# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 186/1596 data_NL9901 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16.50 H9 N2 F4 S2 Cl I2 Co' _chemical_formula_weight 723.56 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0171 0.0103 '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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'I' 'I' -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Co' 'Co' 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 5.988(2) _cell_length_b 16.777(3) _cell_length_c 23.539(3) _cell_angle_alpha 90.00 _cell_angle_beta 96.29(2) _cell_angle_gamma 90.00 _cell_volume 2350.6(8) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 22 _cell_measurement_theta_min 2.90 _cell_measurement_theta_max 12.45 _exptl_crystal_description 'platy prisms' _exptl_crystal_colour Blue _exptl_crystal_size_max 0.90 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.045 _exptl_crystal_density_method ? _exptl_crystal_F_000 1360 _exptl_absorpt_coefficient_mu 3.685 _exptl_absorpt_correction_type Ellipsoidal _exptl_absorpt_correction_T_min 0.3423 _exptl_absorpt_correction_T_max 0.4271 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 8.02 _diffrn_reflns_number 4546 _diffrn_reflns_av_R_equivalents 0.0287 _diffrn_reflns_av_sigmaI/netI 0.0600 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 2.12 _diffrn_reflns_theta_max 25.00 _reflns_number_total 4123 _reflns_number_observed 2906 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 352 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0815P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3771 _refine_ls_number_parameters 271 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0867 _refine_ls_R_factor_obs 0.0559 _refine_ls_wR_factor_all 0.1697 _refine_ls_wR_factor_obs 0.1354 _refine_ls_goodness_of_fit_all 1.040 _refine_ls_goodness_of_fit_obs 1.097 _refine_ls_restrained_S_all 1.152 _refine_ls_restrained_S_obs 1.097 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Co Co 0.3220(2) 0.28460(7) 0.05106(5) 0.0381(3) Uani 1 d . . I1 I 0.50192(13) 0.20175(4) 0.13641(3) 0.0585(2) Uani 1 d . . I2 I 0.56607(13) 0.35246(5) -0.01840(3) 0.0592(2) Uani 1 d . . N1 N 0.1365(13) 0.3696(4) 0.0861(3) 0.040(2) Uani 1 d . . C2 C 0.0096(18) 0.3502(6) 0.1287(4) 0.049(2) Uani 1 d . . H2A H 0.0114(18) 0.2977(6) 0.1415(4) 0.059 Uiso 1 calc R . C3 C -0.1204(17) 0.4043(6) 0.1535(4) 0.046(2) Uani 1 d . . H3A H -0.2063(17) 0.3884(6) 0.1821(4) 0.056 Uiso 1 calc R . C4 C -0.1232(16) 0.4812(6) 0.1360(3) 0.045(2) Uani 1 d . . C5 C 0.0003(20) 0.5035(6) 0.0913(4) 0.054(2) Uani 1 d . . H5A H -0.0026(20) 0.5557(6) 0.0779(4) 0.065 Uiso 1 calc R . C6 C 0.1254(17) 0.4464(6) 0.0678(4) 0.047(2) Uani 1 d . . H6A H 0.2065(17) 0.4608(6) 0.0379(4) 0.056 Uiso 1 calc R . S7 S -0.2840(6) 0.5574(2) 0.16429(11) 0.0693(9) Uani 1 d . . C8 C -0.3011(18) 0.5222(6) 0.2350(3) 0.047(2) Uani 1 d . . C9 C -0.1326(18) 0.5390(6) 0.2772(4) 0.048(2) Uani 1 d . . F9 F 0.0536(13) 0.5762(5) 0.2667(4) 0.084(2) Uani 1 d . . C10 C -0.1537(18) 0.5189(6) 0.3339(4) 0.049(2) Uani 1 d . . F10 F 0.0102(14) 0.5376(5) 0.3740(3) 0.081(2) Uani 1 d . . C11 C -0.3439(17) 0.4816(6) 0.3492(4) 0.045(2) Uani 1 d . . C12 C -0.5104(17) 0.4631(7) 0.3049(5) 0.054(2) Uani 1 d . . F12 F -0.6984(13) 0.4282(6) 0.3173(4) 0.089(2) Uani 1 d . . C13 C -0.4871(19) 0.4843(7) 0.2496(4) 0.054(2) Uani 1 d . . F13 F -0.6537(14) 0.4642(6) 0.2090(3) 0.094(3) Uani 1 d . . S14 S -0.3982(6) 0.4670(2) 0.41996(12) 0.0818(12) Uani 1 d . . C15 C -0.1924(17) 0.4004(6) 0.4492(4) 0.045(2) Uani 1 d . . C16 C -0.0340(20) 0.3616(7) 0.4206(4) 0.056(3) Uani 1 d . . H16A H -0.0286(20) 0.3707(7) 0.3818(4) 0.068 Uiso 1 calc R . C17 C 0.1148(19) 0.3097(6) 0.4494(4) 0.052(2) Uani 1 d . . H17A H 0.2233(19) 0.2854(6) 0.4298(4) 0.062 Uiso 1 calc R . N18 N 0.1090(13) 0.2927(5) 0.5051(3) 0.042(2) Uani 1 d . . C19 C -0.0466(19) 0.3305(6) 0.5321(4) 0.052(2) Uani 1 d . . H19A H -0.0512(19) 0.3202(6) 0.5707(4) 0.062 Uiso 1 calc R . C20 C -0.1956(19) 0.3822(6) 0.5064(4) 0.053(3) Uani 1 d . . H20A H -0.3015(19) 0.4058(6) 0.5271(4) 0.064 Uiso 1 calc R . C30 C 0.2547(56) 0.7144(16) 0.1943(16) 0.090(9) Uani 0.50 d P . H30A H 0.2958(56) 0.6719(16) 0.2214(16) 0.108 Uiso 0.50 calc PR . H30B H 0.1950(56) 0.6897(16) 0.1586(16) 0.108 Uiso 0.50 calc PR . Cl1 Cl 0.0461(16) 0.7688(6) 0.2191(3) 0.097(2) Uani 0.50 d P . Cl2 Cl 0.4782(19) 0.7617(6) 0.1836(6) 0.120(3) Uani 0.50 d P . 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 Co 0.0437(6) 0.0391(6) 0.0314(5) 0.0003(4) 0.0039(4) -0.0077(5) I1 0.0633(4) 0.0604(4) 0.0502(4) 0.0123(3) -0.0010(3) -0.0069(3) I2 0.0593(4) 0.0665(4) 0.0532(4) 0.0132(3) 0.0131(3) -0.0111(4) N1 0.046(4) 0.036(4) 0.036(3) -0.002(3) 0.006(3) -0.004(3) C2 0.062(6) 0.041(5) 0.045(5) -0.003(4) 0.012(4) -0.005(5) C3 0.052(5) 0.053(5) 0.035(4) 0.001(4) 0.011(4) -0.006(4) C4 0.049(5) 0.057(5) 0.027(4) -0.008(4) -0.004(4) 0.010(4) C5 0.076(7) 0.051(5) 0.035(4) 0.012(4) 0.004(4) 0.009(5) C6 0.054(5) 0.048(5) 0.039(4) 0.002(4) 0.005(4) -0.005(4) S7 0.106(2) 0.069(2) 0.0346(11) 0.0124(11) 0.0151(14) 0.039(2) C8 0.065(6) 0.051(5) 0.026(4) 0.003(4) 0.003(4) 0.020(5) C9 0.057(6) 0.042(5) 0.045(5) 0.004(4) 0.010(4) 0.004(4) F9 0.065(4) 0.091(5) 0.094(5) 0.030(4) 0.001(4) -0.016(4) C10 0.059(6) 0.053(5) 0.032(4) -0.003(4) -0.005(4) 0.014(5) F10 0.091(5) 0.088(5) 0.055(4) -0.009(3) -0.029(4) 0.001(4) C11 0.055(5) 0.053(5) 0.030(4) 0.009(4) 0.008(4) 0.022(4) C12 0.042(5) 0.059(6) 0.061(6) 0.009(5) 0.012(4) 0.011(5) F12 0.059(4) 0.104(6) 0.104(6) 0.024(5) 0.011(4) -0.012(4) C13 0.056(6) 0.061(6) 0.043(5) -0.004(4) -0.011(4) 