Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2004 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Dr Paul Wood' _publ_contact_author_address ; Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UNITED KINGDOM ; _publ_contact_author_email PTW22@CAM.AC.UK _publ_section_title ; Hydrothermal synthesis and magnetic properties of novel Mn(II) and Zn(II) materials with thiolato- carboxylate donor ligand frameworks ; loop_ _publ_author_name 'Paul Wood' 'Simon M. Humphrey' 'Richard A. Mole' 'J. Rawson' data_pw0312 _database_code_depnum_ccdc_archive 'CCDC 231140' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C56 H34 Mn5 O18 S8' _chemical_formula_sum 'C56 H34 Mn5 O18 S8' _chemical_formula_weight 1526.01 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' 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' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.9619(2) _cell_length_b 12.0924(3) _cell_length_c 13.6786(4) _cell_angle_alpha 82.3830(10) _cell_angle_beta 86.7680(12) _cell_angle_gamma 78.8418(8) _cell_volume 1440.79(6) _cell_formula_units_Z 1 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 8544 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.88 _exptl_crystal_description 'square plate' _exptl_crystal_colour colourless _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.759 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 767 _exptl_absorpt_coefficient_mu 1.430 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.750 _exptl_absorpt_correction_T_max 0.908 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_reflns_number 14738 _diffrn_reflns_av_R_equivalents 0.0505 _diffrn_reflns_av_sigmaI/netI 0.0639 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.54 _diffrn_reflns_theta_max 27.92 _reflns_number_total 6820 _reflns_number_gt 5221 _reflns_threshold_expression >2sigma(I) _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0152P)^2^+2.3483P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6820 _refine_ls_number_parameters 462 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0662 _refine_ls_R_factor_gt 0.0428 _refine_ls_wR_factor_ref 0.0927 _refine_ls_wR_factor_gt 0.0819 _refine_ls_goodness_of_fit_ref 1.035 _refine_ls_restrained_S_all 1.035 _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 0.0000 -0.5000 0.5000 0.01763(14) Uani 1 2 d S . . Mn2 Mn 0.36450(5) -0.52406(4) 0.59594(3) 0.01613(10) Uani 1 1 d . . . Mn3 Mn 0.27373(5) -0.59319(4) 0.35546(3) 0.02057(11) Uani 1 1 d . . . S1 S 0.39748(9) -0.90823(6) 0.67795(6) 0.02711(18) Uani 1 1 d . . . S2 S 0.22639(10) -0.45117(8) 0.87289(6) 0.0321(2) Uani 1 1 d . . . S3 S 0.44768(9) -0.07433(6) 0.65286(6) 0.02588(18) Uani 1 1 d . . . S4 S 0.25963(10) -0.47832(7) 0.02160(6) 0.02937(19) Uani 1 1 d . . . O1 O 0.0399(3) -0.62943(19) 0.62457(16) 