3(7) . . ? N16 C49 C50 119.7(5) . . ? N16 C49 S4 117.2(5) . . ? C50 C49 S4 123.1(5) . . ? N17 C50 O4 127.7(5) . . ? N17 C50 C49 116.3(5) . . ? O4 C50 C49 115.9(5) . . ? N18 C51 N19 125.5(6) . . ? N18 C51 C52 113.9(6) . . ? N19 C51 C52 120.6(6) . . ? N20 C52 C53 121.9(6) . . ? N20 C52 C51 114.3(6) . . ? C53 C52 C51 123.8(6) . . ? C54 C53 C52 119.0(7) . . ? C54 C53 H53 120.5 . . ? C52 C53 H53 120.5 . . ? C53 C54 C55 119.0(7) . . ? C53 C54 H54 120.5 . . ? C55 C54 H54 120.5 . . ? C56 C55 C54 118.3(7) . . ? C56 C55 H55 120.9 . . ? C54 C55 H55 120.9 . . ? N20 C56 C55 123.6(7) . . ? N20 C56 H56 118.2 . . ? C55 C56 H56 118.2 . . ? C58 C57 C62 120.5(7) . . ? C58 C57 S5 129.0(6) . . ? C62 C57 S5 110.4(5) . . ? C59 C58 C57 118.3(8) . . ? C59 C58 H58 120.9 . . ? C57 C58 H58 120.9 . . ? C58 C59 C60 121.7(8) . . ? C58 C59 H59 119.1 . . ? C60 C59 H59 119.1 . . ? C61 C60 C59 120.2(8) . . ? C61 C60 H60 119.9 . . ? C59 C60 H60 119.9 . . ? C62 C61 C60 118.8(8) . . ? C62 C61 H61 120.6 . . ? C60 C61 H61 120.6 . . ? C61 C62 N21 127.0(7) . . ? C61 C62 C57 120.3(7) . . ? N21 C62 C57 112.7(6) . . ? N21 C63 C64 119.7(6) . . ? N21 C63 S5 117.3(5) . . ? C64 C63 S5 122.9(5) . . ? O5 C64 N22 126.9(6) . . ? O5 C64 C63 116.5(6) . . ? N22 C64 C63 116.6(6) . . ? N23 C65 N24 124.3(6) . . ? N23 C65 C66 114.3(6) . . ? N24 C65 C66 121.4(7) . . ? N25 C66 C67 122.1(7) . . ? N25 C66 C65 114.0(6) . . ? C67 C66 C65 123.9(7) . . ? C68 C67 C66 117.6(8) . . ? C68 C67 H67 121.2 . . ? C66 C67 H67 121.2 . . ? C69 C68 C67 120.4(7) . . ? C69 C68 H68 119.8 . . ? C67 C68 H68 119.8 . . ? C68 C69 C70 118.8(7) . . ? C68 C69 H69 120.6 . . ? C70 C69 H69 120.6 . . ? N25 C70 C69 123.0(7) . . ? N25 C70 H70 118.5 . . ? C69 C70 H70 118.5 . . ? C76 C71 C72 119.2(9) . . ? C76 C71 S6 110.5(6) . . ? C72 C71 S6 130.4(8) . . ? C73 C72 C71 119.8(10) . . ? C73 C72 H72 120.1 . . ? C71 C72 H72 120.1 . . ? C72 C73 C74 120.1(9) . . ? C72 C73 H73 120.0 . . ? C74 C73 H73 120.0 . . ? C75 C74 C73 121.3(9) . . ? C75 C74 H74 119.3 . . ? C73 C74 H74 119.3 . . ? C74 C75 C76 118.3(8) . . ? C74 C75 H75 120.9 . . ? C76 C75 H75 120.9 . . ? C71 C76 N26 112.1(7) . . ? C71 C76 C75 121.4(7) . . ? N26 C76 C75 126.5(7) . . ? N26 C77 C78 119.3(6) . . ? N26 C77 S6 117.0(5) . . ? C78 C77 S6 123.6(5) . . ? N27 C78 O6 126.5(5) . . ? N27 C78 C77 117.1(5) . . ? O6 C78 C77 116.4(5) . . ? N28 C79 N29 125.7(6) . . ? N28 C79 C80 113.7(6) . . ? N29 C79 C80 120.6(6) . . ? N30 C80 C81 122.3(6) . . ? N30 C80 C79 113.9(6) . . ? C81 C80 C79 123.7(6) . . ? C80 C81 C82 119.5(7) . . ? C80 C81 H81 120.2 . . ? C82 C81 H81 120.2 . . ? C83 C82 C81 118.8(7) . . ? C83 C82 H82 120.6 . . ? C81 C82 H82 120.6 . . ? C82 C83 C84 118.5(7) . . ? C82 C83 H83 120.8 . . ? C84 C83 H83 120.8 . . ? N30 C84 C83 122.9(7) . . ? N30 C84 H84 118.6 . . ? C83 C84 H84 118.6 . . ? F8 B1 F10 120.2(13) . . ? F8 B1 F7 114.0(11) . . ? F10 B1 F7 109.1(16) . . ? F8 B1 F9 97.7(17) . . ? F10 B1 F9 103.7(11) . . ? F7 B1 F9 110.8(13) . . ? F15 B2 F11 113.6(11) . . ? F11 B2 F14 121.8(15) . . ? F11 B2 F13 109.7(11) . . ? F14 B2 F13 106.4(13) . . ? F15 B2 F17 117.8(15) . . ? F11 B2 F17 115.6(12) . . ? F11 B2 F12 104.8(9) . . ? F14 B2 F12 102.5(12) . . ? F13 B2 F12 111.3(15) . . ? F15 B2 F16 105.3(16) . . ? F11 B2 F16 105.9(13) . . ? F14 B2 F16 132.3(15) . . ? F17 B2 F16 95.5(16) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.524 _refine_diff_density_min -0.755 _refine_diff_density_rms 0.099 data_3 _database_code_depnum_ccdc_archive 'CCDC 807492' #TrackingRef 'Submission.cif' # start Validation Reply Form _vrf_PLAT306_3 ; PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) ....... O6 RESPONSE: This is a lattice solvent water molecule. The corresponding hydrogen atoms could not be located in difference map positions and were therefore omitted from the model. They were included in the formula for the calculation of intensive properties. ; # end Validation Reply Form _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H32 cu4 N28 O4, 4(Cl O4), 4(H2 O)' _chemical_formula_sum 'C36 H40 Cl4 Cu4 N28 O24' _chemical_formula_weight 1644.88 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' Cl Cl 0.1484 0.1585 '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' 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' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'I 41/a' _symmetry_space_group_name_Hall '-I 4ad' _symmetry_Int_Tables_number 88 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y+3/4, x+1/4, z+1/4' '-x+1/2, -y, z+1/2' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-y+5/4, x+3/4, z+3/4' '-x+1, -y+1/2, z+1' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'y-3/4, -x-1/4, -z-1/4' 'x-1/2, y, -z-1/2' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'y-1/4, -x+1/4, -z+1/4' 'x, y+1/2, -z' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 14.7586(16) _cell_length_b 14.7586(16) _cell_length_c 27.279(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 5941.8(11) _cell_formula_units_Z 4 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 9791 _cell_measurement_theta_min 2.4575 _cell_measurement_theta_max 30.5672 _exptl_crystal_description Prism _exptl_crystal_colour Green _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.839 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3312 _exptl_absorpt_coefficient_mu 1.696 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.8757 _exptl_absorpt_correction_T_min 0.8328 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 26011 _diffrn_reflns_av_R_equivalents 0.0267 _diffrn_reflns_av_sigmaI/netI 0.0133 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -34 _diffrn_reflns_limit_l_max 34 _diffrn_reflns_theta_min 2.63 _diffrn_reflns_theta_max 26.50 _reflns_number_total 3084 _reflns_number_gt 2978 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Acta Cryst.2008, A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst.2008, A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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^)+(0.1433P)^2^+19.5622P] 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 3084 _refine_ls_number_parameters 218 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0830 _refine_ls_R_factor_gt 0.0813 _refine_ls_wR_factor_ref 0.2390 _refine_ls_wR_factor_gt 0.2364 _refine_ls_goodness_of_fit_ref 1.113 _refine_ls_restrained_S_all 1.113 _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 Cu1 Cu 0.17529(4) 0.31727(4) 0.10815(2) 0.0525(3) Uani 1 1 d . . . Cl1 Cl 0.34791(14) 0.50717(13) 0.08461(7) 0.0893(6) Uani 1 1 d . . . O1 O 0.0555(2) 0.3725(2) 0.09634(11) 0.0522(8) Uani 1 1 d . . . O2 O 0.3847(4) 0.4486(4) 0.1197(2) 0.0973(17) Uani 1 1 d . . . O3 O 0.2535(6) 0.5025(7) 0.0892(3) 0.160(3) Uani 1 1 d . . . O4 O 0.3571(6) 0.4702(7) 0.0346(2) 0.151(3) Uani 1 1 d . . . O5 O 0.3879(15) 0.5845(10) 0.0831(6) 0.343(14) Uani 1 1 d . . . O6 O 0.5787(5) 0.6985(8) 0.0763(4) 0.182(5) Uani 1 1 d . . . N1 N -0.1069(3) 0.4393(3) 0.07286(16) 0.0522(9) Uani 1 1 d . . . N2 N -0.1806(4) 0.4672(4) 0.0485(2) 0.0763(15) Uani 1 1 d . . . H1 H -0.2293 0.4910 0.0619 0.092 Uiso 1 1 calc R . . N3 N -0.0867(3) 0.4164(3) -0.00765(17) 0.0599(11) Uani 1 1 d . . . N4 N 0.0898(3) 0.3388(3) 0.01526(15) 0.0538(10) Uani 1 1 d . . . N5 N 0.1648(3) 0.3034(3) 0.03888(18) 0.0556(10) Uani 1 1 d . . . N6 N 0.2409(4) 0.2759(4) -0.03443(18) 0.0713(13) Uani 1 1 d . . . H3 H 0.1960 0.2969 -0.0524 0.086 Uiso 1 1 calc R . . H4 H 0.2904 0.2554 -0.0486 0.086 Uiso 1 1 calc R . . N7 N 0.2933(3) 0.2529(3) 0.09363(18) 0.0613(11) Uani 1 1 d . . . C1 C -0.1685(3) 0.4533(3) 0.00120(16) 0.0502(11) Uani 1 1 d . . . H2 H -0.2119 0.4674 -0.0234 0.060 Uiso 1 1 calc R . . C2 C -0.0510(4) 0.4083(3) 0.03640(18) 0.0501(11) Uani 1 1 d . . . C3 C 0.0368(4) 0.3709(3) 0.04943(17) 0.0499(10) Uani 1 1 d . . . C4 C 0.2341(4) 0.2751(4) 0.0136(2) 0.0575(12) Uani 1 1 d . . . C5 C 0.3056(4) 0.2376(4) 0.0451(2) 0.0592(12) Uani 1 1 d . . . C6 C 0.3770(5) 0.1852(5) 0.0282(3) 0.0779(17) Uani 1 1 d . . . H5 H 0.3861 0.1761 -0.0059 0.094 Uiso 1 1 calc R . . C7 C 0.4337(6) 0.1471(6) 0.0616(3) 0.100(3) Uani 1 1 d . . . H6 H 0.4827 0.1103 0.0508 0.120 Uiso 1 1 calc R . . C8 C 0.4208(6) 0.1611(7) 0.1100(3) 0.104(3) Uani 1 1 d . . . H7 H 0.4594 0.1332 0.1334 0.125 Uiso 1 1 calc R . . C9 C 0.3504(5) 0.2168(6) 0.1251(3) 0.084(2) Uani 1 1 d . . . H8 H 0.3432 0.2292 0.1591 0.101 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 Cu1 0.0571(4) 0.0611(4) 0.0393(4) -0.0019(2) 0.0030(2) 0.0011(3) Cl1 0.0940(12) 0.0884(12) 0.0857(12) 0.0277(9) -0.0260(10) -0.0134(9) O1 0.0582(19) 0.064(2) 0.0344(16) -0.0014(14) 0.0003(14) 0.0029(16) O2 0.092(3) 0.131(5) 0.069(3) 0.020(3) -0.016(3) 0.025(3) O3 0.124(6) 0.234(10) 0.121(6) 0.054(6) -0.035(5) 0.061(6) O4 0.149(6) 0.225(9) 0.078(4) 0.041(5) 0.003(4) 0.046(6) O5 0.53(3) 0.207(12) 0.290(17) 0.114(12) -0.23(2) -0.233(18) O6 0.096(5) 0.269(12) 0.181(8) 0.110(8) 0.043(5) 0.034(6) N1 0.058(2) 0.049(2) 0.050(2) 0.0024(17) -0.0066(18) -0.0009(18) N2 0.076(3) 0.061(3) 0.092(4) 0.009(3) -0.015(3) -0.003(2) N3 0.077(3) 0.059(2) 0.044(2) 