0.003(5) F13 0.073(5) 0.139(8) 0.063(4) -0.011(5) -0.026(4) -0.011(5) S14 0.098(2) 0.110(3) 0.0420(13) 0.0267(15) 0.0275(14) 0.069(2) C15 0.055(5) 0.048(5) 0.035(4) 0.006(4) 0.013(4) 0.016(4) C16 0.074(7) 0.062(6) 0.036(4) 0.013(4) 0.021(5) 0.025(5) C17 0.064(6) 0.057(6) 0.037(5) 0.012(4) 0.019(4) 0.025(5) N18 0.050(4) 0.047(4) 0.029(3) 0.005(3) 0.008(3) 0.004(4) C19 0.071(7) 0.060(6) 0.026(4) 0.004(4) 0.013(4) 0.014(5) C20 0.071(7) 0.064(6) 0.028(4) 0.011(4) 0.020(4) 0.030(5) C30 0.104(22) 0.052(14) 0.119(25) 0.028(15) 0.028(19) 0.015(14) Cl1 0.109(6) 0.112(6) 0.074(4) 0.021(4) 0.025(4) 0.029(5) Cl2 0.122(8) 0.084(5) 0.161(9) 0.003(6) 0.044(7) 0.003(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Co N1 2.037(7) . ? Co N18 2.044(8) 4_565 ? Co I2 2.5747(13) . ? Co I1 2.5796(14) . ? N1 C6 1.357(12) . ? N1 C2 1.362(12) . ? C2 C3 1.368(14) . ? C3 C4 1.354(14) . ? C4 C5 1.402(14) . ? C4 S7 1.774(9) . ? C5 C6 1.370(14) . ? S7 C8 1.779(8) . ? C8 C13 1.36(2) . ? C8 C9 1.366(14) . ? C9 F9 1.325(12) . ? C9 C10 1.395(13) . ? C10 F10 1.323(12) . ? C10 C11 1.381(15) . ? C11 C12 1.396(15) . ? C11 S14 1.750(8) . ? C12 F12 1.329(13) . ? C12 C13 1.373(15) . ? C13 F13 1.346(12) . ? S14 C15 1.747(10) . ? C15 C20 1.384(12) . ? C15 C16 1.385(13) . ? C16 C17 1.372(14) . ? C17 N18 1.345(11) . ? N18 C19 1.342(12) . ? N18 Co 2.044(8) 4_566 ? C19 C20 1.339(14) . ? C30 Cl2 1.60(3) . ? C30 Cl1 1.70(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Co N18 108.8(3) . 4_565 ? N1 Co I2 108.7(2) . . ? N18 Co I2 108.0(2) 4_565 . ? N1 Co I1 105.2(2) . . ? N18 Co I1 104.7(2) 4_565 . ? I2 Co I1 121.01(6) . . ? C6 N1 C2 116.7(8) . . ? C6 N1 Co 123.1(6) . . ? C2 N1 Co 120.2(6) . . ? N1 C2 C3 123.0(9) . . ? C4 C3 C2 119.4(9) . . ? C3 C4 C5 119.5(9) . . ? C3 C4 S7 124.2(8) . . ? C5 C4 S7 116.3(8) . . ? C6 C5 C4 118.2(9) . . ? N1 C6 C5 123.1(9) . . ? C4 S7 C8 101.6(4) . . ? C13 C8 C9 118.2(8) . . ? C13 C8 S7 121.6(8) . . ? C9 C8 S7 119.9(8) . . ? F9 C9 C8 122.0(9) . . ? F9 C9 C10 117.4(10) . . ? C8 C9 C10 120.6(10) . . ? F10 C10 C11 119.4(9) . . ? F10 C10 C9 119.1(10) . . ? C11 C10 C9 121.5(9) . . ? C10 C11 C12 116.7(8) . . ? C10 C11 S14 123.8(8) . . ? C12 C11 S14 119.2(8) . . ? F12 C12 C13 120.0(10) . . ? F12 C12 C11 119.2(10) . . ? C13 C12 C11 120.8(10) . . ? F13 C13 C8 120.1(10) . . ? F13 C13 C12 117.7(11) . . ? C8 C13 C12 122.2(10) . . ? C15 S14 C11 105.5(4) . . ? C20 C15 C16 116.9(9) . . ? C20 C15 S14 116.1(7) . . ? C16 C15 S14 126.9(7) . . ? C17 C16 C15 120.1(8) . . ? N18 C17 C16 122.1(9) . . ? C19 N18 C17 117.0(8) . . ? C19 N18 Co 118.3(6) . 4_566 ? C17 N18 Co 124.7(6) . 4_566 ? C20 C19 N18 123.7(8) . . ? C19 C20 C15 120.2(8) . . ? Cl2 C30 Cl1 116.5(18) . . ? _refine_diff_density_max 1.250 _refine_diff_density_min -0.628 _refine_diff_density_rms 0.155 data_NL9810 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C38 H28 N6 O2 F8 S6 Mn' _chemical_formula_weight 999.96 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Mn' 'Mn' -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 15.1019(9) _cell_length_b 7.7834(8) _cell_length_c 18.025(3) _cell_angle_alpha 90.00 _cell_angle_beta 101.445(7) _cell_angle_gamma 90.00 _cell_volume 2076.6(4) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 21 _cell_measurement_theta_min 10.99 _cell_measurement_theta_max 22.60 _exptl_crystal_description plates _exptl_crystal_colour Clear _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.599 _exptl_crystal_density_method ? _exptl_crystal_F_000 1014 _exptl_absorpt_coefficient_mu 6.114 _exptl_absorpt_correction_type ellipsoidal _exptl_absorpt_correction_T_min 0.1312 _exptl_absorpt_correction_T_max 0.3144 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3210 _diffrn_reflns_av_R_equivalents 0.0306 _diffrn_reflns_av_sigmaI/netI 0.0619 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.99 _diffrn_reflns_theta_max 60.00 _reflns_number_total 3079 _reflns_number_observed 2104 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.1091P)^2^+0.2734P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0004(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 3079 _refine_ls_number_parameters 301 _refine_ls_number_restraints 4 _refine_ls_R_factor_all 0.1036 _refine_ls_R_factor_obs 0.0697 _refine_ls_wR_factor_all 0.1966 _refine_ls_wR_factor_obs 0.1708 _refine_ls_goodness_of_fit_all 1.075 _refine_ls_goodness_of_fit_obs 1.153 _refine_ls_restrained_S_all 1.077 _refine_ls_restrained_S_obs 1.155 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Mn Mn 0.5000 0.0000 0.0000 0.0425(4) Uani 1 d S . N1 N 0.6432(3) 0.0261(7) -0.0270(3) 0.0456(12) Uani 1 d . . C2 C 0.6519(4) 0.0811(10) -0.0943(3) 0.0498(15) Uani 1 d . . H2A H 0.5999(4) 0.1179(10) -0.1272(3) 0.060 Uiso 1 calc R . C3 C 0.7318(4) 0.0883(10) -0.1197(3) 0.0482(15) Uani 1 d . . H3A H 0.7335(4) 0.1290(10) -0.1679(3) 0.058 Uiso 1 calc R . C4 C 0.8107(4) 0.0326(8) -0.0711(3) 0.0429(14) Uani 1 d . . C5 C 0.8036(4) -0.0257(9) -0.0001(3) 0.0461(14) Uani 1 d . . H5A H 0.8547(4) -0.0632(9) 0.0337(3) 0.055 Uiso 1 calc R . C6 C 0.7209(4) -0.0279(9) 0.0201(3) 0.0476(15) Uani 1 d . . H6A H 0.7173(4) -0.0679(9) 0.0681(3) 0.057 Uiso 1 calc R . S7 S 0.91882(11) 0.0365(4) -0.09237(9) 0.0768(8) Uani 1 d . . C8 C 0.8990(4) 0.0523(10) -0.1921(3) 0.051(2) Uani 1 d . . C9 C 0.8969(4) 0.2092(11) -0.2280(4) 0.056(2) Uani 1 d . . F9 F 0.8980(4) 0.3549(7) -0.1888(3) 0.0804(14) Uani 1 d . . C10 C 0.8939(4) 0.2199(9) -0.3046(4) 0.051(2) Uani 1 d . . F10 F 0.8938(4) 0.3768(6) -0.3355(3) 0.0756(13) Uani 1 d . . C11 C 0.8948(4) 0.0748(9) -0.3491(3) 0.0460(14) Uani 1 d . . C12 C 0.8937(4) -0.0822(10) -0.3126(4) 