0.0296(5) Uani 1 1 d . . . O2 O 0.2873(2) -0.67255(17) 0.65641(16) 0.0244(5) Uani 1 1 d . . . O3 O 0.1898(2) -0.40988(17) 0.67151(14) 0.0211(4) Uani 1 1 d . . . O4 O -0.0459(2) -0.37930(17) 0.61395(14) 0.0213(4) Uani 1 1 d . . . O5 O 0.5616(3) -0.27357(17) 0.59548(16) 0.0273(5) Uani 1 1 d . . . O6 O 0.4564(2) -0.37504(16) 0.50368(14) 0.0195(4) Uani 1 1 d . . . O7 O 0.4623(2) -0.45914(18) 0.30037(15) 0.0256(5) Uani 1 1 d . . . O8 O 0.2953(3) -0.51333(19) 0.21424(15) 0.0296(5) Uani 1 1 d . . . O9 O 0.2305(2) -0.49278(19) 0.46794(15) 0.0180(4) Uani 1 1 d . . . H9 H 0.238(5) -0.437(3) 0.450(3) 0.032(12) Uiso 1 1 d . . . C1 C 0.1221(3) -0.7878(2) 0.7406(2) 0.0186(6) Uani 1 1 d . . . C2 C 0.2208(4) -0.8935(2) 0.7478(2) 0.0202(6) Uani 1 1 d . . . C3 C 0.1793(4) -0.9840(3) 0.8103(2) 0.0274(7) Uani 1 1 d . . . H3 H 0.246(4) -1.052(3) 0.815(2) 0.014(8) Uiso 1 1 d . . . C4 C 0.0472(4) -0.9699(3) 0.8664(2) 0.0318(8) Uani 1 1 d . . . H4 H 0.020(5) -1.031(3) 0.910(3) 0.048(11) Uiso 1 1 d . . . C5 C -0.0498(4) -0.8644(3) 0.8621(2) 0.0305(8) Uani 1 1 d . . . H5 H -0.146(5) -0.853(3) 0.900(3) 0.042(11) Uiso 1 1 d . . . C6 C -0.0111(4) -0.7749(3) 0.7977(2) 0.0241(7) Uani 1 1 d . . . H6 H -0.088(4) -0.701(3) 0.791(3) 0.038(10) Uiso 1 1 d . . . C7 C 0.1522(3) -0.6890(2) 0.6683(2) 0.0194(6) Uani 1 1 d . . . C8 C -0.0141(3) -0.3184(2) 0.7680(2) 0.0188(6) Uani 1 1 d . . . C9 C 0.0533(4) -0.3475(3) 0.8597(2) 0.0223(6) Uani 1 1 d . . . C10 C -0.0170(4) -0.2954(3) 0.9402(2) 0.0308(8) Uani 1 1 d . . . H10 H 0.024(5) -0.317(3) 0.998(3) 0.040(11) Uiso 1 1 d . . . C11 C -0.1488(4) -0.2155(3) 0.9299(3) 0.0372(9) Uani 1 1 d . . . H11 H -0.195(5) -0.181(3) 0.986(3) 0.045(11) Uiso 1 1 d . . . C12 C -0.2154(4) -0.1849(3) 0.8386(3) 0.0342(8) Uani 1 1 d . . . H12 H -0.301(5) -0.127(3) 0.825(3) 0.042(11) Uiso 1 1 d . . . C13 C -0.1489(4) -0.2370(3) 0.7590(2) 0.0260(7) Uani 1 1 d . . . H13 H -0.195(4) -0.220(3) 0.697(3) 0.032(9) Uiso 1 1 d . . . C14 C 0.0499(3) -0.3732(2) 0.6787(2) 0.0178(6) Uani 1 1 d . . . C15 C 0.3519(3) -0.1772(2) 0.5026(2) 0.0207(6) Uani 1 1 d . . . C16 C 0.3350(3) -0.0777(2) 0.5490(2) 0.0211(6) Uani 1 1 d . . . C17 C 0.2285(4) 0.0165(3) 0.5129(3) 0.0277(7) Uani 1 1 d . . . H17 H 0.212(4) 0.085(3) 0.543(3) 0.039(10) Uiso 1 1 d . . . C18 C 0.1434(4) 0.0142(3) 0.4324(3) 0.0316(8) Uani 1 1 d . . . H18 H 0.067(4) 0.081(3) 0.410(3) 0.034(10) Uiso 1 1 d . . . C19 C 0.1614(4) -0.0819(3) 0.3852(3) 0.0318(8) Uani 1 1 d . . . H19 H 0.098(5) -0.084(3) 0.329(3) 0.057(13) Uiso 1 1 d . . . C20 C 0.2648(4) -0.1771(3) 0.4214(2) 0.0269(7) Uani 1 1 d . . . H20 H 0.280(4) -0.241(3) 0.387(2) 0.026(9) Uiso 1 1 d . . . C21 C 0.4636(3) -0.2817(2) 0.5357(2) 0.0199(6) Uani 1 1 d . . . C22 C 0.4127(3) -0.3649(3) 0.1360(2) 0.0227(6) Uani 1 1 d . . . C23 C 0.3540(4) -0.3658(3) 0.0428(2) 