0.0106(18) -0.008(2) -0.010(2) N4 0.064(2) 0.059(2) 0.038(2) -0.0023(17) 0.0005(18) -0.0072(19) N5 0.060(2) 0.058(2) 0.048(2) -0.0019(19) 0.0083(18) -0.0043(19) N6 0.072(3) 0.093(4) 0.049(3) -0.010(2) 0.015(2) 0.000(3) N7 0.059(2) 0.068(3) 0.057(3) 0.009(2) 0.009(2) 0.004(2) C1 0.062(3) 0.052(2) 0.036(2) 0.0106(18) -0.011(2) -0.004(2) C2 0.066(3) 0.048(2) 0.036(2) 0.0034(18) -0.003(2) -0.012(2) C3 0.061(3) 0.049(2) 0.039(2) -0.0003(19) 0.002(2) -0.010(2) C4 0.064(3) 0.055(3) 0.054(3) -0.005(2) 0.009(2) -0.009(2) C5 0.065(3) 0.054(3) 0.058(3) -0.001(2) 0.014(2) -0.006(2) C6 0.073(4) 0.083(4) 0.078(4) 0.002(3) 0.022(3) 0.009(3) C7 0.091(5) 0.112(6) 0.096(6) 0.019(5) 0.035(4) 0.036(5) C8 0.078(5) 0.137(8) 0.097(6) 0.041(5) 0.016(4) 0.033(5) C9 0.073(4) 0.117(6) 0.064(4) 0.023(4) 0.015(3) 0.012(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 N5 1.907(5) . ? Cu1 O1 1.973(4) . ? Cu1 N1 1.981(4) 14 ? Cu1 N7 2.023(5) . ? Cu1 O1 2.331(3) 14 ? Cl1 O5 1.285(10) . ? Cl1 O2 1.399(5) . ? Cl1 O3 1.401(9) . ? Cl1 O4 1.476(8) . ? O1 C3 1.310(6) . ? O1 Cu1 2.331(3) 12_666 ? N1 N2 1.339(7) . ? N1 C2 1.371(7) . ? N1 Cu1 1.981(4) 12_666 ? N2 C1 1.318(8) . ? N2 H1 0.8800 . ? N3 C2 1.318(7) . ? N3 C1 1.346(7) . ? N4 C3 1.306(6) . ? N4 N5 1.383(6) . ? N5 C4 1.302(7) . ? N6 C4 1.314(7) . ? N6 H3 0.8800 . ? N6 H4 0.8800 . ? N7 C9 1.316(9) . ? N7 C5 1.355(7) . ? C1 H2 0.9500 . ? C2 C3 1.453(8) . ? C4 C5 1.469(8) . ? C5 C6 1.387(8) . ? C6 C7 1.358(11) . ? C6 H5 0.9500 . ? C7 C8 1.351(12) . ? C7 H6 0.9500 . ? C8 C9 1.387(11) . ? C8 H7 0.9500 . ? C9 H8 0.9500 . ? 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 N5 Cu1 O1 79.04(16) . . ? N5 Cu1 N1 168.89(18) . 14 ? O1 Cu1 N1 97.29(15) . 14 ? N5 Cu1 N7 79.9(2) . . ? O1 Cu1 N7 158.95(18) . . ? N1 Cu1 N7 103.57(19) 14 . ? N5 Cu1 O1 114.64(16) . 14 ? O1 Cu1 O1 96.22(19) . 14 ? N1 Cu1 O1 76.05(16) 14 14 ? N7 Cu1 O1 91.56(17) . 14 ? O5 Cl1 O2 113.1(7) . . ? O5 Cl1 O3 120.2(13) . . ? O2 Cl1 O3 107.1(4) . . ? O5 Cl1 O4 104.9(10) . . ? O2 Cl1 O4 111.6(4) . . ? O3 Cl1 O4 99.0(5) . . ? C3 O1 Cu1 110.0(3) . . ? C3 O1 Cu1 111.2(3) . 12_666 ? Cu1 O1 Cu1 138.40(16) . 12_666 ? N2 N1 C2 103.4(5) . . ? N2 N1 Cu1 138.0(4) . 12_666 ? C2 N1 Cu1 118.5(3) . 12_666 ? C1 N2 N1 109.2(5) . . ? C1 N2 H1 125.4 . . ? N1 N2 H1 125.4 . . ? C2 N3 C1 103.4(5) . . ? C3 N4 N5 106.5(4) . . ? C4 N5 N4 120.1(5) . . ? C4 N5 Cu1 119.7(4) . . ? N4 N5 Cu1 119.1(3) . . ? C4 N6 H3 120.0 . . ? C4 N6 H4 120.0 . . ? H3 N6 H4 120.0 . . ? C9 N7 C5 119.0(5) . . ? C9 N7 Cu1 127.8(5) . . ? C5 N7 Cu1 112.6(4) . . ? N2 C1 N3 111.1(5) . . ? N2 C1 H2 124.5 . . ? N3 C1 H2 124.5 . . ? N3 C2 N1 113.0(5) . . ? N3 C2 C3 127.9(5) . . ? N1 C2 C3 119.1(4) . . ? N4 C3 O1 125.3(5) . . ? N4 C3 C2 119.9(4) . . ? O1 C3 C2 114.9(4) . . ? N5 C4 N6 125.9(6) . . ? N5 C4 C5 112.0(5) . . ? N6 C4 C5 122.1(5) . . ? N7 C5 C6 121.3(6) . . ? N7 C5 C4 114.4(5) . . ? C6 C5 C4 124.2(6) . . ? C7 C6 C5 118.5(7) . . ? C7 C6 H5 120.7 . . ? C5 C6 H5 120.7 . . ? C8 C7 C6 120.3(7) . . ? C8 C7 H6 119.8 . . ? C6 C7 H6 119.8 . . ? C7 C8 C9 119.1(8) . . ? C7 C8 H7 120.4 . . ? C9 C8 H7 120.4 . . ? N7 C9 C8 121.7(7) . . ? N7 C9 H8 119.1 . . ? C8 C9 H8 119.1 . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.039 _refine_diff_density_min -0.718 _refine_diff_density_rms 0.114 data_4 _database_code_depnum_ccdc_archive 'CCDC 807493' #TrackingRef 'Submission.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H40 N24 Ni4 O20, 4(C4 H10 O)' _chemical_formula_sum 'C52 H80 N24 Ni4 O24' _chemical_formula_weight 1660.15 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' Ni Ni 0.3393 1.1124 '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' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'F d d d' _symmetry_space_group_name_Hall '-F 2uv 2vw' _symmetry_Int_Tables_number 70 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/4, z+1/4' 'x+1/4, -y, z+1/4' '-x+1/4, -y+3/4, z+1/2' 'x, y+1/2, z+1/2' '-x, y+3/4, z+3/4' 'x+1/4, -y+1/2, z+3/4' '-x+1/4, -y+5/4, z+1' 'x+1/2, y, z+1/2' '-x+1/2, y+1/4, z+3/4' 'x+3/4, -y, z+3/4' '-x+3/4, -y+3/4, z+1' 'x+1/2, y+1/2, z' '-x+1/2, y+3/4, z+1/4' 'x+3/4, -y+1/2, z+1/4' '-x+3/4, -y+5/4, z+1/2' '-x, -y, -z' 'x, -y-1/4, -z-1/4' '-x-1/4, y, -z-1/4' 'x-1/4, y-3/4, -z-1/2' '-x, -y+1/2, -z+1/2' 'x, -y+1/4, -z+1/4' '-x-1/4, y+1/2, -z+1/4' 'x-1/4, y-1/4, -z' '-x+1/2, -y, -z+1/2' 'x+1/2, -y-1/4, -z+1/4' '-x+1/4, y, -z+1/4' 'x+1/4, y-3/4, -z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/4, -z-1/4' '-x+1/4, y+1/2, -z-1/4' 'x+1/4, y-1/4, -z-1/2' _cell_length_a 19.798(2) _cell_length_b 23.098(2) _cell_length_c 32.469(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 14848(3) _cell_formula_units_Z 8 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 12156 _cell_measurement_theta_min 2.0574 _cell_measurement_theta_max 30.7671 _exptl_crystal_description Prism _exptl_crystal_colour Green _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.485 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 6912 _exptl_absorpt_coefficient_mu 1.087 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.9176 _exptl_absorpt_correction_T_min 0.8253 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 34050 _diffrn_reflns_av_R_equivalents 0.0356 _diffrn_reflns_av_sigmaI/netI 0.0183 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -40 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 2.71 _diffrn_reflns_theta_max 26.50 _reflns_number_total 3841 _reflns_number_gt 3788 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Acta Cryst. 2008. A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst. 2008. A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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. H5, H6 and H10 were initially located in difference map positions and refined positionally with fixed displacement ellipses. In the final round of least squares they were refined on a riding model. All other hydrogen atoms were introduced in calculated positions and refined on a riding model. DELU and DFIX restraints were applied to the lattice solvent ether molecule. ; _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^)+(0.0472P)^2^+221.4210P] 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 3841 _refine_ls_number_parameters 237 _refine_ls_number_restraints 11 _refine_ls_R_factor_all 0.0713 _refine_ls_R_factor_gt 0.0703 _refine_ls_wR_factor_ref 0.1711 _refine_ls_wR_factor_gt 0.1706 _refine_ls_goodness_of_fit_ref 1.207 _refine_ls_restrained_S_all 1.209 _refine_ls_shift/su_max 0.004 _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 Ni1 Ni 0.6250 0.24473(3) 0.1250 0.0323(2) Uani 1 2 d S . . Ni2 Ni 0.48377(4) 0.1250 0.1250 0.0313(2) Uani 1 2 d S . . O1 O 0.55374(15) 0.18105(13) 0.14762(9) 0.0320(7) Uani 1 1 d . . . O2 O 0.45426(19) 0.05251(15) 0.20231(10) 0.0459(9) Uani 1 1 d . . . H10 H 0.4349 0.0330 0.1786 0.055 Uiso 1 1 d . . . O3 O 0.40365(19) 0.07270(15) 0.10165(12) 0.0504(9) Uani 1 1 d . . . O4 O 0.3697(3) -0.00836(18) 0.07634(13) 0.0761(15) Uani 1 1 d . . . O5 O 0.4047(2) -0.00504(18) 0.13902(12) 0.0639(12) Uani 1 1 d . . . O6 O 0.7709(3) 0.3630(3) 0.29306(18) 0.111(2) Uani 1 1 d DU . . N1 N 0.6981(2) 0.30963(18) 0.13459(13) 0.0459(10) Uani 1 1 d . . . N2 N 0.6708(3) 0.2963(2) 0.24422(12) 0.0507(12) Uani 1 1 d . . . H5 H 0.6997 0.3231 0.2579 0.061 Uiso 1 1 d . . . H6 H 0.6468 0.2742 0.2629 0.061 Uiso 1 1 d . . . N3 N 0.6332(2) 0.24763(15) 0.18578(11) 0.0340(8) Uani 1 1 d . . . N4 N 0.5967(2) 0.20999(15) 0.21098(11) 0.0327(8) Uani 1 1 d . . . N5 N 0.48896(19) 0.09753(16) 0.18402(11) 0.0352(8) Uani 1 1 d . . . N6 N 0.3927(2) 0.01991(19) 0.10551(13) 0.0453(10) Uani 1 1 d . . . C1 C 0.7319(4) 0.3386(3) 0.10617(18) 0.0631(17) Uani 1 1 d . . . H1 H 0.7250 0.3291 0.0780 0.076 Uiso 1 1 calc R . . C2 C 0.7774(5) 0.3828(3) 0.1160(2) 0.088(3) Uani 1 1 d . . . H2 H 0.7997 0.4037 0.0948 0.106 Uiso 1 1 calc R . . C3 C 0.7895(4) 0.3955(3) 0.1563(2) 0.083(3) Uani 1 1 d . . . H3 H 0.8207 0.4250 0.1636 0.100 Uiso 1 1 calc R . . C4 C 0.7555(4) 0.3648(3) 0.18680(19) 0.069(2) Uani 1 1 d . . . H4 H 0.7636 0.3723 0.2151 0.083 Uiso 1 1 calc R . . C5 C 0.7092(3) 0.3227(2) 0.17473(16) 0.0471(13) Uani 1 1 d . . . C6 C 0.6692(3) 0.2866(2) 0.20378(14) 0.0392(11) Uani 1 1 d . . . C7 C 0.5592(2) 0.17709(18) 0.18769(13) 0.0310(9) Uani 1 1 d . . . C8 C 0.5220(2) 0.1301(2) 0.20883(13) 0.0340(9) Uani 1 1 d . . . C9 C 0.5243(3) 0.1217(2) 0.25432(14) 0.0457(12) Uani 1 1 d . . . H7 H 0.5385 0.1578 0.2676 0.055 Uiso 1 1 calc R . . H8 H 0.5566 0.0909 0.2610 0.055 Uiso 1 1 calc R . . H9 H 0.4794 0.1107 0.2643 0.055 Uiso 1 1 calc R . . C10 C 0.7099(8) 0.4507(7) 0.2832(5) 0.199(7) Uani 1 1 d DU . . H11 H 0.7049 0.4310 0.2566 0.239 Uiso 1 1 calc R . . H12 H 0.7434 0.4817 0.2807 0.239 Uiso 1 1 calc R . . H13 H 0.6663 0.4672 0.2915 0.239 Uiso 1 1 calc R . . C11 C 0.7325(5) 0.4084(5) 0.3149(3) 0.137(4) Uani 1 1 d DU . . H14 H 0.7615 0.4277 0.3355 0.165 Uiso 1 1 calc R . . H15 H 0.6931 0.3913 0.3291 0.165 Uiso 1 1 calc R . . C12 C 0.8040(7) 0.3152(5) 0.3188(4) 0.170(5) Uani 1 1 d DU . . H16 H 0.8360 0.3331 0.3385 0.204 Uiso 1 1 calc R . . H17 H 0.7687 0.2950 0.3349 0.204 Uiso 1 1 calc R . . C13 C 0.8403(7) 0.2727(7) 0.2937(5) 0.207(8) Uani 1 1 d DU . . H18 H 0.8766 0.2554 0.3101 0.249 Uiso 1 1 calc R . . H19 H 0.8595 0.2919 0.2695 0.249 Uiso 1 1 calc R . . H20 H 0.8089 0.2423 0.2848 0.249 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 Ni1 0.0446(5) 0.0283(4) 0.0240(4) 0.000 0.0056(3) 0.000 Ni2 0.0361(4) 0.0314(4) 0.0265(4) 0.0037(3) 0.000 0.000 O1 0.0391(17) 0.0362(16) 0.0207(14) 0.0037(12) 0.0030(12) -0.0036(13) O2 0.055(2) 0.0471(19) 0.0353(17) 0.0091(15) 0.0025(15) -0.0220(17) O3 0.049(2) 0.0401(19) 0.062(2) 0.0088(17) -0.0174(18) -0.0080(16) O4 0.118(4) 0.058(2) 0.052(2) 0.011(2) -0.031(3) -0.040(3) O5 0.087(3) 0.061(2) 0.043(2) 0.0158(18) -0.016(2) -0.038(2) O6 0.102(4) 0.154(6) 0.077(4) -0.043(3) 0.018(3) -0.061(4) N1 0.063(3) 0.039(2) 0.036(2) -0.0010(17) 0.0107(19) -0.016(2) N2 0.068(3) 0.055(3) 0.029(2) -0.0084(19) 0.008(2) -0.026(2) N3 0.044(2) 0.0315(18) 0.0265(18) -0.0006(14) 0.0086(16) -0.0057(16) N4 0.042(2) 0.0322(19) 0.0237(17) 0.0017(14) 0.0058(15) -0.0046(16) N5 0.038(2) 0.037(2) 0.0311(19) 0.0076(16) 0.0030(16) -0.0064(16) N6 0.049(3) 0.047(2) 0.040(2) 0.0080(19) -0.0066(19) -0.0164(19) C1 0.088(5) 0.060(4) 0.041(3) 0.000(3) 0.017(3) -0.030(3) C2 0.133(7) 0.074(5) 0.057(4) -0.008(3) 0.029(4) -0.060(5) C3 0.114(6) 0.070(4) 0.065(4) -0.015(3) 0.029(4) -0.060(4) C4 0.097(5) 0.064(4) 0.046(3) -0.015(3) 0.020(3) -0.044(4) C5 0.061(3) 0.040(3) 0.040(3) -0.006(2) 0.013(2) -0.020(2) C6 0.050(3) 0.035(2) 0.033(2) -0.0066(19) 0.008(2) -0.008(2) C7 0.036(2) 0.031(2) 0.026(2) 0.0015(16) 0.0060(17) 0.0007(18) C8 0.040(2) 0.035(2) 0.028(2) 0.0035(18) 0.0039(18) -0.0032(19) C9 0.058(3) 0.052(3) 0.027(2) 0.005(2) 0.004(2) -0.014(2) C10 0.171(15) 0.222(16) 0.206(15) -0.064(10) 0.054(13) 0.024(12) C11 0.107(7) 0.202(10) 0.103(7) -0.089(6) 0.049(6) -0.076(6) C12 0.212(17) 0.173(12) 0.125(11) -0.018(7) -0.016(9) -0.055(8) C13 0.159(13) 0.202(13) 0.26(2) -0.107(13) -0.088(12) -0.020(9) _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 Ni1 N3 1.981(4) . ? Ni1 N3 1.981(4) 27_655 ? Ni1 N1 2.106(4) 27_655 ? Ni1 N1 2.106(4) . ? Ni1 O1 2.166(3) . ? Ni1 O1 2.166(3) 27_655 ? Ni2 N5 2.021(4) . ? Ni2 N5 2.021(4) 22 ? Ni2 O1 2.033(3) 22 ? Ni2 O1 2.033(3) . ? Ni2 O3 2.133(3) . ? Ni2 O3 2.133(3) 22 ? O1 C7 1.308(5) . ? O2 N5 1.381(5) . ? O2 H10 0.9693 . ? O3 N6 1.245(5) . ? O4 N6 1.237(6) . ? O5 N6 1.254(5) . ? O6 C11 1.476(10) . ? O6 C12 1.530(9) . ? N1 C1 1.322(7) . ? N1 C5 1.356(7) . ? N2 C6 1.332(6) . ? N2 H5 0.9525 . ? N2 H6 0.9244 . ? N3 C6 1.289(6) . ? N3 N4 1.395(5) . ? N4 C7 1.305(6) . ? N5 C8 1.281(6) . ? C1 C2 1.398(9) . ? C1 H1 0.9500 . ? C2 C3 1.364(10) . ? C2 H2 0.9500 . ? C3 C4 1.391(8) . ? C3 H3 0.9500 . ? C4 C5 1.392(7) . ? C4 H4 0.9500 . ? C5 C6 1.486(6) . ? C7 C8 1.481(6) . ? C8 C9 1.491(6) . ? C9 H7 0.9800 . ? C9 H8 0.9800 . ? C9 H9 0.9800 . ? C10 C11 1.487(14) . ? C10 H11 0.9800 . ? C10 H12 0.9800 . ? C10 H13 0.9800 . ? C11 H14 0.9900 . ? C11 H15 0.9900 . ? C12 C13 1.464(14) . ? C12 H16 0.9900 . ? C12 H17 0.9900 . ? C13 H18 0.9800 . ? C13 H19 0.9800 . ? C13 H20 0.9800 . ? 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 N3 Ni1 N3 176.1(2) . 27_655 ? N3 Ni1 N1 100.34(16) . 27_655 ? N3 Ni1 N1 76.84(15) 27_655 27_655 ? N3 Ni1 N1 76.84(15) . . ? N3 Ni1 N1 100.34(16) 27_655 . ? N1 Ni1 N1 89.2(3) 27_655 . ? N3 Ni1 O1 74.85(13) . . ? N3 Ni1 O1 107.90(14) 27_655 . ? N1 Ni1 O1 94.94(15) 27_655 . ? N1 Ni1 O1 151.68(13) . . ? N3 Ni1 O1 107.89(14) . 27_655 ? N3 Ni1 O1 74.85(13) 27_655 27_655 ? N1 Ni1 O1 151.68(13) 27_655 27_655 ? N1 Ni1 O1 94.94(15) . 27_655 ? O1 Ni1 O1 94.48(16) . 27_655 ? N5 Ni2 N5 174.2(2) . 22 ? N5 Ni2 O1 96.19(14) . 22 ? N5 Ni2 O1 79.79(13) 22 22 ? N5 Ni2 O1 79.79(13) . . ? N5 Ni2 O1 96.20(14) 22 . ? O1 Ni2 O1 94.12(17) 22 . ? N5 Ni2 O3 101.36(15) . . ? N5 Ni2 O3 83.03(15) 22 . ? O1 Ni2 O3 91.01(14) 22 . ? O1 Ni2 O3 174.60(14) . . ? N5 Ni2 O3 83.03(15) . 22 ? N5 Ni2 O3 101.36(15) 22 22 ? O1 Ni2 O3 174.60(14) 22 22 ? O1 Ni2 O3 91.01(14) . 22 ? O3 Ni2 O3 83.9(2) . 22 ? C7 O1 Ni2 111.7(3) . . ? C7 O1 Ni1 109.3(3) . . ? Ni2 O1 Ni1 138.89(14) . . ? N5 O2 H10 101.8 . . ? N6 O3 Ni2 130.4(3) . . ? C11 O6 C12 118.1(8) . . ? C1 N1 C5 118.4(5) . . ? C1 N1 Ni1 127.2(4) . . ? C5 N1 Ni1 114.3(3) . . ? C6 N2 H5 125.6 . . ? C6 N2 H6 122.8 . . ? H5 N2 H6 111.2 . . ? C6 N3 N4 117.1(4) . . ? C6 N3 Ni1 121.4(3) . . ? N4 N3 Ni1 121.4(3) . . ? C7 N4 N3 108.5(3) . . ? C8 N5 O2 115.2(4) . . ? C8 N5 Ni2 116.0(3) . . ? O2 N5 Ni2 128.2(3) . . ? O4 N6 O3 120.3(4) . . ? O4 N6 O5 119.4(4) . . ? O3 N6 O5 120.3(4) . . ? N1 C1 C2 122.5(6) . . ? N1 C1 H1 118.8 . . ? C2 C1 H1 118.8 . . ? C3 C2 C1 119.3(6) . . ? C3 C2 H2 120.4 . . ? C1 C2 H2 120.4 . . ? C2 C3 C4 119.2(6) . . ? C2 C3 H3 120.4 . . ? C4 C3 H3 120.4 . . ? C3 C4 C5 118.3(6) . . ? C3 C4 H4 120.8 . . ? C5 C4 H4 120.8 . . ? N1 C5 C4 122.2(5) . . ? N1 C5 C6 113.5(4) . . ? C4 C5 C6 124.3(5) . . ? N3 C6 N2 125.3(4) . . ? N3 C6 C5 113.5(4) . . ? N2 C6 C5 121.2(4) . . ? N4 C7 O1 125.6(4) . . ? N4 C7 C8 116.2(4) . . ? O1 C7 C8 118.1(4) . . ? N5 C8 C7 113.1(4) . . ? N5 C8 C9 124.2(4) . . ? C7 C8 C9 122.6(4) . . ? C8 C9 H7 109.5 . . ? C8 C9 H8 109.5 . . ? H7 C9 H8 109.5 . . ? C8 C9 H9 109.5 . . ? H7 C9 H9 109.5 . . ? H8 C9 H9 109.5 . . ? C11 C10 H11 109.5 . . ? C11 C10 H12 109.5 . . ? H11 C10 H12 109.5 . . ? C11 C10 H13 109.5 . . ? H11 C10 H13 109.5 . . ? H12 C10 H13 109.5 . . ? O6 C11 C10 106.9(9) . . ? O6 C11 H14 110.3 . . ? C10 C11 H14 110.3 . . ? O6 C11 H15 110.3 . . ? C10 C11 H15 110.3 . . ? H14 C11 H15 108.6 . . ? C13 C12 O6 113.0(12) . . ? C13 C12 H16 109.0 . . ? O6 C12 H16 109.0 . . ? C13 C12 H17 109.0 . . ? O6 C12 H17 109.0 . . ? H16 C12 H17 107.8 . . ? C12 C13 H18 109.5 . . ? C12 C13 H19 109.5 . . ? H18 C13 H19 109.5 . . ? C12 C13 H20 109.5 . . ? H18 C13 H20 109.5 . . ? H19 C13 H20 109.5 . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.531 _refine_diff_density_min -0.599 _refine_diff_density_rms 0.086 data_4a _database_code_depnum_ccdc_archive 'CCDC 807494' #TrackingRef 'Submission.cif' # start Validation Reply Form _vrf_PLAT601_4A ; PROBLEM: Structure Contains Solvent Accessible VOIDS of . 254.00 A**3 RESPONSE: No significant residual peaks remained in the difference map so the Platon Squeeze procedure was used to examine this problem. The following voids were identified, with their corresponding volumes and electron counts [0.250 0.750 -0.024] --> 255 A^3^, 17 e- and [0.750 0.250 -0.015] --> 255 A^3^ 17 e-. It was found that refining against the new .hkp file did NOT significantly improve the data statistics, therefore the solvent accessible void was left untreated in the model and the model was refined against the original data. ; # end Validation Reply Form _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C40 H56 N24 Ni4 O24' _chemical_formula_sum 'C40 H56 N24 Ni4 O24' _chemical_formula_weight 1491.83 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' Ni Ni 0.3393 1.1124 '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' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'P 42/n' _symmetry_space_group_name_Hall '-P 4bc' _symmetry_Int_Tables_number 86 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x+1/2, z+1/2' '-x+1/2, -y+1/2, z' 'y+1/2, -x, z+1/2' '-x, -y, -z' 'y, -x-1/2, -z-1/2' 'x-1/2, y-1/2, -z' '-y-1/2, x, -z-1/2' _cell_length_a 17.217(4) _cell_length_b 17.217(4) _cell_length_c 11.169(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3310.8(14) _cell_formula_units_Z 2 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 12308 _cell_measurement_theta_min 2.1735 _cell_measurement_theta_max 31.0397 _exptl_crystal_description Rod _exptl_crystal_colour 'Light Green' _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.497 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1536 _exptl_absorpt_coefficient_mu 1.210 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.9770 _exptl_absorpt_correction_T_min 0.8837 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 25511 _diffrn_reflns_av_R_equivalents 0.0531 _diffrn_reflns_av_sigmaI/netI 0.0240 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.99 _diffrn_reflns_theta_max 24.98 _reflns_number_total 2916 _reflns_number_gt 2831 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXL-97 (Acta Cryst. 