0.0510(15) Uani 1 d . . F12 F 0.8937(4) -0.2279(6) -0.3521(3) 0.0802(14) Uani 1 d . . C13 C 0.8955(4) -0.0917(10) -0.2366(4) 0.056(2) Uani 1 d . . F13 F 0.8967(4) -0.2490(7) -0.2051(3) 0.0801(14) Uani 1 d . . S14 S 0.90599(12) 0.0899(3) -0.44412(9) 0.0648(6) Uani 1 d . . C15 C 0.7983(4) 0.0244(9) -0.4930(3) 0.0463(14) Uani 1 d . . C16 C 0.7897(5) -0.0487(9) -0.5630(4) 0.058(2) Uani 1 d . . H16A H 0.8402(5) -0.0652(9) -0.5845(4) 0.069 Uiso 1 calc R . C17 C 0.7055(7) -0.0977(10) -0.6014(4) 0.069(2) Uani 1 d . . H17A H 0.7009(7) -0.1486(10) -0.6486(4) 0.083 Uiso 1 calc R . N18 N 0.6289(5) -0.0761(9) -0.5744(3) 0.066(2) Uani 1 d . . C19 C 0.6370(5) -0.0020(11) -0.5073(4) 0.059(2) Uani 1 d . . H19A H 0.5852(5) 0.0141(11) -0.4874(4) 0.071 Uiso 1 calc R . C20 C 0.7204(5) 0.0538(10) -0.4646(4) 0.053(2) Uani 1 d . . H20A H 0.7235(5) 0.1090(10) -0.4184(4) 0.064 Uiso 1 calc R . N21 N 0.4492(4) 0.1910(8) -0.0838(3) 0.0549(14) Uani 1 d . . C22 C 0.4014(5) 0.2532(9) -0.1345(4) 0.0501(15) Uani 1 d . . S23 S 0.3312(2) 0.3345(3) -0.20609(11) 0.0827(7) Uani 1 d . . O30 O 0.5211(4) 0.2011(7) 0.0920(3) 0.0592(12) Uani 1 d D . H30A H 0.4816(52) 0.2848(90) 0.0891(51) 0.083(30) Uiso 1 d D . C31 C 0.5901(9) 0.2063(22) 0.1589(7) 0.065(4) Uani 0.65 d PD 1 H31A H 0.6143(9) 0.3218(22) 0.1669(7) 0.078 Uiso 0.65 calc PR 1 H31B H 0.6391(9) 0.1295(22) 0.1536(7) 0.078 Uiso 0.65 calc PR 1 C32 C 0.5510(11) 0.1536(23) 0.2232(8) 0.083(4) Uani 0.65 d PD 1 H32A H 0.5968(11) 0.1566(23) 0.2685(8) 0.124 Uiso 0.65 calc PR 1 H32B H 0.5277(11) 0.0390(23) 0.2150(8) 0.124 Uiso 0.65 calc PR 1 H32C H 0.5030(11) 0.2307(23) 0.2283(8) 0.124 Uiso 0.65 calc PR 1 C31' C 0.5489(17) 0.1852(41) 0.1729(7) 0.063(7) Uani 0.35 d PD 2 H31C H 0.5174(17) 0.0880(41) 0.1893(7) 0.075 Uiso 0.35 calc PR 2 H31D H 0.5294(17) 0.2872(41) 0.1960(7) 0.075 Uiso 0.35 calc PR 2 C32' C 0.6466(15) 0.1623(33) 0.2020(12) 0.072(7) Uani 0.35 d PD 2 H32D H 0.6578(15) 0.1531(33) 0.2562(12) 0.108 Uiso 0.35 calc PR 2 H32E H 0.6787(15) 0.2594(33) 0.1878(12) 0.108 Uiso 0.35 calc PR 2 H32F H 0.6668(15) 0.0596(33) 0.1810(12) 0.108 Uiso 0.35 calc PR 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 Mn 0.0330(6) 0.0548(8) 0.0396(7) 0.0066(6) 0.0070(5) 0.0041(6) N1 0.037(2) 0.058(3) 0.041(2) 0.003(2) 0.007(2) 0.002(2) C2 0.032(3) 0.070(4) 0.046(3) 0.004(3) 0.004(2) 0.003(3) C3 0.035(3) 0.070(4) 0.037(3) 0.015(3) 0.001(2) 0.001(3) C4 0.033(3) 0.060(4) 0.035(3) -0.002(2) 0.003(2) -0.001(3) C5 0.039(3) 0.062(4) 0.035(3) -0.002(3) 0.002(2) 0.004(3) C6 0.034(3) 0.070(5) 0.038(3) 0.008(3) 0.004(2) -0.004(3) S7 0.0319(7) 0.161(2) 0.0363(8) 0.0076(10) 0.0028(6) -0.0011(10) C8 0.033(3) 0.077(5) 0.040(3) 0.003(3) 0.005(2) -0.003(3) C9 0.043(3) 0.074(5) 0.049(4) -0.020(3) 0.006(3) 0.002(3) F9 0.083(3) 0.084(3) 0.074(3) -0.027(2) 0.014(2) 0.000(3) C10 0.040(3) 0.061(4) 0.050(3) 0.005(3) 0.005(3) -0.003(3) F10 0.081(3) 0.063(3) 0.079(3) 0.014(2) 0.009(2) -0.002(2) C11 0.034(3) 0.065(4) 0.038(3) -0.002(3) 0.006(2) -0.003(3) C12 0.044(3) 0.059(4) 0.049(3) -0.009(3) 0.006(3) -0.001(3) F12 0.094(3) 0.071(3) 0.074(3) -0.020(2) 0.013(2) 0.000(3) C13 0.039(3) 0.070(5) 0.057(4) 0.018(4) 0.004(3) 0.000(3) F13 0.079(3) 0.077(3) 0.082(3) 0.029(2) 0.010(2) 0.003(2) S14 0.0447(8) 0.110(2) 0.0417(8) 0.0002(9) 0.0131(6) -0.0077(9) C15 0.043(3) 0.059(4) 0.036(3) 0.004(3) 0.006(2) 0.001(3) C16 0.073(4) 0.056(4) 0.046(3) 0.001(3) 0.015(3) 0.000(3) C17 0.098(6) 0.054(4) 0.049(4) -0.008(3) 0.001(4) -0.003(4) N18 0.072(4) 0.061(4) 0.057(3) 0.005(3) -0.006(3) -0.011(3) C19 0.050(4) 0.068(4) 0.057(4) -0.001(3) 0.004(3) -0.006(3) C20 0.046(3) 0.062(4) 0.051(3) -0.006(3) 0.006(3) -0.002(3) N21 0.045(3) 0.064(4) 0.056(3) 0.008(3) 0.010(2) 0.008(3) C22 0.051(3) 0.053(4) 0.046(3) 0.002(3) 0.009(3) 0.006(3) S23 0.091(2) 0.093(2) 0.0537(10) 0.0024(10) -0.0099(10) 0.0327(13) O30 0.057(3) 0.065(3) 0.051(3) -0.003(2) -0.001(2) 0.007(2) C31 0.058(8) 0.090(10) 0.046(7) -0.009(6) 0.006(7) -0.005(8) C32 0.085(10) 0.103(11) 0.058(8) -0.016(7) 0.007(7) -0.011(8) C31' 0.050(14) 0.113(21) 0.021(12) -0.001(11) 0.000(9) 0.006(14) C32' 0.079(15) 0.075(15) 0.045(10) -0.007(10) -0.028(11) 0.001(12) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn N21 2.149(6) . ? Mn N21 2.149(6) 3_655 ? Mn O30 2.256(5) . ? Mn O30 2.256(5) 3_655 ? Mn N1 2.318(5) 3_655 ? Mn N1 2.318(5) . ? N1 C2 1.318(8) . ? N1 C6 1.371(8) . ? C2 C3 1.374(9) . ? C3 C4 1.400(8) . ? C4 C5 1.381(8) . ? C4 S7 1.750(6) . ? C5 C6 1.368(9) . ? S7 C8 1.767(6) . ? C8 C13 1.372(11) . ? C8 C9 1.380(11) . ? C9 F9 1.335(9) . ? C9 C10 1.375(9) . ? C10 F10 1.342(8) . ? C10 C11 1.386(10) . ? C11 C12 1.390(10) . ? C11 S14 1.759(6) . ? C12 F12 1.339(8) . ? C12 C13 1.367(9) . ? C13 F13 1.348(9) . ? S14 C15 1.765(6) . ? C15 C16 1.366(9) . ? C15 C20 1.391(9) . ? C16 C17 1.375(12) . ? C17 N18 1.350(12) . ? N18 C19 1.324(10) . ? C19 C20 1.409(10) . ? N21 C22 1.152(9) . ? C22 S23 1.628(6) . ? O30 C31 1.429(11) . ? O30 C31' 1.440(12) . ? C31 C32 1.46(2) . ? C31' C32' 1.48(2) . ? 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 N21 Mn N21 180.0 . 3_655 ? N21 Mn O30 90.9(2) . . ? N21 Mn O30 89.1(2) 3_655 . ? N21 Mn O30 89.1(2) . 3_655 ? N21 Mn O30 90.9(2) 3_655 3_655 ? O30 Mn O30 180.0 . 3_655 ? N21 Mn N1 89.4(2) . 3_655 ? N21 Mn N1 90.6(2) 3_655 3_655 ? O30 Mn N1 84.7(2) . 