0.0243(7) Uani 1 1 d . . . C24 C 0.3713(4) -0.2770(3) -0.0315(2) 0.0321(8) Uani 1 1 d . . . H24 H 0.337(4) -0.281(3) -0.095(3) 0.032(10) Uiso 1 1 d . . . C25 C 0.4411(4) -0.1898(3) -0.0127(3) 0.0387(9) Uani 1 1 d . . . H25 H 0.455(4) -0.132(3) -0.065(3) 0.038(10) Uiso 1 1 d . . . C26 C 0.4987(4) -0.1891(3) 0.0785(3) 0.0384(9) Uani 1 1 d . . . H26 H 0.551(5) -0.127(3) 0.091(3) 0.052(12) Uiso 1 1 d . . . C27 C 0.4843(4) -0.2767(3) 0.1520(3) 0.0306(8) Uani 1 1 d . . . H27 H 0.523(4) -0.274(3) 0.210(3) 0.037(10) Uiso 1 1 d . . . C28 C 0.3921(4) -0.4511(3) 0.2211(2) 0.0218(6) 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 Mn1 0.0142(3) 0.0231(3) 0.0148(3) -0.0013(2) -0.0026(2) -0.0016(2) Mn2 0.0148(2) 0.0197(2) 0.0142(2) -0.00221(16) -0.00219(16) -0.00317(17) Mn3 0.0190(2) 0.0249(2) 0.0164(2) -0.00199(17) -0.00146(18) -0.00063(18) S1 0.0232(4) 0.0219(4) 0.0378(5) -0.0109(3) 0.0028(3) -0.0043(3) S2 0.0317(5) 0.0422(5) 0.0189(4) -0.0101(3) -0.0093(3) 0.0083(4) S3 0.0244(4) 0.0212(4) 0.0315(4) -0.0093(3) -0.0078(3) 0.0030(3) S4 0.0350(5) 0.0353(5) 0.0182(4) -0.0032(3) -0.0095(3) -0.0052(4) O1 0.0237(12) 0.0316(12) 0.0288(12) 0.0118(9) -0.0075(10) -0.0025(10) O2 0.0220(12) 0.0211(11) 0.0299(12) 0.0011(9) -0.0034(9) -0.0057(9) O3 0.0182(11) 0.0267(11) 0.0186(10) -0.0077(8) -0.0011(8) -0.0012(9) O4 0.0200(11) 0.0291(11) 0.0162(10) -0.0066(8) -0.0056(8) -0.0039(9) O5 0.0258(12) 0.0222(11) 0.0343(12) -0.0089(9) -0.0125(10) 0.0010(9) O6 0.0194(11) 0.0185(10) 0.0216(10) -0.0058(8) 0.0020(8) -0.0049(8) O7 0.0233(12) 0.0369(13) 0.0164(10) 0.0009(9) -0.0080(9) -0.0061(10) O8 0.0349(14) 0.0387(13) 0.0187(11) 0.0009(9) -0.0058(10) -0.0174(11) O9 0.0163(11) 0.0220(12) 0.0164(10) -0.0007(8) -0.0025(8) -0.0060(9) C1 0.0229(16) 0.0177(14) 0.0152(13) -0.0018(11) -0.0026(11) -0.0037(11) C2 0.0237(16) 0.0177(14) 0.0200(14) -0.0033(11) -0.0023(12) -0.0051(12) C3 0.033(2) 0.0181(16) 0.0286(17) -0.0009(13) -0.0030(14) 0.0003(14) C4 0.041(2) 0.0306(18) 0.0239(17) 0.0017(14) -0.0023(15) -0.0116(16) C5 0.033(2) 0.0343(19) 0.0232(17) -0.0030(13) 0.0080(14) -0.0075(15) C6 0.0273(18) 0.0220(16) 0.0200(15) -0.0008(12) 0.0014(13) 0.0011(13) C7 0.0226(16) 0.0184(14) 0.0169(14) -0.0038(11) -0.0004(12) -0.0024(12) C8 0.0172(15) 0.0230(15) 0.0175(14) -0.0059(11) -0.0021(11) -0.0047(11) C9 0.0196(16) 0.0269(16) 0.0217(15) -0.0070(12) -0.0030(12) -0.0038(12) C10 0.0275(19) 0.045(2) 0.0210(17) -0.0127(15) -0.0009(14) -0.0025(15) C11 0.028(2) 0.054(2) 0.0316(19) -0.0223(17) 0.0058(15) -0.0013(16) C12 0.0225(18) 0.039(2) 0.040(2) -0.0159(16) -0.0032(15) 0.0044(15) C13 0.0250(18) 0.0295(17) 0.0247(16) -0.0066(13) -0.0043(13) -0.0048(13) C14 0.0213(16) 0.0157(14) 0.0169(14) -0.0002(10) -0.0022(11) -0.0050(11) C15 0.0177(15) 0.0210(15) 0.0223(15) -0.0017(11) -0.0009(12) -0.0015(12) C16 