2008. A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst. 2008. A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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^)+(0.0975P)^2^+13.5361P] 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 2916 _refine_ls_number_parameters 209 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1113 _refine_ls_R_factor_gt 0.1088 _refine_ls_wR_factor_ref 0.2633 _refine_ls_wR_factor_gt 0.2611 _refine_ls_goodness_of_fit_ref 1.253 _refine_ls_restrained_S_all 1.263 _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 Ni1 Ni 0.66497(6) 0.61301(6) 0.25205(7) 0.0474(4) Uani 1 1 d . . . O1 O 0.7767(3) 0.6438(3) 0.3156(4) 0.0453(11) Uani 1 1 d . . . O2 O 0.9737(3) 0.6973(4) 0.4803(5) 0.0678(16) Uani 1 1 d . . . H2O H 1.0057 0.7239 0.4268 0.082 Uiso 1 1 d . . . O3 O 0.6916(4) 0.4939(3) 0.2714(5) 0.0641(15) Uani 1 1 d U . . H3O H 0.6511 0.4541 0.2688 0.075 Uiso 1 1 d . . . O4 O 0.4261(4) 0.6055(4) 0.7239(6) 0.0766(18) Uani 1 1 d . . . O5 O 0.4894(5) 0.6826(6) 0.8372(8) 0.123(3) Uani 1 1 d . . . O6 O 0.4048(6) 0.6025(6) 0.9119(7) 0.127(3) Uani 1 1 d . . . N1 N 0.5455(4) 0.5884(4) 0.2700(6) 0.0549(16) Uani 1 1 d . . . N2 N 0.5669(4) 0.6266(5) 0.5882(5) 0.0654(19) Uani 1 1 d . . . H1N H 0.5222 0.6252 0.6161 0.078 Uiso 1 1 d . . . H2N H 0.6126 0.6295 0.6212 0.078 Uiso 1 1 d . . . N3 N 0.6481(4) 0.6308(4) 0.4230(5) 0.0504(15) Uani 1 1 d . . . N4 N 0.7104(3) 0.6491(4) 0.4973(5) 0.0505(15) Uani 1 1 d . . . N5 N 0.9028(4) 0.6809(4) 0.4256(6) 0.0517(15) Uani 1 1 d . . . N6 N 0.4410(5) 0.6308(5) 0.8266(8) 0.082(2) Uani 1 1 d . . . C1 C 0.4949(5) 0.5675(5) 0.1853(7) 0.067(2) Uani 1 1 d . . . H1 H 0.5125 0.5613 0.1053 0.080 Uiso 1 1 calc R . . C2 C 0.4178(6) 0.5546(6) 0.2114(8) 0.072(2) Uani 1 1 d . . . H2 H 0.3828 0.5400 0.1496 0.087 Uiso 1 1 calc R . . C3 C 0.3915(5) 0.5628(7) 0.3265(9) 0.082(3) Uani 1 1 d . . . H3 H 0.3387 0.5528 0.3452 0.098 Uiso 1 1 calc R . . C4 C 0.4429(5) 0.5859(6) 0.4152(8) 0.071(2) Uani 1 1 d . . . H4 H 0.4253 0.5936 0.4950 0.085 Uiso 1 1 calc R . . C5 C 0.5197(4) 0.5976(5) 0.3859(6) 0.0543(19) Uani 1 1 d . . . C6 C 0.5807(4) 0.6204(4) 0.4708(6) 0.0491(17) Uani 1 1 d . . . C7 C 0.7720(4) 0.6545(4) 0.4328(6) 0.0504(17) Uani 1 1 d . . . C8 C 0.8462(4) 0.6735(4) 0.4962(6) 0.0487(16) Uani 1 1 d . . . C9 C 0.8481(5) 0.6808(5) 0.6305(6) 0.061(2) Uani 1 1 d . . . H9A H 0.8440 0.6292 0.6667 0.073 Uiso 1 1 calc R . . H9B H 0.8045 0.7131 0.6572 0.073 Uiso 1 1 calc R . . H9C H 0.8971 0.7051 0.6550 0.073 Uiso 1 1 calc R . . C10 C 0.7400(7) 0.4585(8) 0.3810(14) 0.120(4) Uani 1 1 d U . . H10A H 0.7882 0.4879 0.3912 0.144 Uiso 1 1 calc R . . H10B H 0.7523 0.4040 0.3644 0.144 Uiso 1 1 calc R . . H10C H 0.7090 0.4619 0.4544 0.144 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 Ni1 0.0587(6) 0.0569(6) 0.0265(6) 0.0022(4) 0.0023(4) -0.0026(4) O1 0.057(3) 0.058(3) 0.020(2) 0.0006(19) 0.0010(19) 0.001(2) O2 0.063(3) 0.098(4) 0.042(3) -0.007(3) -0.001(3) -0.010(3) O3 0.079(4) 0.059(3) 0.055(3) 0.005(3) 0.008(3) -0.006(3) O4 0.078(4) 0.098(5) 0.054(4) -0.006(3) 0.009(3) -0.025(4) O5 0.112(6) 0.152(8) 0.106(7) -0.047(6) 0.021(5) -0.048(6) O6 0.170(8) 0.159(8) 0.052(4) -0.010(5) 0.025(5) -0.055(7) N1 0.057(4) 0.063(4) 0.044(3) 0.002(3) -0.001(3) -0.009(3) N2 0.060(4) 0.104(6) 0.032(3) 0.004(3) 0.005(3) -0.012(4) N3 0.061(4) 0.062(4) 0.028(3) 0.004(3) -0.001(3) -0.003(3) N4 0.056(4) 0.068(4) 0.027(3) 0.002(3) 0.001(3) -0.007(3) N5 0.051(3) 0.066(4) 0.038(3) -0.006(3) -0.002(3) 0.004(3) N6 0.083(6) 0.099(6) 0.063(5) -0.010(5) 0.007(4) -0.011(5) C1 0.081(6) 0.078(6) 0.041(4) -0.001(4) -0.009(4) 0.001(5) C2 0.076(6) 0.080(6) 0.061(5) 0.011(5) -0.005(5) -0.026(5) C3 0.059(5) 0.119(8) 0.067(6) 0.006(6) -0.003(5) -0.026(5) C4 0.067(5) 0.101(7) 0.045(4) 0.004(4) -0.001(4) -0.023(5) C5 0.061(5) 0.069(5) 0.033(4) 0.006(3) -0.002(3) -0.009(4) C6 0.061(5) 0.052(4) 0.034(4) 0.008(3) 0.007(3) -0.002(3) C7 0.063(5) 0.062(4) 0.026(3) 0.002(3) 0.003(3) 0.005(4) C8 0.055(4) 0.058(4) 0.033(3) 0.002(3) 0.000(3) 0.006(3) C9 0.069(5) 0.088(6) 0.026(4) 0.001(4) -0.006(3) -0.002(4) C10 0.084(8) 0.125(10) 0.150(12) -0.012(9) -0.007(7) -0.015(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 Ni1 N3 1.956(6) . ? Ni1 N5 2.022(6) 6_576 ? Ni1 O1 2.075(5) 6_576 ? Ni1 N1 2.110(7) . ? Ni1 O3 2.112(6) . ? Ni1 O1 2.118(5) . ? O1 C7 1.325(8) . ? O1 Ni1 2.075(5) 8_756 ? O2 N5 1.394(8) . ? O2 H2O 0.9338 . ? O3 C10 1.601(15) . ? O3 H3O 0.9782 . ? O4 N6 1.253(10) . ? O5 N6 1.226(11) . ? O6 N6 1.238(10) . ? N1 C1 1.336(10) . ? N1 C5 1.377(9) . ? N2 C6 1.336(9) . ? N2 H1N 0.8294 . ? N2 H2N 0.8716 . ? N3 C6 1.289(9) . ? N3 N4 1.392(8) . ? N4 C7 1.285(9) . ? N5 C8 1.260(9) . ? N5 Ni1 2.022(6) 8_756 ? C1 C2 1.376(12) . ? C1 H1 0.9500 . ? C2 C3 1.369(13) . ? C2 H2 0.9500 . ? C3 C4 1.386(12) . ? C3 H3 0.9500 . ? C4 C5 1.377(11) . ? C4 H4 0.9500 . ? C5 C6 1.470(10) . ? C7 C8 1.496(10) . ? C8 C9 1.506(9) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? 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 N3 Ni1 N5 178.5(3) . 6_576 ? N3 Ni1 O1 100.7(2) . 6_576 ? N5 Ni1 O1 77.8(2) 6_576 6_576 ? N3 Ni1 N1 78.1(2) . . ? N5 Ni1 N1 101.4(3) 6_576 . ? O1 Ni1 N1 92.7(2) 6_576 . ? N3 Ni1 O3 94.8(2) . . ? N5 Ni1 O3 86.6(2) 6_576 . ? O1 Ni1 O3 164.44(19) 6_576 . ? N1 Ni1 O3 90.4(2) . . ? N3 Ni1 O1 76.6(2) . . ? N5 Ni1 O1 103.9(2) 6_576 . ? O1 Ni1 O1 93.0(2) 6_576 . ? N1 Ni1 O1 154.7(2) . . ? O3 Ni1 O1 90.7(2) . . ? C7 O1 Ni1 113.1(4) . 8_756 ? C7 O1 Ni1 108.1(4) . . ? Ni1 O1 Ni1 138.8(2) 8_756 . ? N5 O2 H2O 109.6 . . ? C10 O3 Ni1 124.1(6) . . ? C10 O3 H3O 97.3 . . ? Ni1 O3 H3O 121.5 . . ? C1 N1 C5 119.1(7) . . ? C1 N1 Ni1 128.5(6) . . ? C5 N1 Ni1 112.4(5) . . ? C6 N2 H1N 122.2 . . ? C6 N2 H2N 104.9 . . ? H1N N2 H2N 132.8 . . ? C6 N3 N4 118.5(6) . . ? C6 N3 Ni1 121.1(5) . . ? N4 N3 Ni1 120.2(4) . . ? C7 N4 N3 108.6(6) . . ? C8 N5 O2 115.1(6) . . ? C8 N5 Ni1 119.8(5) . 8_756 ? O2 N5 Ni1 125.1(4) . 8_756 ? O5 N6 O6 123.6(9) . . ? O5 N6 O4 118.6(9) . . ? O6 N6 O4 117.7(9) . . ? N1 C1 C2 121.5(8) . . ? N1 C1 H1 119.3 . . ? C2 C1 H1 119.3 . . ? C3 C2 C1 120.0(9) . . ? C3 C2 H2 120.0 . . ? C1 C2 H2 120.0 . . ? C2 C3 C4 119.3(8) . . ? C2 C3 H3 120.3 . . ? C4 C3 H3 120.3 . . ? C5 C4 C3 118.9(8) . . ? C5 C4 H4 120.5 . . ? C3 C4 H4 120.5 . . ? N1 C5 C4 121.1(7) . . ? N1 C5 C6 114.0(6) . . ? C4 C5 C6 124.9(7) . . ? N3 C6 N2 123.8(7) . . ? N3 C6 C5 114.4(6) . . ? N2 C6 C5 121.8(7) . . ? N4 C7 O1 126.5(7) . . ? N4 C7 C8 117.1(6) . . ? O1 C7 C8 116.5(6) . . ? N5 C8 C7 112.7(6) . . ? N5 C8 C9 126.7(7) . . ? C7 C8 C9 120.6(7) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? O3 C10 H10A 109.5 . . ? O3 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? O3 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 24.98 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 1.081 _refine_diff_density_min -0.655 _refine_diff_density_rms 0.103 data_5 _database_code_depnum_ccdc_archive 'CCDC 807495' #TrackingRef 'Submission.cif' # start Validation Reply Form _vrf_PLAT306_5 ; PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) ....... O7 RESPONSE: O7 is a lattice solvent water molecule for which the corresponding H-atoms could not be located in difference map positions. These atoms were omitted from the model, but included in the formula for the calculation of intensive properties. ; # end Validation Reply Form _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C40 H56 Cu4 N20 O12, 4(C F3 O3 S), H2 O' _chemical_formula_sum 'C44 H58 Cu4 F12 N20 O25 S4' _chemical_formula_weight 1877.47 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Cu Cu 0.3201 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0000 '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 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'I -4' _symmetry_space_group_name_Hall 'I -4' _symmetry_Int_Tables_number 82 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'y, -x, -z' '-x, -y, z' '-y, x, -z' 'x+1/2, y+1/2, z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, -z+1/2' _cell_length_a 18.5170(4) _cell_length_b 18.5170(4) _cell_length_c 11.0066(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3773.94(15) _cell_formula_units_Z 2 _cell_measurement_temperature 158(2) _cell_measurement_reflns_used 17617 _cell_measurement_theta_min 3.1 _cell_measurement_theta_max 27.5 _exptl_crystal_description Prism _exptl_crystal_colour Green _exptl_crystal_size_max 0.4600 _exptl_crystal_size_mid 0.1300 _exptl_crystal_size_min 0.1000 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.652 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1900 _exptl_absorpt_coefficient_mu 1.336 _exptl_absorpt_correction_type none _exptl_special_details ; ? ; _diffrn_ambient_temperature 158(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 2283 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0118 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.08 _diffrn_reflns_theta_max 26.48 _reflns_number_total 2058 _reflns_number_gt 2030 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'FS-PROCESS-AUTO(Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'FS-PROCESS-AUTO(Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_structure_solution 'SHELXL-97 (Acta Cryst. 