3_655 ? O30 Mn N1 95.3(2) 3_655 3_655 ? N21 Mn N1 90.6(2) . . ? N21 Mn N1 89.4(2) 3_655 . ? O30 Mn N1 95.3(2) . . ? O30 Mn N1 84.7(2) 3_655 . ? N1 Mn N1 180.0 3_655 . ? C2 N1 C6 116.2(5) . . ? C2 N1 Mn 119.3(4) . . ? C6 N1 Mn 124.3(4) . . ? N1 C2 C3 125.0(6) . . ? C2 C3 C4 118.3(5) . . ? C5 C4 C3 117.9(5) . . ? C5 C4 S7 117.1(4) . . ? C3 C4 S7 124.9(5) . . ? C6 C5 C4 119.6(5) . . ? C5 C6 N1 123.0(5) . . ? C4 S7 C8 104.3(3) . . ? C13 C8 C9 117.0(6) . . ? C13 C8 S7 121.1(6) . . ? C9 C8 S7 121.5(5) . . ? F9 C9 C10 118.4(7) . . ? F9 C9 C8 120.4(6) . . ? C10 C9 C8 121.2(7) . . ? F10 C10 C9 117.9(7) . . ? F10 C10 C11 120.1(6) . . ? C9 C10 C11 121.9(7) . . ? C10 C11 C12 116.2(6) . . ? C10 C11 S14 121.5(5) . . ? C12 C11 S14 122.1(5) . . ? F12 C12 C13 119.0(7) . . ? F12 C12 C11 119.5(6) . . ? C13 C12 C11 121.4(7) . . ? F13 C13 C12 117.8(7) . . ? F13 C13 C8 120.0(6) . . ? C12 C13 C8 122.2(7) . . ? C11 S14 C15 102.2(3) . . ? C16 C15 C20 118.5(6) . . ? C16 C15 S14 119.4(5) . . ? C20 C15 S14 122.1(5) . . ? C15 C16 C17 119.2(7) . . ? N18 C17 C16 123.8(7) . . ? C19 N18 C17 117.0(7) . . ? N18 C19 C20 122.9(7) . . ? C15 C20 C19 118.6(6) . . ? C22 N21 Mn 158.0(6) . . ? N21 C22 S23 177.7(7) . . ? C31 O30 Mn 127.8(7) . . ? C31' O30 Mn 130.9(13) . . ? O30 C31 C32 108.6(11) . . ? O30 C31' C32' 116.1(18) . . ? _refine_diff_density_max 0.623 _refine_diff_density_min -0.657 _refine_diff_density_rms 0.095 data_NL9802 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C36 H28 Br2 F8 Mn N4 O2 S4' _chemical_formula_weight 1043.62 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Mn' 'Mn' -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Br' 'Br' -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pna2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z+1/2' _cell_length_a 14.7441(10) _cell_length_b 9.6438(13) _cell_length_c 27.253(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3875.0(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 32 _cell_measurement_theta_min 9.20 _cell_measurement_theta_max 34.44 _exptl_crystal_description 'rhombic plates' _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.789 _exptl_crystal_density_method ? _exptl_crystal_F_000 2076 _exptl_absorpt_coefficient_mu 7.909 _exptl_absorpt_correction_type 'Lamina [0 0 1]' _exptl_absorpt_correction_T_min 0.3074 _exptl_absorpt_correction_T_max 0.7776 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2804 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0776 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 0 _diffrn_reflns_theta_min 3.24 _diffrn_reflns_theta_max 60.01 _reflns_number_total 2804 _reflns_number_observed 2144 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0820P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00031(7) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.00 _refine_ls_number_reflns 2804 _refine_ls_number_parameters 515 _refine_ls_number_restraints 7 _refine_ls_R_factor_all 0.0832 _refine_ls_R_factor_obs 0.0577 _refine_ls_wR_factor_all 0.1481 _refine_ls_wR_factor_obs 0.1306 _refine_ls_goodness_of_fit_all 1.052 _refine_ls_goodness_of_fit_obs 1.096 _refine_ls_restrained_S_all 1.053 _refine_ls_restrained_S_obs 1.097 _refine_ls_shift/esd_max -0.034 _refine_ls_shift/esd_mean 0.004 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Mn Mn 0.3994(2) 0.4999(3) 1.05182(12) 0.0272(5) Uani 1 d . . Br1 Br 0.54651(12) 0.4628(2) 0.99549(6) 0.0373(4) Uani 1 d . . Br2 Br 0.25220(12) 0.5384(2) 1.10766(6) 0.0366(4) Uani 1 d . . N1 N 0.4744(9) 0.4046(14) 1.1185(5) 0.027(3) Uani 1 d . . C2 C 0.4612(11) 0.4581(17) 1.1619(6) 0.030(3) Uani 1 d . . H2A H 0.4242(11) 0.5359(17) 1.1646(6) 0.036 Uiso 1 calc R . C3 C 0.5008(12) 0.4028(17) 1.2053(6) 0.031(4) Uani 1 d . . H3A H 0.4921(12) 0.4451(17) 1.2356(6) 0.037 Uiso 1 calc R . C4 C 0.5528(11) 0.2835(13) 1.2008(6) 0.023(3) Uani 1 d . . C5 C 0.5676(12) 0.2301(15) 1.1538(7) 0.028(4) Uani 1 d . . H5A H 0.6031(12) 0.1514(15) 1.1492(7) 0.034 Uiso 1 calc R . C6 C 0.5284(12) 0.2968(18) 1.1150(7) 0.033(4) Uani 1 d . . H6A H 0.5410(12) 0.2634(18) 1.0837(7) 0.040 Uiso 1 calc R . S7 S 0.6056(4) 0.2282(4) 1.2555(2) 0.0383(11) Uani 1 d . . C8 C 0.6315(11) 0.0498(17) 1.2442(6) 0.028(4) Uani 1 d . . F9 F 0.7890(8) 0.0991(11) 1.2385(4) 0.046(3) Uani 1 d . . C9 C 0.7204(13) 0.0111(19) 1.2416(7) 0.036(4) Uani 1 d . . F10 F 0.8294(7) -0.1680(12) 1.2376(5) 0.051(3) Uani 1 d . . C10 C 0.7393(12) -0.1313(21) 1.2408(6) 0.033(4) Uani 1 d . . C11 C 0.6752(13) -0.2306(18) 1.2439(6) 0.032(4) Uani 1 d . . F12 F 0.5197(9) -0.2796(13) 1.2489(5) 0.054(3) Uani 1 d . . C12 C 0.5863(16) -0.1858(22) 1.2445(6) 0.044(5) Uani 1 d . . F13 F 0.4769(7) -0.0108(12) 1.2466(5) 0.048(3) Uani 1 d . . C13 C 0.5656(14) -0.0481(22) 1.2449(6) 0.038(4) Uani 1 d . . S14 S 0.7058(5) -0.4080(5) 1.2545(2) 0.0480(14) Uani 1 d . . C15 C 0.7285(12) -0.4746(19) 1.1953(8) 0.038(4) Uani 1 d . . C16 C 0.6937(15) -0.4252(17) 1.1505(8) 0.044(5) Uani 1 d . . H16A H 0.6598(15) -0.3440(17) 1.1487(8) 0.052 Uiso 1 calc R . C17 C 0.7124(13) -0.5036(17) 1.1098(8) 0.039(4) Uani 1 d . . H17A H 0.6876(13) -0.4733(17) 1.0804(8) 0.046 Uiso 1 calc R . N18 N 0.7621(11) -0.6177(15) 1.1080(7) 0.043(4) Uani 1 d . . C19 C 0.7981(13) -0.6616(18) 1.1512(8) 0.043(5) Uani 1 d . . H19A H 0.8349(13) -0.7399(18) 1.1514(8) 0.052 Uiso 1 calc R . C20 C 0.7814(13) -0.5922(18) 1.1953(7) 0.037(4) Uani 1 d . . H20A H 0.8059(13) -0.6254(18) 1.2244(7) 0.044 Uiso 1 calc R . N21 N 0.3252(9) 0.5912(14) 0.9843(5) 0.027(3) Uani 1 d . . C22 C 0.2675(11) 0.7055(18) 0.9883(7) 0.031(4) Uani 1 d . . H22A H 0.2559(11) 0.7423(18) 1.0192(7) 0.038 Uiso 1 calc R . C23 C 0.2267(12) 0.7662(17) 0.9476(6) 0.027(4) Uani 1 d . . H23A H 0.1894(12) 0.8433(17) 0.9512(6) 0.032 Uiso 1 calc R . C24 C 0.2426(12) 0.7092(18) 0.9008(6) 0.029(4) Uani 1 d . . C25 C 0.2992(12) 0.5939(18) 0.8985(6) 0.030(4) Uani 1 d . . H25A H 0.3113(12) 0.5539(18) 0.8682(6) 0.036 Uiso 1 calc R . C26 C 0.3368(11) 0.5389(18) 0.9388(6) 0.031(4) Uani 1 d . . H26A H 0.3728(11) 0.4604(18) 0.9352(6) 0.038 Uiso 1 calc R . S27 S 0.1922(4) 0.7650(4) 0.8467(2) 0.0385(11) Uani 1 d . . C28 C 0.1611(11) 0.9374(18) 0.8579(6) 0.027(4) Uani 1 d . . C29 C 0.0727(12) 0.9875(17) 0.8584(7) 0.034(4) Uani 1 d . . F29 F 0.0066(7) 0.8883(13) 0.8555(6) 0.058(3) Uani 1 d . . F30 F -0.0359(7) 1.1544(12) 0.8603(6) 0.054(3) Uani 1 d . . C30 C 0.0510(12) 1.1209(22) 0.8608(7) 0.038(5) Uani 1 d . . C31 C 0.1156(14) 1.2279(20) 0.8609(7) 0.038(5) Uani 1 d . . F32 F 0.2721(9) 1.2759(12) 0.8642(6) 0.064(4) Uani 1 d . . C32 C 0.2036(13) 1.1807(19) 0.8617(8) 0.035(5) Uani 1 d . . F33 F 0.3157(7) 1.0082(12) 0.8603(5) 0.049(3) Uani 1 d . . C33 C 0.2274(12) 1.0432(20) 0.8612(6) 0.032(4) Uani 1 d . . S34 S 0.0874(5) 1.3994(5) 0.8528(2) 0.0507(14) Uani 1 d . . C35 C 0.0643(11) 1.4702(18) 0.9119(7) 0.031(4) Uani 1 d . . C36 C 0.1008(12) 1.4253(16) 0.9535(7) 0.032(4) Uani 1 d . . H36A H 0.1357(12) 1.3450(16) 0.9541(7) 0.038 Uiso 1 calc R . C37 C 0.0860(14) 1.5000(17) 0.9959(8) 0.045(5) Uani 1 d . . H37A H 0.1096(14) 1.4677(17) 1.0254(8) 0.054 Uiso 1 calc R . N38 N 0.0374(11) 1.6204(16) 0.9953(8) 0.049(4) Uani 1 d . . C39 C 0.0024(14) 1.6621(23) 0.9532(8) 0.049(6) Uani 1 d . . H39A H -0.0320(14) 1.7429(23) 0.9533(8) 0.059 Uiso 1 calc R . C40 C 0.0135(12) 1.5934(19) 0.9089(7) 0.038(4) Uani 1 d . . H40A H -0.0106(12) 1.6263(19) 0.8796(7) 0.046 Uiso 1 calc R . O50 O 0.3415(10) 0.2925(11) 1.0362(5) 0.041(3) Uani 1 d . . C50 C 0.3822(13) 0.1765(18) 1.0088(9) 0.048(6) Uani 1 d . . H50A H 0.4295(13) 0.2115(18) 0.9873(9) 0.058 Uiso 1 calc R . H50B H 0.4097(13) 0.1117(18) 1.0316(9) 0.058 Uiso 1 calc R . C51 C 0.3145(20) 0.1061(33) 0.9800(12) 0.091(10) Uani 1 d . . H51A H 0.3422(20) 0.0309(33) 0.9624(12) 0.136 Uiso 1 calc R . H51B H 0.2880(20) 0.1700(33) 0.9571(12) 0.136 Uiso 1 calc R . H51C H 0.2682(20) 0.0704(33) 1.0013(12) 0.136 Uiso 1 calc R . O60 O 0.4563(9) 0.7075(12) 1.0679(5) 0.039(3) Uani 1 d . . C60 C 0.4178(15) 0.8147(23) 1.0953(8) 0.050(5) Uani 1 d . . H60A H 0.3677(15) 0.7782(23) 1.1144(8) 0.060 Uiso 1 calc R . H60B H 0.3938(15) 0.8844(23) 1.0732(8) 0.060 Uiso 1 calc R . C61 C 0.4845(19) 0.8802(28) 1.1288(10) 0.073(8) Uani 1 d U . H61A H 0.4555(19) 0.9532(28) 1.1470(10) 0.110 Uiso 1 calc R . H61B H 0.5337(19) 0.9181(28) 1.1100(10) 0.110 Uiso 1 calc R . H61C H 0.5075(19) 0.8119(28) 1.1512(10) 0.110 Uiso 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 Mn 0.0305(11) 0.0263(10) 0.0247(9) 0.0031(8) -0.0023(9) 0.0025(8) Br1 0.0327(9) 0.0424(9) 0.0368(9) 0.0040(9) 0.0068(9) 0.0013(8) Br2 0.0303(8) 0.0453(9) 0.0341(8) 0.0043(9) 0.0037(8) 0.0010(9) N1 0.025(7) 0.026(7) 0.029(8) 0.007(6) -0.007(6) 0.012(5) C2 0.021(8) 0.027(8) 0.041(9) 0.008(8) -0.003(8) 0.005(7) C3 0.042(10) 0.021(8) 0.031(8) 0.003(7) 0.003(8) 0.019(7) C4 0.037(9) 0.003(6) 0.028(8) 0.004(6) -0.007(7) 0.006(6) C5 0.034(9) 0.011(7) 0.039(9) 0.003(7) 0.006(8) 0.007(6) C6 0.037(9) 0.034(9) 0.028(9) 0.001(8) 0.011(8) 0.005(8) S7 0.059(3) 0.031(2) 0.025(2) -0.002(2) -0.011(2) 0.016(2) C8 0.032(9) 0.022(8) 0.029(8) -0.010(7) -0.003(7) 0.012(7) F9 0.042(6) 0.036(5) 0.059(7) 0.007(5) 0.002(6) -0.005(5) C9 0.044(11) 0.036(10) 0.028(8) 0.000(7) 0.001(8) -0.007(8) F10 0.036(6) 0.051(6) 0.065(7) 0.002(6) 0.015(6) 0.022(5) C10 0.025(9) 0.050(11) 0.024(8) 0.007(8) 0.006(8) 0.016(8) C11 0.040(11) 0.028(9) 0.029(9) -0.006(7) 0.002(8) 0.003(8) F12 0.054(8) 0.043(7) 0.066(8) 0.001(6) 0.000(7) -0.015(6) C12 0.074(16) 0.037(11) 0.022(10) -0.005(8) -0.001(9) -0.011(10) F13 0.033(6) 0.050(7) 0.061(7) -0.001(5) -0.005(6) 0.014(5) C13 0.039(10) 0.052(12) 0.022(9) -0.008(8) -0.011(8) 0.013(9) S14 0.083(4) 0.024(2) 0.037(2) 0.003(2) 0.002(3) 0.013(3) C15 0.035(9) 0.030(8) 0.047(11) 0.004(8) -0.002(9) -0.002(8) C16 0.068(13) 0.014(8) 0.049(12) 0.012(8) -0.012(11) 0.005(8) C17 0.049(10) 0.034(10) 0.033(9) 0.001(9) 0.005(10) -0.007(8) N18 0.057(10) 0.037(8) 0.036(7) -0.002(9) 0.018(9) 0.007(7) C19 0.043(11) 0.024(8) 0.064(13) 0.016(9) 0.024(11) -0.006(8) C20 0.046(10) 0.023(8) 0.042(10) 0.011(7) 0.008(9) -0.003(8) N21 0.027(7) 0.031(7) 0.024(7) -0.003(5) -0.014(6) 0.002(6) C22 0.029(8) 0.034(9) 0.031(9) -0.006(8) -0.009(8) 0.009(7) C23 0.034(10) 0.028(8) 0.018(7) 0.000(7) 0.011(7) 0.003(7) C24 0.026(8) 0.035(9) 0.025(8) -0.004(7) -0.003(7) -0.007(7) C25 0.032(9) 0.038(9) 0.021(8) -0.013(7) -0.009(7) 0.000(8) C26 0.023(8) 0.035(8) 0.036(9) -0.014(8) 0.011(8) 0.005(7) S27 0.057(3) 0.027(2) 0.031(2) -0.002(2) -0.004(2) 0.012(2) C28 0.028(9) 0.044(10) 0.009(6) 0.008(7) -0.002(6) -0.002(7) C29 0.025(9) 0.026(9) 0.052(11) 0.017(8) -0.008(8) -0.010(7) F29 0.033(6) 0.046(7) 0.094(10) 0.005(7) -0.009(7) -0.009(5) F30 0.034(6) 0.049(7) 0.081(9) 0.012(7) 0.011(6) 0.004(5) C30 0.025(9) 0.051(12) 0.037(10) 0.001(9) -0.002(8) 0.022(9) C31 0.049(12) 0.035(10) 0.029(8) 0.006(8) 0.013(9) 0.016(9) F32 0.064(9) 0.042(7) 0.085(9) 0.002(6) -0.028(7) -0.016(6) C32 0.028(9) 0.028(9) 0.050(12) -0.010(9) 0.001(9) -0.014(8) F33 0.030(6) 0.060(7) 0.057(7) 0.008(6) -0.002(5) 0.009(5) C33 0.024(9) 0.046(10) 0.027(8) -0.005(8) -0.004(7) 0.005(8) S34 0.090(4) 0.034(2) 0.029(2) 0.003(2) -0.002(3) 0.020(3) C35 0.022(8) 0.028(8) 0.043(10) -0.010(8) 0.011(8) -0.001(7) C36 0.026(8) 0.020(8) 0.050(11) -0.008(7) 0.005(8) 0.005(7) C37 0.062(12) 0.036(10) 0.037(9) 0.013(10) 0.010(12) -0.003(8) N38 0.052(10) 0.036(8) 0.059(10) -0.017(10) -0.016(10) 0.007(7) C39 0.042(12) 0.056(13) 0.050(12) -0.028(11) -0.005(10) 0.010(9) C40 0.033(10) 0.038(10) 0.044(10) -0.008(8) -0.023(9) 0.002(8) O50 0.067(8) 0.021(5) 0.034(6) -0.005(5) 