0.0164(15) 0.0225(15) 0.0229(15) -0.0024(12) -0.0007(12) -0.0001(12) C17 0.0272(18) 0.0202(16) 0.0333(18) -0.0035(13) 0.0009(14) 0.0012(13) C18 0.0279(19) 0.0300(18) 0.0316(18) 0.0043(14) -0.0044(15) 0.0034(14) C19 0.0296(19) 0.0355(19) 0.0284(18) 0.0002(14) -0.0089(15) -0.0017(15) C20 0.0275(18) 0.0302(18) 0.0238(16) -0.0051(13) -0.0025(13) -0.0055(14) C21 0.0196(16) 0.0205(15) 0.0196(14) -0.0040(11) 0.0004(12) -0.0027(12) C22 0.0186(16) 0.0292(16) 0.0188(14) 0.0014(12) -0.0027(12) -0.0034(12) C23 0.0196(16) 0.0375(18) 0.0141(14) -0.0016(12) -0.0007(12) -0.0019(13) C24 0.0284(19) 0.048(2) 0.0165(16) 0.0057(14) -0.0046(14) -0.0050(16) C25 0.030(2) 0.051(2) 0.034(2) 0.0154(17) -0.0065(16) -0.0163(17) C26 0.035(2) 0.044(2) 0.037(2) 0.0085(16) -0.0078(16) -0.0190(17) C27 0.0272(18) 0.040(2) 0.0257(17) 0.0022(14) -0.0099(14) -0.0114(15) C28 0.0202(16) 0.0267(16) 0.0167(14) -0.0035(12) 0.0005(12) 0.0000(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 Mn1 O9 2.103(2) . ? Mn1 O9 2.103(2) 2_546 ? Mn1 O1 2.151(2) 2_546 ? Mn1 O1 2.151(2) . ? Mn1 O4 2.242(2) 2_546 ? Mn1 O4 2.242(2) . ? Mn1 Mn3 3.1891(5) . ? Mn1 Mn3 3.1891(5) 2_546 ? Mn2 O2 2.100(2) . ? Mn2 O7 2.124(2) 2_646 ? Mn2 O9 2.130(2) . ? Mn2 O3 2.187(2) . ? Mn2 O6 2.315(2) 2_646 ? Mn2 O6 2.3179(19) . ? Mn3 O5 2.032(2) 2_646 ? Mn3 O8 2.058(2) . ? Mn3 O9 2.059(2) . ? Mn3 O4 2.141(2) 2_546 ? S1 C2 1.794(3) . ? S1 S3 2.0420(11) 1_545 ? S2 C9 1.797(3) . ? S2 S4 2.0463(11) 1_556 ? S3 C16 1.798(3) . ? S3 S1 2.0420(11) 1_565 ? S4 C23 1.797(3) . ? S4 S2 2.0463(11) 1_554 ? O1 C7 1.251(4) . ? O2 C7 1.262(4) . ? O3 C14 1.249(4) . ? O4 C14 1.286(3) . ? O4 Mn3 2.141(2) 2_546 ? O5 C21 1.259(4) . ? O5 Mn3 2.032(2) 2_646 ? O6 C21 1.277(3) . ? O6 Mn2 2.315(2) 2_646 ? O7 C28 1.268(3) . ? O7 Mn2 2.124(2) 2_646 ? O8 C28 1.268(4) . ? C1 C6 1.384(4) . ? C1 C2 1.401(4) . ? C1 C7 1.504(4) . ? C2 C3 1.393(4) . ? C3 C4 1.369(5) . ? C4 C5 1.394(5) . ? C5 C6 1.387(4) . ? C8 C9 1.395(4) . ? C8 C13 1.403(4) . ? C8 C14 1.501(4) . ? C9 C10 1.399(4) . ? C10 C11 1.375(5) . ? C11 C12 1.389(5) . ? C12 C13 1.378(5) . ? C15 C20 1.393(4) . ? C15 C16 1.412(4) . ? C15 C21 1.488(4) . ? C16 C17 1.391(4) . ? C17 C18 1.380(5) . ? C18 C19 1.382(5) . ? C19 C20 1.384(5) . ? C22 C27 1.393(5) . ? C22 C23 1.408(4) . ? C22 C28 1.484(4) . ? C23 C24 1.403(4) . ? C24 C25 1.384(5) . ? C25 C26 1.379(5) . ? C26 C27 1.381(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O9 Mn1 O9 180.00(11) . 2_546 ? O9 Mn1 O1 84.09(8) . 2_546 ? O9 Mn1 O1 95.91(8) 2_546 2_546 ? O9 Mn1 O1 95.91(8) . . ? O9 Mn1 O1 84.09(8) 2_546 . ? O1 Mn1 O1 180.0 2_546 . ? O9 Mn1 O4 81.41(8) . 2_546 ? O9 Mn1 O4 98.59(8) 2_546 2_546 ? O1 Mn1 O4 84.66(8) 2_546 2_546 ? O1 Mn1 O4 95.34(8) . 