2008. A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst. 2008. A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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. C11 and C12 were each half-occupancy PARTs of a disordered methanol molecule. The C11-O6 and C12-O6 bonds were each treated with SIMU and DFIX restraints. The methanolic and lattice solvent water H-atoms could not be located in difference map positions and were hence omitted from the model. These atoms were included in the formula for the calculation of intensive properties. MERG 4 was used and the Flack parameter was not determined. ; _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^)+(0.0674P)^2^+8.3187P] 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 2058 _refine_ls_number_parameters 256 _refine_ls_number_restraints 14 _refine_ls_R_factor_all 0.0357 _refine_ls_R_factor_gt 0.0353 _refine_ls_wR_factor_ref 0.1027 _refine_ls_wR_factor_gt 0.1024 _refine_ls_goodness_of_fit_ref 1.089 _refine_ls_restrained_S_all 1.097 _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 0.08359(3) 0.37250(3) 0.23427(5) 0.02121(16) Uani 1 1 d . . . S1 S 0.20891(7) 0.12266(7) 0.14396(13) 0.0326(3) Uani 1 1 d . . . F1 F 0.2130(5) -0.0107(5) 0.0759(14) 0.214(7) Uani 1 1 d . . . F2 F 0.1294(4) 0.0118(4) 0.1924(13) 0.175(6) Uani 1 1 d . . . F3 F 0.2368(5) 0.0057(4) 0.2607(12) 0.181(6) Uani 1 1 d . . . O1 O -0.01841(16) 0.39334(18) 0.1835(3) 0.0243(7) Uani 1 1 d . . . O2 O -0.20617(18) 0.4564(2) 0.0396(4) 0.0324(8) Uani 1 1 d . . . H2O H -0.2371 0.4591 0.0952 0.039 Uiso 1 1 calc R . . O3 O 0.2838(2) 0.1284(3) 0.1091(5) 0.0613(14) Uani 1 1 d . . . O4 O 0.1585(3) 0.1396(4) 0.0513(5) 0.0714(17) Uani 1 1 d . . . O5 O 0.1943(2) 0.1535(3) 0.2601(5) 0.0551(12) Uani 1 1 d . . . O6 O 0.0601(2) 0.2241(3) 0.2602(6) 0.0662(15) Uani 1 1 d DU . . O7 O 0.0000 0.0000 0.5000 0.095(4) Uani 1 4 d S . . N1 N 0.1901(2) 0.3431(2) 0.2177(4) 0.0247(8) Uani 1 1 d . . . N2 N 0.1657(3) 0.3582(3) -0.1084(4) 0.0343(10) Uani 1 1 d . . . H2A H 0.1304 0.3698 -0.1582 0.041 Uiso 1 1 calc R . . H2B H 0.2082 0.3459 -0.1375 0.041 Uiso 1 1 calc R . . N3 N 0.0941(2) 0.3767(2) 0.0629(3) 0.0235(7) Uani 1 1 d . . . N4 N 0.0347(2) 0.3963(2) -0.0081(4) 0.0241(8) Uani 1 1 d . . . N5 N -0.1407(2) 0.4338(2) 0.0883(4) 0.0238(8) Uani 1 1 d . . . C1 C 0.2377(3) 0.3288(3) 0.3049(5) 0.0293(10) Uani 1 1 d . . . H1 H 0.2226 0.3318 0.3873 0.035 Uiso 1 1 calc R . . C2 C 0.3087(3) 0.3096(3) 0.2802(5) 0.0316(11) Uani 1 1 d . . . H2 H 0.3417 0.2998 0.3442 0.038 Uiso 1 1 calc R . . C3 C 0.3304(3) 0.3049(3) 0.1599(5) 0.0334(11) Uani 1 1 d . . . H3 H 0.3784 0.2911 0.1402 0.040 Uiso 1 1 calc R . . C4 C 0.2809(3) 0.3206(3) 0.0683(5) 0.0318(10) Uani 1 1 d . . . H4 H 0.2946 0.3179 -0.0148 0.038 Uiso 1 1 calc R . . C5 C 0.2122(3) 0.3400(2) 0.1006(5) 0.0247(9) Uani 1 1 d . . . C6 C 0.1548(3) 0.3593(2) 0.0108(5) 0.0250(9) Uani 1 1 d . . . C7 C -0.0201(2) 0.4037(2) 0.0664(4) 0.0225(9) Uani 1 1 d . . . C8 C -0.0892(2) 0.4278(2) 0.0117(4) 0.0225(9) Uani 1 1 d . . . C9 C -0.0962(3) 0.4443(3) -0.1206(4) 0.0285(10) Uani 1 1 d . . . H9A H -0.1439 0.4290 -0.1494 0.034 Uiso 1 1 calc R . . H9B H -0.0587 0.4184 -0.1658 0.034 Uiso 1 1 calc R . . H9C H -0.0906 0.4964 -0.1336 0.034 Uiso 1 1 calc R . . C10 C 0.1929(7) 0.0286(5) 0.1739(17) 0.118(6) Uani 1 1 d . . . C11 C 0.0091(9) 0.1548(10) 0.251(3) 0.103(7) Uani 0.50 1 d PDU A 1 H11A H -0.0404 0.1683 0.2733 0.123 Uiso 0.50 1 calc PR A 1 H11B H 0.0266 0.1175 0.3074 0.123 Uiso 0.50 1 calc PR A 1 H11C H 0.0099 0.1361 0.1681 0.123 Uiso 0.50 1 calc PR A 1 C12 C 0.0056(8) 0.1966(11) 0.1798(18) 0.073(5) Uani 0.50 1 d PDU A 2 H12A H -0.0137 0.1513 0.2126 0.088 Uiso 0.50 1 calc PR A 2 H12B H 0.0268 0.1876 0.0996 0.088 Uiso 0.50 1 calc PR A 2 H12C H -0.0335 0.2320 0.1723 0.088 Uiso 0.50 1 calc PR A 2 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 0.0233(3) 0.0256(3) 0.0147(3) 0.00074(19) 0.0004(2) 0.0020(2) S1 0.0314(6) 0.0375(6) 0.0288(6) 0.0008(6) -0.0056(5) 0.0038(5) F1 0.163(9) 0.115(6) 0.36(2) -0.150(10) -0.040(11) -0.004(6) F2 0.108(5) 0.099(5) 0.319(16) 0.071(7) -0.043(8) -0.066(4) F3 0.168(8) 0.081(4) 0.296(15) 0.100(7) -0.111(9) -0.023(4) O1 0.0236(15) 0.0321(17) 0.0171(15) 0.0022(13) -0.0004(12) 0.0023(13) O2 0.0252(16) 0.048(2) 0.0243(17) 0.0025(16) -0.0029(14) 0.0101(14) O3 0.036(2) 0.093(4) 0.055(3) -0.006(3) 0.006(2) 0.007(2) O4 0.049(3) 0.118(5) 0.046(3) 0.031(3) -0.015(2) 0.001(3) O5 0.036(2) 0.090(3) 0.039(3) -0.022(3) -0.001(2) 0.005(2) O6 0.048(2) 0.088(4) 0.063(4) -0.038(3) 0.000(3) 0.016(2) O7 0.094(6) 0.094(6) 0.098(12) 0.000 0.000 0.000 N1 0.0292(19) 0.0242(17) 0.021(2) 0.0000(16) 0.0022(16) 0.0023(14) N2 0.034(2) 0.050(3) 0.019(2) -0.0010(19) 0.0040(17) 0.0070(19) N3 0.0261(19) 0.027(2) 0.0174(17) 0.0001(16) -0.0003(15) 0.0007(15) N4 0.0278(19) 0.0277(18) 0.0167(18) 0.0008(15) -0.0020(15) 0.0024(15) N5 0.0266(19) 0.0253(19) 0.0197(18) 0.0005(16) -0.0061(16) -0.0017(14) C1 0.030(2) 0.032(2) 0.027(3) 0.003(2) -0.001(2) 0.0053(19) C2 0.029(2) 0.035(2) 0.030(3) 0.002(2) -0.002(2) 0.0044(19) C3 0.027(2) 0.038(3) 0.035(3) -0.001(2) 0.003(2) 0.008(2) C4 0.033(2) 0.036(2) 0.027(3) -0.002(2) 0.005(2) 0.004(2) C5 0.029(2) 0.023(2) 0.022(2) 0.0004(18) 0.0008(19) 0.0007(17) C6 0.030(2) 0.024(2) 0.021(2) -0.0015(17) 0.0004(19) 0.0010(17) C7 0.027(2) 0.0218(19) 0.019(2) -0.0005(17) -0.0028(17) -0.0018(16) C8 0.028(2) 0.022(2) 0.017(2) -0.0003(17) -0.0032(17) -0.0020(17) C9 0.038(3) 0.033(2) 0.015(2) 0.0021(18) -0.0022(19) -0.001(2) C10 0.114(9) 0.044(4) 0.197(17) -0.007(7) -0.060(10) -0.010(5) C11 0.071(10) 0.131(15) 0.106(15) -0.058(14) -0.032(12) 0.047(11) C12 0.041(7) 0.101(12) 0.078(11) -0.048(10) -0.027(7) 0.031(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 Cu1 N3 1.898(4) . ? Cu1 N5 1.994(4) 8 ? Cu1 O1 2.007(3) . ? Cu1 N1 2.053(4) . ? Cu1 O1 2.255(3) 8 ? S1 O4 1.417(5) . ? S1 O5 1.426(5) . ? S1 O3 1.443(5) . ? S1 C10 1.797(10) . ? F1 C10 1.35(2) . ? F2 C10 1.234(15) . ? F3 C10 1.324(15) . ? O1 C7 1.303(6) . ? O1 Cu1 2.255(3) 6_455 ? O2 N5 1.390(5) . ? O2 H2O 0.8400 . ? O6 C12 1.436(12) . ? O6 C11 1.597(17) . ? N1 C1 1.331(7) . ? N1 C5 1.354(6) . ? N2 C6 1.328(7) . ? N2 H2A 0.8800 . ? N2 H2B 0.8800 . ? N3 C6 1.302(6) . ? N3 N4 1.397(5) . ? N4 C7 1.312(6) . ? N5 C8 1.278(6) . ? N5 Cu1 1.994(4) 6_455 ? C1 C2 1.389(7) . ? C1 H1 0.9500 . ? C2 C3 1.385(8) . ? C2 H2 0.9500 . ? C3 C4 1.393(8) . ? C3 H3 0.9500 . ? C4 C5 1.370(7) . ? C4 H4 0.9500 . ? C5 C6 1.494(7) . ? C7 C8 1.484(6) . ? C8 C9 1.493(6) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? 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 N3 Cu1 N5 174.16(18) . 8 ? N3 Cu1 O1 79.14(15) . . ? N5 Cu1 O1 98.30(15) 8 . ? N3 Cu1 N1 79.87(17) . . ? N5 Cu1 N1 102.10(16) 8 . ? O1 Cu1 N1 158.38(16) . . ? N3 Cu1 O1 110.08(15) . 8 ? N5 Cu1 O1 75.35(14) 8 8 ? O1 Cu1 O1 96.77(18) . 8 ? N1 Cu1 O1 95.23(13) . 8 ? O4 S1 O5 115.6(3) . . ? O4 S1 O3 115.2(3) . . ? O5 S1 O3 113.1(3) . . ? O4 S1 C10 103.7(5) . . ? O5 S1 C10 101.1(6) . . ? O3 S1 C10 106.1(5) . . ? C7 O1 Cu1 109.0(3) . . ? C7 O1 Cu1 110.4(3) . 6_455 ? Cu1 O1 Cu1 140.14(17) . 6_455 ? N5 O2 H2O 109.5 . . ? C1 N1 C5 118.5(4) . . ? C1 N1 Cu1 128.7(4) . . ? C5 N1 Cu1 112.7(3) . . ? C6 N2 H2A 120.0 . . ? C6 N2 H2B 120.0 . . ? H2A N2 H2B 120.0 . . ? C6 N3 N4 119.8(4) . . ? C6 N3 Cu1 121.0(3) . . ? N4 N3 Cu1 119.1(3) . . ? C7 N4 N3 106.6(4) . . ? C8 N5 O2 115.0(4) . . ? C8 N5 Cu1 122.8(3) . 6_455 ? O2 N5 Cu1 122.2(3) . 6_455 ? N1 C1 C2 122.5(5) . . ? N1 C1 H1 118.8 . . ? C2 C1 H1 118.8 . . ? C3 C2 C1 118.5(5) . . ? C3 C2 H2 120.8 . . ? C1 C2 H2 120.8 . . ? C2 C3 C4 119.3(5) . . ? C2 C3 H3 120.4 . . ? C4 C3 H3 120.4 . . ? C5 C4 C3 118.5(5) . . ? C5 C4 H4 120.7 . . ? C3 C4 H4 120.7 . . ? N1 C5 C4 122.6(5) . . ? N1 C5 C6 113.9(4) . . ? C4 C5 C6 123.5(5) . . ? N3 C6 N2 124.7(5) . . ? N3 C6 C5 112.5(4) . . ? N2 C6 C5 122.8(5) . . ? O1 C7 N4 125.8(4) . . ? O1 C7 C8 117.8(4) . . ? N4 C7 C8 116.4(4) . . ? N5 C8 C7 113.7(4) . . ? N5 C8 C9 124.2(4) . . ? C7 C8 C9 122.2(4) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? F2 C10 F3 112.6(15) . . ? F2 C10 F1 104.9(11) . . ? F3 C10 F1 103.6(11) . . ? F2 C10 S1 115.6(9) . . ? F3 C10 S1 109.9(8) . . ? F1 C10 S1 109.3(12) . . ? O6 C11 H11A 109.5 . . ? O6 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? O6 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? O6 C12 H12A 109.5 . . ? O6 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? O6 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.48 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.875 _refine_diff_density_min -0.640 _refine_diff_density_rms 0.088 data_6 _database_code_depnum_ccdc_archive 'CCDC 807496' #TrackingRef 'Submission.