0.017(7) 0.007(6) C50 0.042(10) 0.021(8) 0.082(17) -0.009(10) 0.011(11) -0.001(7) C51 0.087(20) 0.094(20) 0.090(22) -0.050(18) -0.021(17) -0.024(17) O60 0.045(7) 0.035(6) 0.039(6) -0.009(5) 0.006(6) -0.008(6) C60 0.059(13) 0.050(11) 0.043(12) -0.010(9) 0.032(10) -0.010(10) C61 0.078(14) 0.075(14) 0.067(13) -0.053(12) -0.030(11) -0.007(11) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn O60 2.215(12) . ? Mn O50 2.216(12) . ? Mn N1 2.317(13) . ? Mn N21 2.315(13) . ? Mn Br2 2.677(3) . ? Mn Br1 2.681(3) . ? N1 C2 1.31(2) . ? N1 C6 1.31(2) . ? C2 C3 1.42(2) . ? C3 C4 1.39(2) . ? C4 C5 1.40(2) . ? C4 S7 1.76(2) . ? C5 C6 1.37(3) . ? S7 C8 1.79(2) . ? C8 C13 1.35(3) . ? C8 C9 1.37(3) . ? F9 C9 1.32(2) . ? C9 C10 1.40(3) . ? F10 C10 1.38(2) . ? C10 C11 1.35(3) . ? C11 C12 1.38(3) . ? C11 S14 1.79(2) . ? F12 C12 1.34(3) . ? C12 C13 1.36(3) . ? F13 C13 1.36(2) . ? S14 C15 1.77(2) . ? C15 C20 1.38(3) . ? C15 C16 1.41(3) . ? C16 C17 1.37(3) . ? C17 N18 1.32(2) . ? N18 C19 1.36(3) . ? C19 C20 1.40(3) . ? N21 C26 1.35(2) . ? N21 C22 1.40(2) . ? C22 C23 1.39(2) . ? C23 C24 1.41(2) . ? C24 C25 1.39(2) . ? C24 S27 1.74(2) . ? C25 C26 1.34(3) . ? S27 C28 1.75(2) . ? C28 C29 1.39(2) . ? C28 C33 1.42(3) . ? C29 C30 1.33(3) . ? C29 F29 1.37(2) . ? F30 C30 1.32(2) . ? C30 C31 1.40(3) . ? C31 C32 1.38(3) . ? C31 S34 1.72(2) . ? F32 C32 1.37(2) . ? C32 C33 1.37(3) . ? F33 C33 1.34(2) . ? S34 C35 1.78(2) . ? C35 C36 1.33(3) . ? C35 C40 1.41(3) . ? C36 C37 1.38(3) . ? C37 N38 1.36(2) . ? N38 C39 1.32(3) . ? C39 C40 1.39(3) . ? O50 C50 1.47(2) . ? C50 C51 1.44(3) . ? O60 C60 1.40(2) . ? C60 C61 1.48(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O60 Mn O50 179.5(6) . . ? O60 Mn N1 91.3(5) . . ? O50 Mn N1 88.7(5) . . ? O60 Mn N21 89.5(5) . . ? O50 Mn N21 90.5(5) . . ? N1 Mn N21 178.9(6) . . ? O60 Mn Br2 94.0(3) . . ? O50 Mn Br2 85.5(3) . . ? N1 Mn Br2 89.8(4) . . ? N21 Mn Br2 90.9(4) . . ? O60 Mn Br1 85.8(3) . . ? O50 Mn Br1 94.7(3) . . ? N1 Mn Br1 90.6(3) . . ? N21 Mn Br1 88.7(4) . . ? Br2 Mn Br1 179.61(15) . . ? C2 N1 C6 118.0(14) . . ? C2 N1 Mn 118.9(10) . . ? C6 N1 Mn 123.1(12) . . ? N1 C2 C3 123.0(14) . . ? C4 C3 C2 117.7(16) . . ? C3 C4 C5 118.2(15) . . ? C3 C4 S7 114.9(13) . . ? C5 C4 S7 126.4(12) . . ? C6 C5 C4 118.0(14) . . ? N1 C6 C5 124.9(16) . . ? C4 S7 C8 103.9(7) . . ? C13 C8 C9 120.0(16) . . ? C13 C8 S7 121.0(13) . . ? C9 C8 S7 118.5(14) . . ? F9 C9 C8 124.2(17) . . ? F9 C9 C10 118.4(18) . . ? C8 C9 C10 117.3(17) . . ? C11 C10 F10 119.8(17) . . ? C11 C10 C9 123.8(17) . . ? F10 C10 C9 116.4(18) . . ? C10 C11 C12 116.4(16) . . ? C10 C11 S14 120.7(15) . . ? C12 C11 S14 122.4(15) . . ? F12 C12 C13 119.6(21) . . ? F12 C12 C11 119.1(19) . . ? C13 C12 C11 121.1(20) . . ? C8 C13 F13 120.5(17) . . ? C8 C13 C12 121.2(19) . . ? F13 C13 C12 118.3(20) . . ? C15 S14 C11 104.3(8) . . ? C20 C15 C16 118.9(19) . . ? C20 C15 S14 114.1(15) . . ? C16 C15 S14 126.9(15) . . ? C17 C16 C15 116.2(16) . . ? N18 C17 C16 127.0(20) . . ? C17 N18 C19 116.3(18) . . ? N18 C19 C20 121.8(17) . . ? C15 C20 C19 119.7(18) . . ? C26 N21 C22 116.4(14) . . ? C26 N21 Mn 121.9(11) . . ? C22 N21 Mn 121.7(11) . . ? C23 C22 N21 122.2(16) . . ? C22 C23 C24 119.1(15) . . ? C25 C24 C23 116.9(16) . . ? C25 C24 S27 117.8(13) . . ? C23 C24 S27 125.2(14) . . ? C26 C25 C24 121.9(15) . . ? C25 C26 N21 123.5(15) . . ? C24 S27 C28 105.0(8) . . ? C29 C28 C33 113.3(15) . . ? C29 C28 S27 125.2(13) . . ? C33 C28 S27 121.0(13) . . ? C30 C29 F29 120.6(17) . . ? C30 C29 C28 124.3(16) . . ? F29 C29 C28 115.1(15) . . ? F30 C30 C29 118.0(19) . . ? F30 C30 C31 118.6(17) . . ? C29 C30 C31 123.3(16) . . ? C32 C31 C30 113.4(16) . . ? C32 C31 S34 123.2(16) . . ? C30 C31 S34 122.9(15) . . ? F32 C32 C33 117.5(17) . . ? F32 C32 C31 118.4(17) . . ? C33 C32 C31 124.1(17) . . ? F33 C33 C32 119.3(17) . . ? F33 C33 C28 119.1(16) . . ? C32 C33 C28 121.4(17) . . ? C31 S34 C35 107.3(9) . . ? C36 C35 C40 122.7(17) . . ? C36 C35 S34 124.7(13) . . ? C40 C35 S34 111.9(14) . . ? C35 C36 C37 118.8(15) . . ? N38 C37 C36 121.2(20) . . ? C39 N38 C37 118.4(19) . . ? N38 C39 C40 124.4(19) . . ? C39 C40 C35 114.6(18) . . ? C50 O50 Mn 128.7(11) . . ? C51 C50 O50 110.6(19) . . ? C60 O60 Mn 128.4(11) . . ? O60 C60 C61 112.1(20) . . ? _refine_diff_density_max 0.803 _refine_diff_density_min -0.622 _refine_diff_density_rms 0.121 data_NL9811 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C25 H14 N5 O6 Cl2 F6 S3 Cd' _chemical_formula_weight 873.89 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cd' 'Cd' 0.1185 4.6533 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/c 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 28.714(3) _cell_length_b 8.2439(13) _cell_length_c 28.736(3) _cell_angle_alpha 90.00 _cell_angle_beta 96.633(9) _cell_angle_gamma 90.00 _cell_volume 6756.7(15) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 57 _cell_measurement_theta_min 3.08 _cell_measurement_theta_max 22.50 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.718 _exptl_crystal_density_method ? _exptl_crystal_F_000 3448 _exptl_absorpt_coefficient_mu 9.096 _exptl_absorpt_correction_type ellipsoidal _exptl_absorpt_correction_T_min 0.0958 _exptl_absorpt_correction_T_max 0.2925 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5441 _diffrn_reflns_av_R_equivalents 0.0368 _diffrn_reflns_av_sigmaI/netI 0.0627 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -32 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 3.10 _diffrn_reflns_theta_max 62.01 _reflns_number_total 5323 _reflns_number_observed 3967 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0677P)^2^+8.6492P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00010(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 5323 _refine_ls_number_parameters 453 _refine_ls_number_restraints 36 _refine_ls_R_factor_all 0.0761 _refine_ls_R_factor_obs 0.0521 _refine_ls_wR_factor_all 0.1406 _refine_ls_wR_factor_obs 0.1240 _refine_ls_goodness_of_fit_all 1.036 _refine_ls_goodness_of_fit_obs 1.073 _refine_ls_restrained_S_all 1.046 _refine_ls_restrained_S_obs 1.085 _refine_ls_shift/esd_max -0.013 _refine_ls_shift/esd_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Cd Cd 0.665163(15) 0.22467(6) 0.61435(2) 0.0496(2) Uani 1 d . . N1 N 0.6083(2) 0.4269(7) 0.6121(2) 0.0548(13) Uani 1 d . . C2 C 0.5698(3) 0.4157(9) 0.6336(3) 0.060(2) Uani 1 d . . H2A H 0.5678(3) 0.3306(9) 0.6545(3) 0.073 Uiso 1 calc R . C3 C 0.5325(2) 0.5236(10) 0.6266(3) 0.062(2) Uani 1 d . . H3A H 0.5066(2) 0.5125(10) 0.6431(3) 0.075 Uiso 1 calc R . C4 C 0.5348(2) 0.6476(8) 0.5948(3) 0.0535(15) Uani 1 d . . C5 C 0.5748(2) 0.6626(9) 0.5728(3) 0.059(2) Uani 1 d . . H5A H 0.5779(2) 0.7472(9) 0.5520(3) 0.070 Uiso 1 calc R . C6 C 0.6102(2) 0.5492(9) 0.5823(3) 0.059(2) Uani 1 d . . H6A H 0.6369(2) 0.5594(9) 0.5670(3) 0.071 Uiso 1 calc R . S7 S 0.48641(7) 0.7777(3) 0.58714(8) 0.0785(6) Uani 1 d . . C8 C 0.4970(2) 0.8999(9) 0.5394(3) 0.059(2) Uani 1 d . . F9 F 0.4902(2) 0.6785(6) 0.4871(2) 0.0879(15) Uani 1 d . . C9 C 0.4951(2) 0.8370(9) 0.4935(3) 0.062(2) Uani 1 d . . F10 F 0.5031(2) 1.1320(6) 0.5865(2) 0.0772(12) Uani 1 d . . C10 C 0.5013(2) 1.0639(9) 0.5437(3) 0.057(2) Uani 1 d . . N11 N 0.7231(2) 0.0658(8) 0.5876(2) 0.0591(14) Uani 1 d . . C12 C 0.7288(3) -0.0901(11) 0.5982(4) 0.083(3) Uani 1 d . . H12A H 0.7092(3) -0.1380(11) 0.6178(4) 0.100 Uiso 1 calc R . C13 C 0.7629(4) -0.1832(12) 0.5813(4) 0.092(3) Uani 1 d . . H13A H 0.7657(4) -0.2925(12) 0.5891(4) 0.111 Uiso 1 calc R . C14 C 0.7925(3) -0.1143(11) 0.5530(3) 0.068(2) Uani 1 d . . C15 C 0.7862(3) 0.0445(11) 0.5415(3) 0.076(2) Uani 1 d . . H15A H 0.8055(3) 0.0948(11) 0.5219(3) 0.091 Uiso 1 calc R . C16 C 0.7515(3) 0.1289(10) 0.5589(3) 0.075(2) Uani 1 d . . H16A H 0.7473(3) 0.2371(10) 0.5503(3) 0.090 Uiso 1 calc R . S17 S 0.83603(9) -0.2279(4) 0.52800(8) 0.0916(8) Uani 1 d . . C18 C 0.6379(3) 0.1692(11) 0.9217(3) 0.070(2) Uani 1 d . . F19 F 0.6847(2) -0.0600(8) 0.9399(2) 0.092(2) Uani 1 d . . C19 C 0.6505(2) 0.0125(10) 0.9120(3) 0.063(2) Uani 1 d . . F20 F 0.6429(3) -0.2238(8) 0.8686(2) 0.111(2) Uani 1 d . . C20 C 0.6287(3) -0.0714(11) 0.8748(3) 0.073(2) Uani 1 d . . N21 N 0.6376(2) 0.0834(8) 0.6749(2) 0.0563(13) Uani 1 d . . C21 C 0.5938(3) -0.0049(13) 0.8451(3) 0.076(2) Uani 1 d . . F22 F 0.5469(2) 0.2281(12) 0.8259(3) 0.136(3) Uani 1 d . . C22 C 0.5812(3) 0.1540(14) 0.8544(3) 0.081(3) Uani 1 d . . F23 F 0.5886(3) 0.3912(9) 0.8990(3) 0.126(2) Uani 1 d . . C23 C 0.6028(3) 0.2393(11) 0.8917(3) 0.077(2) Uani 1 d . . C24 C 0.5947(3) -0.0333(11) 0.7503(3) 0.068(2) Uani 1 d . . C25 C 0.5753(3) -0.0599(11) 0.7055(3) 0.072(2) Uani 1 d . . H25A H 0.5472(3) -0.1162(11) 0.6997(3) 0.086 Uiso 1 calc R . C26 C 0.5972(3) -0.0035(10) 0.6688(3) 0.062(2) Uani 1 d . . H26A H 0.5839(3) -0.0258(10) 0.6385(3) 0.075 Uiso 1 calc R . S27 S 0.56587(10) -0.1110(4) 0.79672(8) 0.1084(11) Uani 1 d . . C29 C 0.6562(3) 0.1052(12) 0.7187(3) 0.073(2) Uani 1 d . . H29A H 0.6846(3) 0.1603(12) 0.7239(3) 0.088 Uiso 1 calc R . C30 C 0.6362(3) 0.0512(13) 0.7575(3) 0.078(2) Uani 1 d . . H30A H 0.6504(3) 0.0716(13) 0.7877(3) 0.094 Uiso 1 calc R . O40 O 0.6451(2) 0.2455(8) 0.5285(2) 0.076(2) Uani 1 d . . N40 N 0.6195(2) 0.1180(10) 0.5268(2) 0.071(2) Uani 1 d . . O41 O 0.6127(2) 0.0545(8) 0.5650(2) 0.077(2) Uani 1 d . . O42 O 0.6029(2) 0.0564(13) 0.4902(2) 0.118(3) Uani 1 d . . N50 N 0.7388(2) 0.4366(9) 0.6493(3) 0.071(2) Uani 1 d . . O50 O 0.7180(2) 0.4571(7) 0.6094(2) 0.0694(14) Uani 1 d . . O51 O 0.7258(2) 0.3225(9) 0.6739(2) 0.088(2) Uani 1 d . . O52 O 0.7715(3) 0.5241(11) 0.6640(3) 0.115(3) Uani 1 d . . C50 C 0.6946(9) 0.6178(33) 0.7622(11) 0.222(13) Uani 1 d . . Cl51 Cl 0.7064(7) 0.4447(23) 0.8001(7) 0.239(9) Uani 0.50 d PU 1 Cl52 Cl 0.6640(7) 0.6309(23) 0.7104(5) 0.219(10) Uani 0.50 d PU 2 Cl53 Cl 0.6373(10) 0.5548(33) 0.7375(9) 0.306(13) Uani 0.50 d PU 1 Cl54 Cl 0.6714(11) 0.4700(36) 0.7944(10) 0.301(10) Uani 0.50 d PU 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 Cd 0.0458(2) 0.0529(3) 0.0509(3) 0.0077(2) 0.0098(2) 0.0037(2) N1 0.056(3) 0.050(3) 0.059(3) 0.011(3) 0.011(2) 0.013(2) C2 0.062(4) 0.056(4) 0.065(4) 0.020(3) 0.013(3) 0.003(3) C3 0.055(4) 0.063(4) 0.071(4) 0.010(4) 0.021(3) 0.010(3) C4 0.051(3) 0.045(3) 0.065(4) 0.001(3) 0.010(3) 0.007(3) C5 0.059(4) 0.047(4) 0.072(4) 0.016(3) 0.017(3) 0.006(3) C6 0.048(3) 0.061(4) 0.073(5) 0.008(4) 0.022(3) 0.008(3) S7 0.0632(10) 0.0838(13) 0.0936(14) 0.0277(12) 0.0312(9) 0.0288(10) C8 0.046(3) 0.062(4) 0.069(4) 0.008(3) 0.006(3) 0.017(3) F9 0.105(4) 0.048(3) 0.112(4) -0.008(2) 0.015(3) 0.004(2) C9 0.049(3) 0.047(4) 0.088(5) -0.003(4) 0.005(3) 0.007(3) F10 0.083(3) 0.083(3) 0.066(3) -0.015(2) 0.009(2) 0.011(2) C10 0.045(3) 0.058(4) 0.067(4) -0.004(3) 0.005(3) 0.009(3) N11 0.052(3) 0.065(4) 0.064(4) 0.015(3) 0.019(3) 0.006(3) C12 0.088(6) 0.065(5) 0.107(7) 0.030(5) 0.057(5) 0.015(4) C13 0.102(6) 0.070(6) 0.118(8) 0.033(5) 0.065(6) 0.026(5) C14 0.056(4) 0.076(5) 0.075(5) 0.015(4) 0.023(3) 0.013(3) C15 0.071(5) 0.077(6) 0.087(6) 0.012(4) 0.039(4) 0.000(4) C16 0.079(5) 0.056(5) 0.095(6) 0.015(4) 0.030(4) 0.012(4) S17 0.0955(14) 0.114(2) 0.0721(12) 0.0240(13) 0.0400(11) 0.0444(14) C18 0.062(4) 0.088(6) 0.067(4) -0.003(4) 0.030(3) -0.024(4) F19 0.070(3) 0.114(4) 0.092(4) 0.015(3) 