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C44 H48 Mn4 N16 O16, 2(C2 H3 N), 0.5(H2 O)' _chemical_formula_sum 'C48 H55 Mn4 N18 O16.50' _chemical_formula_weight 1367.83 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' Mn Mn 0.3368 0.7283 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 1 2/c 1' _symmetry_space_group_name_Hall '-C 2yc' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 19.148(4) _cell_length_b 19.407(4) _cell_length_c 16.292(3) _cell_angle_alpha 90.00 _cell_angle_beta 102.319(4) _cell_angle_gamma 90.00 _cell_volume 5915.0(19) _cell_formula_units_Z 4 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 12235 _cell_measurement_theta_min 2.4582 _cell_measurement_theta_max 30.7917 _exptl_crystal_description Prism _exptl_crystal_colour Orange _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.536 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2804 _exptl_absorpt_coefficient_mu 0.916 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.9113 _exptl_absorpt_correction_T_min 0.8548 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 34571 _diffrn_reflns_av_R_equivalents 0.0290 _diffrn_reflns_av_sigmaI/netI 0.0190 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.56 _diffrn_reflns_theta_max 26.50 _reflns_number_total 6096 _reflns_number_gt 5951 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Acta Cryst.2008, A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst.2008, A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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^)+(0.0733P)^2^+7.9163P] 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 6096 _refine_ls_number_parameters 398 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0507 _refine_ls_R_factor_gt 0.0497 _refine_ls_wR_factor_ref 0.1351 _refine_ls_wR_factor_gt 0.1341 _refine_ls_goodness_of_fit_ref 1.109 _refine_ls_restrained_S_all 1.109 _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 Mn1 Mn 0.118656(18) 0.346104(17) 0.35838(2) 0.03139(13) Uani 1 1 d . . . Mn2 Mn 0.064566(19) 0.264728(19) 0.12771(2) 0.03493(13) Uani 1 1 d . . . O1 O 0.09211(9) 0.25919(8) 0.26526(10) 0.0324(4) Uani 1 1 d . . . O2 O 0.04396(11) 0.09981(10) 0.10952(14) 0.0535(5) Uani 1 1 d . . . H9 H 0.0277 0.1166 0.0551 0.064 Uiso 1 1 d . . . O3 O -0.00548(9) 0.35205(8) 0.14027(11) 0.0356(4) Uani 1 1 d . . . O4 O -0.12594(11) 0.51513(9) 0.15915(14) 0.0517(5) Uani 1 1 d . . . H18 H -0.1677 0.4943 0.1689 0.062 Uiso 1 1 d . . . O5 O 0.21876(10) 0.36027(9) 0.32911(13) 0.0443(4) Uani 1 1 d . . . O6 O 0.24080(12) 0.47064(10) 0.30667(15) 0.0586(6) Uani 1 1 d . . . O7 O 0.02134(13) 0.25737(13) -0.00063(13) 0.0628(6) Uani 1 1 d . . . O8 O -0.00582(18) 0.14989(17) -0.03746(17) 0.0861(9) Uani 1 1 d . . . O9 O 0.0385(8) 0.0803(6) 0.8328(8) 0.102(4) Uani 0.25 1 d P . . H25 H 0.0004 0.0610 0.8556 0.121 Uiso 0.25 1 d P . . H26 H 0.0831 0.0763 0.8743 0.121 Uiso 0.25 1 d P . . N1 N 0.16015(11) 0.36446(11) 0.50240(13) 0.0379(5) Uani 1 1 d . . . N2 N 0.13755(11) 0.24482(10) 0.42286(13) 0.0333(4) Uani 1 1 d . . . N3 N 0.12462(11) 0.18358(10) 0.37733(14) 0.0352(4) Uani 1 1 d . . . N4 N 0.05864(11) 0.15449(10) 0.16474(15) 0.0378(5) Uani 1 1 d . . . N5 N 0.18087(11) 0.23726(13) 0.11323(14) 0.0424(5) Uani 1 1 d . . . N6 N 0.12282(11) 0.36051(12) 0.12100(14) 0.0404(5) Uani 1 1 d . . . N7 N 0.08800(13) 0.42330(12) 0.12392(15) 0.0445(5) Uani 1 1 d . . . N8 N -0.08334(12) 0.45882(10) 0.15383(13) 0.0383(5) Uani 1 1 d . . . N9 N 0.1965(4) -0.0462(3) 0.4579(6) 0.234(5) Uani 1 1 d . . . C1 C 0.16969(16) 0.42447(14) 0.54356(18) 0.0483(7) Uani 1 1 d . . . H1 H 0.1579 0.4657 0.5122 0.058 Uiso 1 1 calc R . . C2 C 0.19586(16) 0.42995(16) 0.62954(19) 0.0511(7) Uani 1 1 d . . . H2 H 0.2012 0.4737 0.6563 0.061 Uiso 1 1 calc R . . C3 C 0.21381(16) 0.37063(17) 0.67482(18) 0.0498(7) Uani 1 1 d . . . H3 H 0.2320 0.3727 0.7338 0.060 Uiso 1 1 calc R . . C4 C 0.20522(15) 0.30765(15) 0.63400(17) 0.0449(6) Uani 1 1 d . . . H4 H 0.2183 0.2662 0.6644 0.054 Uiso 1 1 calc R . . C5 C 0.17741(13) 0.30599(13) 0.54855(16) 0.0370(5) Uani 1 1 d . . . C6 C 0.16500(14) 0.24139(13) 0.50138(17) 0.0385(5) Uani 1 1 d . . . H5 H 0.1770 0.1983 0.5283 0.046 Uiso 1 1 calc R . . C7 C 0.10162(12) 0.19832(11) 0.29819(16) 0.0326(5) Uani 1 1 d . . . C8 C 0.08501(13) 0.13752(12) 0.24020(18) 0.0380(5) Uani 1 1 d . . . C9 C 0.1008(2) 0.06574(14) 0.2708(2) 0.0596(8) Uani 1 1 d . . . H6 H 0.1413 0.0660 0.3190 0.071 Uiso 1 1 calc R . . H7 H 0.1126 0.0376 0.2257 0.071 Uiso 1 1 calc R . . H8 H 0.0587 0.0464 0.2878 0.071 Uiso 1 1 calc R . . C10 C 0.20953(15) 0.17471(17) 0.10750(18) 0.0490(7) Uani 1 1 d . . . H10 H 0.1805 0.1353 0.1094 0.059 Uiso 1 1 calc R . . C11 C 0.27951(16) 0.1646(2) 0.09891(19) 0.0588(8) Uani 1 1 d . . . H11 H 0.2979 0.1195 0.0950 0.071 Uiso 1 1 calc R . . C12 C 0.32127(16) 0.2219(2) 0.0963(2) 0.0646(9) Uani 1 1 d . . . H12 H 0.3695 0.2168 0.0910 0.078 Uiso 1 1 calc R . . C13 C 0.29322(16) 0.2866(2) 0.1014(2) 0.0610(9) Uani 1 1 d . . . H13 H 0.3216 0.3265 0.0994 0.073 Uiso 1 1 calc R . . C14 C 0.22212(14) 0.29291(17) 0.10956(17) 0.0474(6) Uani 1 1 d . . . C15 C 0.18785(15) 0.35987(17) 0.11293(18) 0.0491(7) Uani 1 1 d . . . H14 H 0.2130 0.4015 0.1093 0.059 Uiso 1 1 calc R . . C16 C 0.02292(13) 0.41201(13) 0.13394(15) 0.0372(5) Uani 1 1 d . . . C17 C -0.02178(15) 0.47352(13) 0.13962(17) 0.0417(6) Uani 1 1 d . . . C18 C 0.00445(19) 0.54524(15) 0.1290(3) 0.0644(9) Uani 1 1 d . . . H15 H 0.0565 0.5469 0.1489 0.077 Uiso 1 1 calc R . . H16 H -0.0180 0.5775 0.1618 0.077 Uiso 1 1 calc R . . H17 H -0.0080 0.5581 0.0695 0.077 Uiso 1 1 calc R . . C19 C 0.25718(14) 0.40812(14) 0.31122(17) 0.0427(6) Uani 1 1 d . . . C20 C 0.32868(16) 0.38829(16) 0.2934(2) 0.0557(7) Uani 1 1 d . . . H19 H 0.3651 0.3892 0.3457 0.067 Uiso 1 1 calc R . . H20 H 0.3417 0.4210 0.2533 0.067 Uiso 1 1 calc R . . H21 H 0.3257 0.3418 0.2695 0.067 Uiso 1 1 calc R . . C21 C 0.00004(16) 0.2118(2) -0.0539(2) 0.0633(10) Uani 1 1 d . . . C22 C -0.0202(2) 0.2348(3) -0.1441(2) 0.0921(16) Uani 1 1 d . . . H22 H 0.0086 0.2749 -0.1523 0.111 Uiso 1 1 calc R . . H23 H -0.0710 0.2472 -0.1579 0.111 Uiso 1 1 calc R . . H24 H -0.0115 0.1972 -0.1808 0.111 Uiso 1 1 calc R . . C23 C 0.1536(3) -0.0160(2) 0.4744(3) 0.0951(16) Uani 1 1 d . . . C24 C 0.1021(3) 0.0253(2) 0.4987(3) 0.0863(12) Uani 1 1 d . . . H27 H 0.1056 0.0208 0.5593 0.104 Uiso 1 1 calc R . . H28 H 0.0544 0.0106 0.4687 0.104 Uiso 1 1 calc R . . H29 H 0.1098 0.0734 0.4850 0.104 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 Mn1 0.0347(2) 0.0254(2) 0.0331(2) 0.00197(12) 0.00489(15) 0.00284(13) Mn2 0.0333(2) 0.0379(2) 0.0341(2) -0.00108(14) 0.00843(16) -0.00413(14) O1 0.0394(9) 0.0252(7) 0.0333(9) 0.0010(6) 0.0095(7) 0.0014(6) O2 0.0584(12) 0.0424(11) 0.0608(13) -0.0242(9) 0.0149(10) -0.0071(9) O3 0.0333(8) 0.0311(8) 0.0411(10) 0.0046(7) 0.0051(7) -0.0057(6) O4 0.0569(12) 0.0281(9) 0.0698(14) -0.0046(8) 0.0128(10) 0.0020(8) O5 0.0389(9) 0.0384(9) 0.0563(12) 0.0053(8) 0.0119(8) -0.0027(7) O6 0.0606(13) 0.0395(11) 0.0785(16) 0.0123(10) 0.0210(11) 0.0008(9) O7 0.0633(14) 0.0835(16) 0.0370(11) -0.0054(10) 0.0002(10) -0.0190(12) O8 0.104(2) 0.099(2) 0.0539(16) -0.0276(14) 0.0139(15) -0.0258(18) O9 0.140(11) 0.088(8) 0.082(8) -0.021(6) 0.034(7) 0.057(8) N1 0.0402(11) 0.0380(10) 0.0327(11) 0.0009(8) 0.0016(8) 0.0086(9) N2 0.0349(10) 0.0300(9) 0.0361(11) 0.0048(8) 0.0099(8) 0.0049(8) N3 0.0404(11) 0.0247(9) 0.0420(12) 0.0038(8) 0.0123(9) 0.0030(8) N4 0.0371(11) 0.0328(10) 0.0463(13) -0.0104(9) 0.0150(9) -0.0050(8) N5 0.0338(11) 0.0608(14) 0.0346(12) 0.0019(10) 0.0119(9) -0.0010(10) N6 0.0366(11) 0.0472(12) 0.0362(11) 0.0014(9) 0.0053(9) -0.0094(9) N7 0.0474(12) 0.0409(12) 0.0438(13) 0.0032(9) 0.0065(10) -0.0148(10) N8 0.0450(12) 0.0262(9) 0.0406(12) -0.0006(8) 0.0022(9) -0.0007(8) N9 0.303(9) 0.104(4) 0.390(11) 0.108(5) 0.288(9) 0.123(5) C1 0.0565(16) 0.0401(14) 0.0424(15) -0.0038(11) -0.0027(12) 0.0131(12) C2 0.0542(16) 0.0511(16) 0.0443(16) -0.0099(12) 0.0019(12) 0.0124(13) C3 0.0484(15) 0.0637(18) 0.0351(14) -0.0025(13) 0.0043(11) 0.0093(13) C4 0.0442(14) 0.0551(16) 0.0339(14) 0.0098(11) 0.0049(11) 0.0078(12) C5 0.0357(12) 0.0394(12) 0.0356(13) 0.0040(10) 0.0072(10) 0.0087(10) C6 0.0394(13) 0.0360(12) 0.0400(14) 0.0088(10) 0.0081(11) 0.0071(10) C7 0.0316(11) 0.0266(10) 0.0423(13) 0.0011(9) 0.0136(9) 0.0009(8) C8 0.0362(12) 0.0283(11) 0.0533(16) -0.0043(10) 0.0183(11) -0.0020(9) C9 0.076(2) 0.0281(13) 0.074(2) -0.0038(13) 0.0157(17) -0.0006(13) C10 0.0437(14) 0.0669(18) 0.0391(14) 0.0080(13) 0.0145(11) 0.0111(13) C11 0.0451(16) 0.088(2) 0.0456(17) 0.0130(15) 0.0159(13) 0.0168(16) C12 0.0342(14) 0.108(3) 0.0519(19) 0.0080(18) 0.0103(13) 0.0084(16) C13 0.0388(15) 0.094(3) 0.0521(18) 0.0022(17) 0.0143(13) -0.0129(16) C14 0.0360(13) 0.0707(19) 0.0360(14) -0.0003(13) 0.0090(10) -0.0078(13) C15 0.0416(14) 0.0622(17) 0.0456(15) -0.0017(13) 0.0137(12) -0.0191(13) C16 0.0394(12) 0.0363(12) 0.0332(12) 0.0026(9) 0.0017(10) -0.0103(10) C17 0.0479(14) 0.0318(12) 0.0421(14) 0.0021(10) 0.0020(11) -0.0097(10) C18 0.068(2) 0.0347(14) 0.091(3) 0.0059(15) 0.0189(18) -0.0131(14) C19 0.0435(13) 0.0413(13) 0.0405(14) 0.0062(11) 0.0024(11) -0.0037(11) C20 0.0438(15) 0.0508(16) 0.073(2) 0.0077(14) 0.0135(14) -0.0054(13) C21 0.0403(15) 0.110(3) 0.0424(17) -0.0190(18) 0.0138(12) -0.0266(17) C22 0.074(2) 0.164(5) 0.0381(18) -0.015(2) 0.0119(16) -0.062(3) C23 0.120(4) 0.066(2) 0.119(4) 0.036(2) 0.067(3) 0.032(2) C24 0.103(3) 0.073(2) 0.088(3) -0.006(2) 0.033(2) 0.023(2) _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 O5 2.0899(19) . ? Mn1 O3 2.1750(17) 2 ? Mn1 N2 2.222(2) . ? Mn1 O1 2.2531(16) . ? Mn1 N8 2.286(2) 2 ? Mn1 N1 2.338(2) . ? Mn2 O7 2.083(2) . ? Mn2 N6 2.183(2) . ? Mn2 O1 2.1926(17) . ? Mn2 O3 2.1977(17) . ? Mn2 N4 2.232(2) . ? Mn2 N5 2.350(2) . ? O1 C7 1.294(3) . ? O2 N4 1.381(3) . ? O2 H9 0.9332 . ? O3 C16 1.298(3) . ? O3 Mn1 2.1749(17) 2 ? O4 N8 1.377(3) . ? O4 H18 0.9397 . ? O5 C19 1.257(3) . ? O6 C19 1.251(3) . ? O7 C21 1.245(4) . ? O8 C21 1.242(5) . ? O9 H25 0.9630 . ? O9 H26 0.9721 . ? N1 C1 1.337(3) . ? N1 C5 1.363(3) . ? N2 C6 1.277(3) . ? N2 N3 1.395(3) . ? N3 C7 1.302(3) . ? N4 C8 1.269(4) . ? N5 C10 1.344(4) . ? N5 C14 1.347(4) . ? N6 C15 1.280(4) . ? N6 N7 1.395(3) . ? N7 C16 1.309(3) . ? N8 C17 1.281(4) . ? N8 Mn1 2.286(2) 2 ? N9 C23 1.090(6) . ? C1 C2 1.388(4) . ? C1 H1 0.9500 . ? C2 C3 1.371(4) . ? C2 H2 0.9500 . ? C3 C4 1.384(4) . ? C3 H3 0.9500 . ? C4 C5 1.381(4) . ? C4 H4 0.9500 . ? C5 C6 1.463(4) . ? C6 H5 0.9500 . ? C7 C8 1.503(3) . ? C8 C9 1.489(4) . ? C9 H6 0.9800 . ? C9 H7 0.9800 . ? C9 H8 0.9800 . ? C10 C11 1.390(4) . ? C10 H10 0.9500 . ? C11 C12 1.376(5) . ? C11 H11 0.9500 . ? C12 C13 1.375(6) . ? C12 H12 0.9500 . ? C13 C14 1.401(4) . ? C13 H13 0.9500 . ? C14 C15 1.462(5) . ? C15 H14 0.9500 . ? C16 C17 1.483(4) . ? C17 C18 1.502(3) . ? C18 H15 0.9800 . ? C18 H16 0.9800 . ? C18 H17 0.9800 . ? C19 C20 1.509(4) . ? C20 H19 0.9800 . ? C20 H20 0.9800 . ? C20 H21 0.9800 . ? C21 C22 1.504(5) . ? C22 H22 0.9800 . ? C22 H23 0.9800 . ? C22 H24 0.9800 . ? C23 C24 1.391(6) . ? C24 H27 0.9800 . ? C24 H28 0.9800 . ? C24 H29 0.9800 . ? 