0.015(3) 0.013(3) C19 0.055(4) 0.077(5) 0.062(4) 0.002(4) 0.023(3) -0.003(3) F20 0.146(5) 0.080(4) 0.112(4) -0.022(3) 0.037(4) 0.001(4) C20 0.083(5) 0.075(6) 0.068(5) 0.003(4) 0.032(4) -0.014(4) N21 0.055(3) 0.061(3) 0.055(3) 0.007(3) 0.012(2) -0.004(2) C21 0.071(5) 0.109(7) 0.053(4) 0.009(4) 0.024(4) -0.026(5) F22 0.099(4) 0.192(8) 0.111(5) 0.025(5) -0.011(4) 0.028(5) C22 0.063(4) 0.109(8) 0.073(5) 0.023(5) 0.019(4) 0.001(5) F23 0.154(6) 0.084(4) 0.144(6) -0.004(4) 0.032(5) 0.032(4) C23 0.079(5) 0.072(6) 0.085(6) 0.008(5) 0.028(4) 0.004(4) C24 0.066(4) 0.086(6) 0.054(4) 0.000(4) 0.010(3) -0.018(4) C25 0.065(4) 0.085(6) 0.066(5) 0.000(4) 0.008(4) -0.026(4) C26 0.062(4) 0.071(5) 0.055(4) 0.001(3) 0.007(3) -0.010(3) S27 0.106(2) 0.160(3) 0.0624(12) -0.0075(14) 0.0264(12) -0.077(2) C29 0.056(4) 0.111(7) 0.051(4) 0.008(4) 0.003(3) -0.023(4) C30 0.064(4) 0.117(7) 0.055(4) 0.005(5) 0.009(3) -0.021(4) O40 0.080(3) 0.086(4) 0.064(3) 0.018(3) 0.021(3) 0.014(3) N40 0.044(3) 0.110(6) 0.060(4) -0.010(4) 0.012(3) 0.020(3) O41 0.068(3) 0.093(4) 0.071(4) -0.007(3) 0.014(3) -0.021(3) O42 0.059(3) 0.223(10) 0.071(4) -0.053(5) 0.005(3) 0.022(4) N50 0.061(4) 0.078(5) 0.077(4) 0.007(4) 0.012(3) -0.014(3) O50 0.065(3) 0.069(3) 0.075(4) 0.013(3) 0.010(3) -0.007(2) O51 0.090(4) 0.099(5) 0.074(4) 0.022(3) 0.002(3) -0.028(3) O52 0.095(5) 0.131(7) 0.116(6) 0.012(5) -0.007(4) -0.059(5) C50 0.198(22) 0.176(22) 0.266(30) 0.002(21) -0.087(22) -0.016(18) Cl51 0.306(21) 0.172(10) 0.202(10) -0.030(8) -0.135(13) -0.001(12) Cl52 0.260(18) 0.221(17) 0.159(10) -0.082(11) -0.052(10) 0.132(15) Cl53 0.335(24) 0.262(20) 0.289(20) -0.110(17) -0.104(16) 0.126(18) Cl54 0.398(28) 0.234(15) 0.255(15) -0.050(13) -0.031(19) -0.004(20) _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 Cd N21 2.309(6) . ? Cd N11 2.317(6) . ? Cd N1 2.329(5) . ? Cd O41 2.399(6) . ? Cd O51 2.434(6) . ? Cd O50 2.459(5) . ? Cd O40 2.474(6) . ? N1 C6 1.328(9) . ? N1 C2 1.328(9) . ? C2 C3 1.391(10) . ? C3 C4 1.379(10) . ? C4 C5 1.378(10) . ? C4 S7 1.749(6) . ? C5 C6 1.385(10) . ? S7 C8 1.756(8) . ? C8 C10 1.361(11) . ? C8 C9 1.413(11) . ? F9 C9 1.325(9) . ? C9 C10 1.358(11) 5_676 ? F10 C10 1.348(9) . ? C10 C9 1.358(11) 5_676 ? N11 C12 1.327(11) . ? N11 C16 1.331(10) . ? C12 C13 1.375(12) . ? C13 C14 1.367(11) . ? C14 C15 1.357(12) . ? C14 S17 1.779(8) . ? C15 C16 1.358(12) . ? S17 C18 1.767(9) 4_646 ? C18 C23 1.376(13) . ? C18 C19 1.378(12) . ? C18 S17 1.767(9) 4_656 ? F19 C19 1.334(9) . ? C19 C20 1.363(12) . ? F20 C20 1.341(11) . ? C20 C21 1.354(13) . ? N21 C29 1.323(10) . ? N21 C26 1.356(9) . ? C21 C22 1.394(15) . ? C21 S27 1.756(9) . ? F22 C22 1.351(11) . ? C22 C23 1.369(14) . ? F23 C23 1.341(11) . ? C24 C25 1.362(11) . ? C24 C30 1.374(11) . ? C24 S27 1.768(8) . ? C25 C26 1.369(11) . ? C29 C30 1.385(11) . ? O40 N40 1.280(10) . ? N40 O42 1.215(9) . ? N40 O41 1.250(9) . ? N50 O52 1.220(9) . ? N50 O50 1.242(9) . ? N50 O51 1.259(9) . ? C50 Cl52 1.64(3) . ? C50 Cl54 1.71(4) . ? C50 Cl53 1.79(4) . ? C50 Cl51 1.80(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N21 Cd N11 106.7(2) . . ? N21 Cd N1 94.7(2) . . ? N11 Cd N1 157.4(2) . . ? N21 Cd O41 84.5(2) . . ? N11 Cd O41 84.2(2) . . ? N1 Cd O41 90.7(2) . . ? N21 Cd O51 85.3(2) . . ? N11 Cd O51 86.4(2) . . ? N1 Cd O51 103.0(2) . . ? O41 Cd O51 163.5(2) . . ? N21 Cd O50 134.8(2) . . ? N11 Cd O50 87.1(2) . . ? N1 Cd O50 82.9(2) . . ? O41 Cd O50 140.4(2) . . ? O51 Cd O50 52.1(2) . . ? N21 Cd O40 136.5(2) . . ? N11 Cd O40 78.5(2) . . ? N1 Cd O40 80.9(2) . . ? O41 Cd O40 52.6(2) . . ? O51 Cd O40 138.0(2) . . ? O50 Cd O40 87.8(2) . . ? C6 N1 C2 116.8(6) . . ? C6 N1 Cd 118.7(4) . . ? C2 N1 Cd 123.7(5) . . ? N1 C2 C3 123.9(7) . . ? C4 C3 C2 118.2(6) . . ? C5 C4 C3 118.6(6) . . ? C5 C4 S7 125.4(6) . . ? C3 C4 S7 116.0(5) . . ? C4 C5 C6 118.7(6) . . ? N1 C6 C5 123.8(6) . . ? C4 S7 C8 104.1(3) . . ? C10 C8 C9 116.2(7) . . ? C10 C8 S7 121.5(6) . . ? C9 C8 S7 121.8(6) . . ? F9 C9 C10 120.0(8) . 5_676 ? F9 C9 C8 118.9(8) . . ? C10 C9 C8 121.0(7) 5_676 . ? F10 C10 C9 118.0(7) . 5_676 ? F10 C10 C8 119.2(7) . . ? C9 C10 C8 122.8(7) 5_676 . ? C12 N11 C16 116.9(7) . . ? C12 N11 Cd 123.1(5) . . ? C16 N11 Cd 120.0(5) . . ? N11 C12 C13 122.3(7) . . ? C14 C13 C12 119.7(8) . . ? C15 C14 C13 118.2(7) . . ? C15 C14 S17 119.2(6) . . ? C13 C14 S17 122.4(7) . . ? C14 C15 C16 119.1(7) . . ? N11 C16 C15 123.9(8) . . ? C18 S17 C14 99.9(3) 4_646 . ? C23 C18 C19 117.3(8) . . ? C23 C18 S17 121.4(8) . 4_656 ? C19 C18 S17 121.3(7) . 4_656 ? F19 C19 C20 118.9(8) . . ? F19 C19 C18 119.4(8) . . ? C20 C19 C18 121.7(8) . . ? F20 C20 C21 120.7(9) . . ? F20 C20 C19 117.4(9) . . ? C21 C20 C19 121.9(9) . . ? C29 N21 C26 116.1(6) . . ? C29 N21 Cd 120.8(5) . . ? C26 N21 Cd 122.2(5) . . ? C20 C21 C22 116.6(9) . . ? C20 C21 S27 122.3(9) . . ? C22 C21 S27 121.0(8) . . ? F22 C22 C23 118.4(10) . . ? F22 C22 C21 119.7(10) . . ? C23 C22 C21 121.9(9) . . ? F23 C23 C22 118.9(9) . . ? F23 C23 C18 120.6(9) . . ? C22 C23 C18 120.5(9) . . ? C25 C24 C30 118.4(7) . . ? C25 C24 S27 118.6(6) . . ? C30 C24 S27 122.9(6) . . ? C24 C25 C26 119.9(7) . . ? N21 C26 C25 122.9(7) . . ? C21 S27 C24 101.9(4) . . ? N21 C29 C30 124.2(7) . . ? C24 C30 C29 118.4(8) . . ? N40 O40 Cd 92.7(4) . . ? O42 N40 O41 119.9(9) . . ? O42 N40 O40 122.8(8) . . ? O41 N40 O40 117.3(7) . . ? N40 O41 Cd 97.1(5) . . ? O52 N50 O50 120.5(7) . . ? O52 N50 O51 120.8(8) . . ? O50 N50 O51 118.6(7) . . ? N50 O50 Cd 94.2(4) . . ? N50 O51 Cd 95.0(5) . . ? Cl52 C50 Cl54 109.6(18) . . ? Cl53 C50 Cl51 96.3(18) . . ? _refine_diff_density_max 0.605 _refine_diff_density_min -0.621 _refine_diff_density_rms 0.089