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 O5 Mn1 O3 163.68(7) . 2 ? O5 Mn1 N2 99.18(7) . . ? O3 Mn1 N2 95.98(7) 2 . ? O5 Mn1 O1 91.77(7) . . ? O3 Mn1 O1 87.96(6) 2 . ? N2 Mn1 O1 69.30(7) . . ? O5 Mn1 N8 97.06(8) . 2 ? O3 Mn1 N8 70.92(7) 2 2 ? N2 Mn1 N8 154.58(8) . 2 ? O1 Mn1 N8 129.63(7) . 2 ? O5 Mn1 N1 94.42(8) . . ? O3 Mn1 N1 96.19(7) 2 . ? N2 Mn1 N1 70.99(8) . . ? O1 Mn1 N1 140.29(7) . . ? N8 Mn1 N1 88.42(7) 2 . ? O7 Mn2 N6 96.08(9) . . ? O7 Mn2 O1 168.53(8) . . ? N6 Mn2 O1 94.53(7) . . ? O7 Mn2 O3 91.52(9) . . ? N6 Mn2 O3 71.13(8) . . ? O1 Mn2 O3 87.77(6) . . ? O7 Mn2 N4 99.98(9) . . ? N6 Mn2 N4 152.35(8) . . ? O1 Mn2 N4 72.05(7) . . ? O3 Mn2 N4 130.29(7) . . ? O7 Mn2 N5 93.77(9) . . ? N6 Mn2 N5 71.51(9) . . ? O1 Mn2 N5 93.73(7) . . ? O3 Mn2 N5 142.60(7) . . ? N4 Mn2 N5 85.05(8) . . ? C7 O1 Mn2 116.77(15) . . ? C7 O1 Mn1 114.38(15) . . ? Mn2 O1 Mn1 128.46(7) . . ? N4 O2 H9 109.3 . . ? C16 O3 Mn1 118.92(16) . 2 ? C16 O3 Mn2 114.18(16) . . ? Mn1 O3 Mn2 126.10(7) 2 . ? N8 O4 H18 101.9 . . ? C19 O5 Mn1 139.53(18) . . ? C21 O7 Mn2 138.6(3) . . ? H25 O9 H26 109.0 . . ? C1 N1 C5 117.2(2) . . ? C1 N1 Mn1 128.09(18) . . ? C5 N1 Mn1 114.67(17) . . ? C6 N2 N3 118.5(2) . . ? C6 N2 Mn1 120.70(17) . . ? N3 N2 Mn1 120.65(15) . . ? C7 N3 N2 108.87(18) . . ? C8 N4 O2 114.6(2) . . ? C8 N4 Mn2 118.54(16) . . ? O2 N4 Mn2 125.13(18) . . ? C10 N5 C14 118.0(2) . . ? C10 N5 Mn2 128.44(19) . . ? C14 N5 Mn2 113.57(19) . . ? C15 N6 N7 119.7(2) . . ? C15 N6 Mn2 121.0(2) . . ? N7 N6 Mn2 119.29(15) . . ? C16 N7 N6 109.4(2) . . ? C17 N8 O4 114.5(2) . . ? C17 N8 Mn1 117.64(17) . 2 ? O4 N8 Mn1 126.62(16) . 2 ? N1 C1 C2 123.7(3) . . ? N1 C1 H1 118.2 . . ? C2 C1 H1 118.2 . . ? C3 C2 C1 118.3(3) . . ? C3 C2 H2 120.9 . . ? C1 C2 H2 120.9 . . ? C2 C3 C4 119.5(3) . . ? C2 C3 H3 120.2 . . ? C4 C3 H3 120.2 . . ? C5 C4 C3 119.1(3) . . ? C5 C4 H4 120.5 . . ? C3 C4 H4 120.5 . . ? N1 C5 C4 122.2(2) . . ? N1 C5 C6 115.5(2) . . ? C4 C5 C6 122.3(2) . . ? N2 C6 C5 117.9(2) . . ? N2 C6 H5 121.1 . . ? C5 C6 H5 121.1 . . ? O1 C7 N3 126.8(2) . . ? O1 C7 C8 117.6(2) . . ? N3 C7 C8 115.6(2) . . ? N4 C8 C9 125.3(2) . . ? N4 C8 C7 113.1(2) . . ? C9 C8 C7 121.6(3) . . ? C8 C9 H6 109.5 . . ? C8 C9 H7 109.5 . . ? H6 C9 H7 109.5 . . ? C8 C9 H8 109.5 . . ? H6 C9 H8 109.5 . . ? H7 C9 H8 109.5 . . ? N5 C10 C11 123.5(3) . . ? N5 C10 H10 118.3 . . ? C11 C10 H10 118.3 . . ? C12 C11 C10 117.9(3) . . ? C12 C11 H11 121.1 . . ? C10 C11 H11 121.1 . . ? C13 C12 C11 119.9(3) . . ? C13 C12 H12 120.0 . . ? C11 C12 H12 120.0 . . ? C12 C13 C14 119.0(3) . . ? C12 C13 H13 120.5 . . ? C14 C13 H13 120.5 . . ? N5 C14 C13 121.7(3) . . ? N5 C14 C15 116.0(2) . . ? C13 C14 C15 122.3(3) . . ? N6 C15 C14 117.8(3) . . ? N6 C15 H14 121.1 . . ? C14 C15 H14 121.1 . . ? O3 C16 N7 125.9(2) . . ? O3 C16 C17 117.3(2) . . ? N7 C16 C17 116.8(2) . . ? N8 C17 C16 113.4(2) . . ? N8 C17 C18 124.8(3) . . ? C16 C17 C18 121.8(3) . . ? C17 C18 H15 109.5 . . ? C17 C18 H16 109.5 . . ? H15 C18 H16 109.5 . . ? C17 C18 H17 109.5 . . ? H15 C18 H17 109.5 . . ? H16 C18 H17 109.5 . . ? O6 C19 O5 125.3(3) . . ? O6 C19 C20 117.5(2) . . ? O5 C19 C20 117.1(2) . . ? C19 C20 H19 109.5 . . ? C19 C20 H20 109.5 . . ? H19 C20 H20 109.5 . . ? C19 C20 H21 109.5 . . ? H19 C20 H21 109.5 . . ? H20 C20 H21 109.5 . . ? O8 C21 O7 124.6(3) . . ? O8 C21 C22 118.8(3) . . ? O7 C21 C22 116.7(4) . . ? C21 C22 H22 109.5 . . ? C21 C22 H23 109.5 . . ? H22 C22 H23 109.5 . . ? C21 C22 H24 109.5 . . ? H22 C22 H24 109.5 . . ? H23 C22 H24 109.5 . . ? N9 C23 C24 176.3(9) . . ? C23 C24 H27 109.5 . . ? C23 C24 H28 109.5 . . ? H27 C24 H28 109.5 . . ? C23 C24 H29 109.5 . . ? H27 C24 H29 109.5 . . ? H28 C24 H29 109.5 . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.594 _refine_diff_density_min -0.408 _refine_diff_density_rms 0.065 data_7 _database_code_depnum_ccdc_archive 'CCDC 807497' #TrackingRef 'Submission.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C40 H38 Mn4 N16 O14, 2(C2 H3 N)' _chemical_formula_sum 'C44 H44 Mn4 N18 O14' _chemical_formula_weight 1268.70 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' Mn Mn 0.3368 0.7283 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 11.2858(17) _cell_length_b 12.7841(17) _cell_length_c 19.247(3) _cell_angle_alpha 90.00 _cell_angle_beta 108.798(3) _cell_angle_gamma 90.00 _cell_volume 2628.8(7) _cell_formula_units_Z 2 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 8200 _cell_measurement_theta_min 2.4261 _cell_measurement_theta_max 30.6497 _exptl_crystal_description Prism _exptl_crystal_colour 'Dark Orange' _exptl_crystal_size_max 0.11 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.603 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1292 _exptl_absorpt_coefficient_mu 1.021 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.9489 _exptl_absorpt_correction_T_min 0.9385 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 10690 _diffrn_reflns_av_R_equivalents 0.0460 _diffrn_reflns_av_sigmaI/netI 0.0626 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 25.50 _reflns_number_total 4869 _reflns_number_gt 3870 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Acta Cryst.2008, A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst.2008, A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _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. H2W was located in its difference map position and was allowed to refine positionally with a fixed thermal parameter (1.2 times that of O2). In the final round of least squares H2W was refined on a riding model. All other H-atoms were introduced in calculated positions and refined on a riding model. ; _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^)+(0.0501P)^2^+3.6594P] 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 4869 _refine_ls_number_parameters 362 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0887 _refine_ls_R_factor_gt 0.0688 _refine_ls_wR_factor_ref 0.1555 _refine_ls_wR_factor_gt 0.1423 _refine_ls_goodness_of_fit_ref 1.110 _refine_ls_restrained_S_all 1.110 _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 Mn1 Mn 0.11083(7) 0.89856(6) 0.40187(4) 0.0384(2) Uani 1 1 d . . . Mn2 Mn 0.13139(7) 1.19869(6) 0.44379(4) 0.0409(2) Uani 1 1 d . . . O1 O 0.1383(3) 1.0616(3) 0.37802(17) 0.0424(8) Uani 1 1 d . . . O2 O 0.2744(4) 1.3390(3) 0.3535(2) 0.0564(10) Uani 1 1 d . . . H2W H 0.2689 1.3811 0.3955 0.067 Uiso 1 1 d . . . O3 O -0.0731(3) 0.9234(3) 0.36409(16) 0.0415(8) Uani 1 1 d . . . O4 O 0.0891(3) 0.7906(3) 0.59925(17) 0.0428(8) Uani 1 1 d . . . O5 O 0.2774(3) 0.8782(3) 0.45556(18) 0.0482(9) Uani 1 1 d . . . O6 O 0.1298(4) 1.3476(3) 0.4900(2) 0.0541(10) Uani 1 1 d . . . O7 O 0.2968(4) 1.4238(3) 0.4768(2) 0.0639(11) Uani 1 1 d . . . N1 N 0.0838(3) 0.7317(3) 0.3548(2) 0.0386(9) Uani 1 1 d . . . N2 N 0.1556(3) 0.9026(3) 0.3042(2) 0.0388(9) Uani 1 1 d . . . N3 N 0.1954(4) 0.9954(3) 0.2811(2) 0.0401(9) Uani 1 1 d . . . N4 N 0.2287(4) 1.2420(3) 0.3619(2) 0.0435(10) Uani 1 1 d . . . N5 N -0.2946(4) 0.8738(3) 0.4578(2) 0.0404(9) Uani 1 1 d . . . N6 N -0.0548(3) 0.8742(3) 0.4806(2) 0.0367(9) Uani 1 1 d . . . N7 N 0.0720(3) 0.8664(3) 0.4897(2) 0.0372(9) Uani 1 1 d . . . N8 N 0.3360(4) 0.8361(3) 0.5234(2) 0.0459(10) Uani 1 1 d . . . N9 N 0.4790(8) 0.5992(8) 0.3179(4) 0.136(3) Uani 1 1 d . . . C1 C 0.0524(5) 0.6456(4) 0.3834(3) 0.0447(12) Uani 1 1 d . . . H1 H 0.0248 0.6518 0.4250 0.054 Uiso 1 1 calc R . . C2 C 0.0584(5) 0.5472(4) 0.3548(3) 0.0520(13) Uani 1 1 d . . . H2 H 0.0367 0.4870 0.3770 0.062 Uiso 1 1 calc R . . C3 C 0.0962(5) 0.5372(4) 0.2938(3) 0.0463(12) Uani 1 1 d . . . H3 H 0.1026 0.4701 0.2741 0.056 Uiso 1 1 calc R . . C4 C 0.1244(5) 0.6256(4) 0.2620(3) 0.0443(12) Uani 1 1 d . . . H4 H 0.1479 0.6209 0.2189 0.053 Uiso 1 1 calc R . . C5 C 0.1181(4) 0.7218(4) 0.2935(3) 0.0409(11) Uani 1 1 d . . . C6 C 0.1529(4) 0.8194(4) 0.2663(3) 0.0426(12) Uani 1 1 d . . . H6 H 0.1729 0.8215 0.2221 0.051 Uiso 1 1 calc R . . C7 C 0.1848(4) 1.0714(4) 0.3241(3) 0.0399(11) Uani 1 1 d . . . C8 C 0.2288(4) 1.1757(4) 0.3119(3) 0.0409(11) Uani 1 1 d . . . C9 C 0.2733(5) 1.1989(4) 0.2479(3) 0.0527(14) Uani 1 1 d . . . H9A H 0.2063 1.2337 0.2092 0.063 Uiso 1 1 calc R . . H9B H 0.2957 1.1333 0.2289 0.063 Uiso 1 1 calc R . . H9C H 0.3467 1.2447 0.2638 0.063 Uiso 1 1 calc R . . C10 C -0.4149(5) 0.8829(4) 0.4513(3) 0.0503(13) Uani 1 1 d . . . H10 H -0.4420 0.8610 0.4909 0.060 Uiso 1 1 calc R . . C11 C -0.5025(5) 0.9232(5) 0.3888(3) 0.0572(15) Uani 1 1 d . . . H11 H -0.5877 0.9294 0.3862 0.069 Uiso 1 1 calc R . . C12 C -0.4649(5) 0.9543(5) 0.3301(3) 0.0557(14) Uani 1 1 d . . . H12 H -0.5240 0.9796 0.2861 0.067 Uiso 1 1 calc R . . C13 C -0.3393(5) 0.9477(4) 0.3373(3) 0.0438(12) Uani 1 1 d . . . H13 H -0.3096 0.9697 0.2988 0.053 Uiso 1 1 calc R . . C14 C -0.2589(4) 0.9085(4) 0.4014(3) 0.0366(10) Uani 1 1 d . . . C15 C -0.1219(4) 0.9019(3) 0.4152(2) 0.0336(10) Uani 1 1 d . . . C16 C 0.1383(4) 0.8219(4) 0.5529(2) 0.0365(11) Uani 1 1 d . . . C17 C 0.2746(5) 0.8114(4) 0.5664(3) 0.0400(11) Uani 1 1 d . . . C18 C 0.3511(5) 0.7658(4) 0.6388(3) 0.0524(14) Uani 1 1 d . . . H18A H 0.4382 0.7584 0.6402 0.063 Uiso 1 1 calc R . . H18B H 0.3176 0.6970 0.6451 0.063 Uiso 1 1 calc R . . H18C H 0.3473 0.8123 0.6786 0.063 Uiso 1 1 calc R . . C19 C 0.2130(5) 1.4164(4) 0.5059(3) 0.0511(13) Uani 1 1 d . . . C20 C 0.2096(6) 1.4974(5) 0.5624(3) 0.0685(17) Uani 1 1 d . . . H20A H 0.1318 1.5377 0.5444 0.082 Uiso 1 1 calc R . . H20B H 0.2813 1.5447 0.5710 0.082 Uiso 1 1 calc R . . H20C H 0.2136 1.4625 0.6084 0.082 Uiso 1 1 calc R . . C21 C 0.4514(6) 0.6163(6) 0.3682(4) 0.080(2) Uani 1 1 d . . . C22 C 0.4171(6) 0.6354(5) 0.4333(3) 0.0654(17) Uani 1 1 d . . . H22A H 0.3688 0.5759 0.4418 0.079 Uiso 1 1 calc R . . H22B H 0.3663 0.6990 0.4265 0.079 Uiso 1 1 calc R . . H22C H 0.4930 0.6441 0.4756 0.079 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 Mn1 0.0359(4) 0.0474(5) 0.0368(4) 0.0019(3) 0.0184(3) 0.0009(3) Mn2 0.0417(4) 0.0452(5) 0.0422(4) 0.0026(3) 0.0224(4) -0.0002(3) O1 0.045(2) 0.049(2) 0.0425(18) 0.0011(16) 0.0262(16) -0.0009(16) O2 0.073(3) 0.042(2) 0.066(2) 0.0041(18) 0.040(2) -0.0087(19) O3 0.0393(19) 0.051(2) 0.0379(18) 0.0066(16) 0.0180(15) 0.0001(15) O4 0.043(2) 0.054(2) 0.0364(18) 0.0054(16) 0.0203(16) 0.0048(16) O5 0.0387(19) 0.069(2) 0.044(2) 0.0033(18) 0.0223(16) -0.0004(17) O6 0.061(2) 0.040(2) 0.066(2) -0.0045(18) 0.027(2) -0.0017(18) O7 0.057(3) 0.073(3) 0.065(3) -0.009(2) 0.025(2) -0.016(2) N1 0.035(2) 0.047(2) 0.036(2) 0.0006(19) 0.0147(18) 0.0068(18) N2 0.033(2) 0.048(2) 0.036(2) 0.0062(19) 0.0131(18) 0.0022(18) N3 0.043(2) 0.041(2) 0.043(2) 0.0051(19) 0.022(2) 0.0003(18) N4 0.047(3) 0.043(2) 0.046(2) 0.007(2) 0.024(2) -0.0027(19) N5 0.036(2) 0.047(2) 0.044(2) 0.0015(19) 0.0206(19) -0.0030(18) N6 0.031(2) 0.041(2) 0.042(2) 0.0000(18) 0.0174(18) -0.0005(17) N7 0.034(2) 0.043(2) 0.038(2) -0.0006(18) 0.0170(18) 0.0042(17) N8 0.036(2) 0.057(3) 0.044(2) 0.000(2) 0.011(2) 0.002(2) N9 0.120(7) 0.216(10) 0.083(5) -0.034(6) 0.047(5) 0.015(6) C1 0.046(3) 0.055(3) 0.037(3) 0.001(2) 0.018(2) 0.002(2) C2 0.045(3) 0.055(3) 0.051(3) 0.007(3) 0.010(3) 0.001(3) C3 0.042(3) 0.047(3) 0.045(3) -0.005(2) 0.007(2) 0.001(2) C4 0.046(3) 0.051(3) 0.039(3) -0.006(2) 0.019(2) 0.004(2) C5 0.035(3) 0.051(3) 0.037(3) 0.002(2) 0.014(2) 0.004(2) C6 0.041(3) 0.052(3) 0.041(3) -0.003(2) 0.021(2) 0.001(2) C7 0.035(3) 0.047(3) 0.039(3) 0.002(2) 0.014(2) 0.001(2) C8 0.040(3) 0.049(3) 0.038(3) 0.005(2) 0.019(2) 0.002(2) C9 0.059(4) 0.057(3) 0.051(3) 0.010(3) 0.031(3) -0.003(3) C10 0.036(3) 0.064(4) 0.058(3) 0.004(3) 0.024(3) -0.003(3) C11 0.035(3) 0.075(4) 0.064(4) 0.010(3) 0.020(3) 0.006(3) C12 0.037(3) 0.074(4) 0.056(3) 0.007(3) 0.014(3) 0.005(3) C13 0.040(3) 0.049(3) 0.046(3) 0.003(2) 0.017(2) 0.002(2) C14 0.033(2) 0.038(3) 0.042(3) -0.005(2) 0.017(2) -0.001(2) C15 0.038(3) 0.031(2) 0.035(2) -0.003(2) 0.018(2) -0.001(2) C16 0.043(3) 0.034(2) 0.035(2) -0.008(2) 0.015(2) -0.003(2) C17 0.040(3) 0.047(3) 0.033(2) 0.001(2) 0.013(2) 0.004(2) C18 0.043(3) 0.062(4) 0.048(3) 0.003(3) 0.011(3) 0.010(3) C19 0.058(4) 0.049(3) 0.048(3) 0.004(3) 0.019(3) -0.002(3) C20 0.078(5) 0.058(4) 0.070(4) -0.008(3) 0.025(4) -0.007(3) C21 0.057(4) 0.107(6) 0.073(5) -0.014(4) 0.018(4) -0.002(4) C22 0.055(4) 0.074(4) 0.072(4) -0.006(3) 0.028(3) -0.006(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 O5 1.848(3) . ? Mn1 N7 1.922(4) . ? Mn1 O3 1.991(3) . ? Mn1 N2 2.098(4) . ? Mn1 O1 2.177(3) . ? Mn1 N1 2.300(4) . ? Mn2 O6 2.104(4) . ? Mn2 N6 2.131(4) 3_576 ? Mn2 O1 2.178(3) . ? Mn2 N4 2.260(4) . ? Mn2 O4 2.360(3) 3_576 ? Mn2 N5 2.364(4) 3_576 ? O1 C7 1.311(5) . ? O2 N4 1.373(5) . ? O2 H2W 0.9889 . ? O3 C15 1.302(5) . ? O4 C16 1.259(5) . ? O4 Mn2 2.360(3) 3_576 ? O5 N8 1.371(5) . ? O6 C19 1.250(6) . ? O7 C19 1.249(6) . ? N1 C1 1.330(6) . ? N1 C5 1.361(6) . ? N2 C6 1.285(6) . ? N2 N3 1.391(5) . ? N3 C7 1.306(6) . ? N4 C8 1.282(6) . ? N5 C10 1.328(6) . ? N5 C14 1.351(6) . ? N5 Mn2 2.364(4) 3_576 ? N6 C15 1.292(6) . ? N6 N7 1.389(5) . ? N6 Mn2 2.131(4) 3_576 ? N7 C16 1.333(6) . ? N8 C17 1.277(6) . ? N9 C21 1.131(8) . ? C1 C2 1.383(7) . ? C1 H1 0.9500 . ? C2 C3 1.378(7) . ? C2 H2 0.9500 . ? C3 C4 1.371(7) . ? C3 H3 0.9500 . ? C4 C5 1.383(7) . ? C4 H4 0.9500 . ? C5 C6 1.454(7) . ? C6 H6 0.9500 . ? C7 C8 1.469(7) . ? C8 C9 1.501(6) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 C11 1.387(7) . ? C10 H10 0.9500 . ? C11 C12 1.386(7) . ? C11 H11 0.9500 . ? C12 C13 1.381(7) . ? C12 H12 0.9500 . ? C13 C14 1.368(7) . ? C13 H13 0.9500 . ? C14 C15 1.485(6) . ? C16 C17 1.481(6) . ? C17 C18 1.501(7) . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? C19 C20 1.511(8) . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 0.9800 . ? C21 C22 1.446(9) . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? 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 O5 Mn1 N7 87.55(15) . . ? O5 Mn1 O3 168.27(13) . . ? N7 Mn1 O3 81.32(14) . . ? O5 Mn1 N2 90.51(14) . . ? N7 Mn1 N2 169.06(16) . . ? O3 Mn1 N2 101.11(13) . . ? O5 Mn1 O1 93.68(14) . . ? N7 Mn1 O1 118.58(14) . . ? O3 Mn1 O1 88.44(13) . . ? N2 Mn1 O1 72.28(14) . . ? O5 Mn1 N1 94.11(15) . . ? N7 Mn1 N1 96.28(15) . . ? O3 Mn1 N1 90.79(14) . . ? N2 Mn1 N1 73.12(15) . . ? O1 Mn1 N1 144.55(12) . . ? O6 Mn2 N6 92.67(14) . 3_576 ? O6 Mn2 O1 168.73(13) . . ? N6 Mn2 O1 98.21(13) 3_576 . ? O6 Mn2 N4 98.37(15) . . ? N6 Mn2 N4 167.87(15) 3_576 . ? O1 Mn2 N4 71.06(13) . . ? O6 Mn2 O4 86.80(14) . 3_576 ? N6 Mn2 O4 69.60(13) 3_576 3_576 ? O1 Mn2 O4 94.24(12) . 3_576 ? N4 Mn2 O4 115.81(13) . 3_576 ? O6 Mn2 N5 97.27(15) . 3_576 ? N6 Mn2 N5 70.41(14) 3_576 3_576 ? O1 Mn2 N5 89.17(13) . 3_576 ? N4 Mn2 N5 103.05(14) . 3_576 ? O4 Mn2 N5 139.95(12) 3_576 3_576 ? C7 O1 Mn1 112.3(3) . . ? C7 O1 Mn2 118.8(3) . . ? Mn1 O1 Mn2 127.84(14) . . ? N4 O2 H2W 105.7 . . ? C15 O3 Mn1 109.6(3) . . ? C16 O4 Mn2 112.9(3) . 3_576 ? N8 O5 Mn1 132.9(3) . . ? C19 O6 Mn2 129.2(4) . . ? C1 N1 C5 118.1(4) . . ? C1 N1 Mn1 128.6(3) . . ? C5 N1 Mn1 112.9(3) . . ? C6 N2 N3 118.4(4) . . ? C6 N2 Mn1 121.3(3) . . ? N3 N2 Mn1 120.2(3) . . ? C7 N3 N2 109.1(4) . . ? C8 N4 O2 114.6(4) . . ? C8 N4 Mn2 118.7(3) . . ? O2 N4 Mn2 126.0(3) . . ? C10 N5 C14 117.2(4) . . ? C10 N5 Mn2 128.3(3) . 3_576 ? C14 N5 Mn2 114.6(3) . 3_576 ? C15 N6 N7 113.5(4) . . ? C15 N6 Mn2 123.1(3) . 3_576 ? N7 N6 Mn2 120.7(3) . 3_576 ? C16 N7 N6 113.5(4) . . ? C16 N7 Mn1 132.3(3) . . ? N6 N7 Mn1 113.1(3) . . ? C17 N8 O5 121.2(4) . . ? N1 C1 C2 122.2(4) . . ? N1 C1 H1 118.9 . . ? C2 C1 H1 118.9 . . ? C3 C2 C1 119.5(5) . . ? C3 C2 H2 120.3 . . ? C1 C2 H2 120.3 . . ? C4 C3 C2 118.9(5) . . ? C4 C3 H3 120.5 . . ? C2 C3 H3 120.5 . . ? C3 C4 C5 119.0(4) . . ? C3 C4 H4 120.5 . . ? C5 C4 H4 120.5 . . ? N1 C5 C4 122.1(5) . . ? N1 C5 C6 114.7(4) . . ? C4 C5 C6 123.2(4) . . ? N2 C6 C5 117.8(4) . . ? N2 C6 H6 121.1 . . ? C5 C6 H6 121.1 . . ? N3 C7 O1 124.9(4) . . ? N3 C7 C8 118.0(4) . . ? O1 C7 C8 117.1(4) . . ? N4 C8 C7 113.4(4) . . ? N4 C8 C9 124.6(5) . . ? C7 C8 C9 122.0(4) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? N5 C10 C11 122.4(5) . . ? N5 C10 H10 118.8 . . ? C11 C10 H10 118.8 . . ? C12 C11 C10 119.6(5) . . ? C12 C11 H11 120.2 . . ? C10 C11 H11 120.2 . . ? C13 C12 C11 118.3(5) . . ? C13 C12 H12 120.9 . . ? C11 C12 H12 120.9 . . ? C14 C13 C12 118.3(5) . . ? C14 C13 H13 120.9 . . ? C12 C13 H13 120.9 . . ? N5 C14 C13 124.2(4) . . ? N5 C14 C15 113.6(4) . . ? C13 C14 C15 122.2(4) . . ? N6 C15 O3 122.5(4) . . ? N6 C15 C14 116.0(4) . . ? O3 C15 C14 121.5(4) . . ? O4 C16 N7 122.4(4) . . ? O4 C16 C17 121.1(4) . . ? N7 C16 C17 116.5(4) . . ? N8 C17 C16 127.8(4) . . ? N8 C17 C18 115.3(4) . . ? C16 C17 C18 116.9(4) . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? O7 C19 O6 124.1(5) . . ? O7 C19 C20 118.0(5) . . ? O6 C19 C20 117.9(5) . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? N9 C21 C22 178.5(10) . . ? C21 C22 H22A 109.5 . . ? C21 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C21 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 25.50 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.422 _refine_diff_density_min -0.456 _refine_diff_density_rms 0.077