2_546 ? O9 Mn1 O4 98.59(8) . . ? O9 Mn1 O4 81.41(8) 2_546 . ? O1 Mn1 O4 95.34(8) 2_546 . ? O1 Mn1 O4 84.66(8) . . ? O4 Mn1 O4 180.00(11) 2_546 . ? O9 Mn1 Mn3 39.47(6) . . ? O9 Mn1 Mn3 140.53(6) 2_546 . ? O1 Mn1 Mn3 79.94(6) 2_546 . ? O1 Mn1 Mn3 100.06(6) . . ? O4 Mn1 Mn3 42.09(5) 2_546 . ? O4 Mn1 Mn3 137.91(5) . . ? O9 Mn1 Mn3 140.53(6) . 2_546 ? O9 Mn1 Mn3 39.47(6) 2_546 2_546 ? O1 Mn1 Mn3 100.06(6) 2_546 2_546 ? O1 Mn1 Mn3 79.94(6) . 2_546 ? O4 Mn1 Mn3 137.91(5) 2_546 2_546 ? O4 Mn1 Mn3 42.09(5) . 2_546 ? Mn3 Mn1 Mn3 180.000(12) . 2_546 ? O2 Mn2 O7 95.02(8) . 2_646 ? O2 Mn2 O9 95.90(8) . . ? O7 Mn2 O9 166.24(8) 2_646 . ? O2 Mn2 O3 94.87(8) . . ? O7 Mn2 O3 97.07(8) 2_646 . ? O9 Mn2 O3 90.33(8) . . ? O2 Mn2 O6 91.44(8) . 2_646 ? O7 Mn2 O6 87.75(8) 2_646 2_646 ? O9 Mn2 O6 83.63(8) . 2_646 ? O3 Mn2 O6 171.69(7) . 2_646 ? O2 Mn2 O6 169.86(8) . . ? O7 Mn2 O6 90.47(8) 2_646 . ? O9 Mn2 O6 77.53(8) . . ? O3 Mn2 O6 92.90(7) . . ? O6 Mn2 O6 80.24(7) 2_646 . ? O5 Mn3 O8 118.66(10) 2_646 . ? O5 Mn3 O9 105.75(9) 2_646 . ? O8 Mn3 O9 117.50(9) . . ? O5 Mn3 O4 114.68(9) 2_646 2_546 ? O8 Mn3 O4 110.63(9) . 2_546 ? O9 Mn3 O4 84.93(8) . 2_546 ? O5 Mn3 Mn1 120.34(7) 2_646 . ? O8 Mn3 Mn1 120.87(7) . . ? O9 Mn3 Mn1 40.50(6) . . ? O4 Mn3 Mn1 44.58(5) 2_546 . ? C2 S1 S3 105.44(10) . 1_545 ? C9 S2 S4 104.25(11) . 1_556 ? C16 S3 S1 103.65(10) . 1_565 ? C23 S4 S2 103.80(10) . 1_554 ? C7 O1 Mn1 137.2(2) . . ? C7 O2 Mn2 128.55(19) . . ? C14 O3 Mn2 143.74(19) . . ? C14 O4 Mn3 125.74(18) . 2_546 ? C14 O4 Mn1 123.98(19) . . ? Mn3 O4 Mn1 93.33(8) 2_546 . ? C21 O5 Mn3 122.52(19) . 2_646 ? C21 O6 Mn2 126.92(18) . 2_646 ? C21 O6 Mn2 124.26(18) . . ? Mn2 O6 Mn2 99.76(7) 2_646 . ? C28 O7 Mn2 163.2(2) . 2_646 ? C28 O8 Mn3 103.97(18) . . ? Mn3 O9 Mn1 100.04(9) . . ? Mn3 O9 Mn2 122.41(11) . . ? Mn1 O9 Mn2 113.21(9) . . ? C6 C1 C2 119.5(3) . . ? C6 C1 C7 118.5(3) . . ? C2 C1 C7 121.9(3) . . ? C3 C2 C1 118.8(3) . . ? C3 C2 S1 121.8(2) . . ? C1 C2 S1 119.4(2) . . ? C4 C3 C2 121.0(3) . . ? C3 C4 C5 120.8(3) . . ? C6 C5 C4 118.4(3) . . ? C1 C6 C5 121.5(3) . . ? O1 C7 O2 125.3(3) . . ? O1 C7 C1 116.6(3) . . ? O2 C7 C1 118.1(3) . . ? C9 C8 C13 119.1(3) . . ? C9 C8 C14 122.5(3) . . ? C13 C8 C14 118.4(3) . . ? C8 C9 C10 118.8(3) . . ? C8 C9 S2 119.9(2) . . ? C10 C9 S2 121.2(2) . . ? C11 C10 C9 121.2(3) . . ? C10 C11 C12 120.2(3) . . ? C13 C12 C11 119.2(3) . . ? C12 C13 C8 121.4(3) . . ? O3 C14 O4 124.4(3) . . ? O3 C14 C8 119.2(3) . . ? O4 C14 C8 116.5(3) . . ? C20 C15 C16 119.3(3) . . ? C20 C15 C21 118.5(3) . . ? C16 C15 C21 122.2(3) . . ? C17 C16 C15 118.3(3) . . ? C17 C16 S3 121.3(2) . . ? C15 C16 S3 120.4(2) . . ? C18 C17 C16 121.2(3) . . ? C17 C18 C19 120.9(3) . . ? C18 C19 C20 118.6(3) . . ? C19 C20 C15 121.6(3) . . ? O5 C21 O6 122.8(3) . . ? O5 C21 C15 117.5(3) . . ? O6 C21 C15 119.7(3) . . ? C27 C22 C23 119.6(3) . . ? C27 C22 C28 118.0(3) . . ? C23 C22 C28 122.2(3) . . ? C24 C23 C22 118.2(3) . . ? C24 C23 S4 121.7(2) . . ? C22 C23 S4 120.1(2) . . ? C25 C24 C23 120.7(3) . . ? C26 C25 C24 121.1(3) . . ? C25 C26 C27 118.9(3) . . ? C26 C27 C22 121.5(3) . . ? O8 C28 O7 120.4(3) . . ? O8 C28 C22 117.8(3) . . ? O7 C28 C22 121.7(3) . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 27.92 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.666 _refine_diff_density_min -0.503 _refine_diff_density_rms 0.107 data_pw0310 _database_code_depnum_ccdc_archive 'CCDC 231141' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C7 H4 O2 S Zn' _chemical_formula_sum 'C7 H4 O2 S Zn' _chemical_formula_weight 217.53 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' 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 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 27.0809(7) _cell_length_b 7.5696(4) _cell_length_c 7.1040(4) _cell_angle_alpha 90.00 _cell_angle_beta 93.11(3) _cell_angle_gamma 90.00 _cell_volume 1454.11(12) _cell_formula_units_Z 8 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 12426 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.88 _exptl_crystal_description sheet _exptl_crystal_colour colourless _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.987 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 864 _exptl_absorpt_coefficient_mu 3.598 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.751 _exptl_absorpt_correction_T_max 0.906 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_reflns_number 7196 _diffrn_reflns_av_R_equivalents 0.0601 _diffrn_reflns_av_sigmaI/netI 0.0461 _diffrn_reflns_limit_h_min -35 _diffrn_reflns_limit_h_max 35 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.51 _diffrn_reflns_theta_max 27.94 _reflns_number_total 1735 _reflns_number_gt 1488 _reflns_threshold_expression >2sigma(I) _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0231P)^2^+10.1445P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1735 _refine_ls_number_parameters 116 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0584 _refine_ls_R_factor_gt 0.0456 _refine_ls_wR_factor_ref 0.1033 _refine_ls_wR_factor_gt 0.0987 _refine_ls_goodness_of_fit_ref 1.199 _refine_ls_restrained_S_all 1.199 _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 Zn1 Zn 0.219510(18) 0.46412(7) 0.15397(7) 0.02274(17) Uani 1 1 d . . . S1 S 0.16791(4) 0.43288(14) -0.11752(15) 0.0226(2) Uani 1 1 d . . . O1 O 0.23011(10) 0.7657(4) -0.2121(4) 0.0245(6) Uani 1 1 d . . . O2 O 0.21050(11) 1.0146(4) -0.0815(4) 0.0261(7) Uani 1 1 d . . . C1 C 0.14612(15) 0.8021(6) -0.1134(6) 0.0219(8) Uani 1 1 d . . . C2 C 0.12994(15) 0.6258(6) -0.1035(6) 0.0231(9) Uani 1 1 d . . . C3 C 0.07993(17) 0.5934(7) -0.0770(7) 0.0309(10) Uani 1 1 d . . . H3 H 0.0701(19) 0.475(7) -0.057(8) 0.031(14) Uiso 1 1 d . . . C4 C 0.04677(18) 0.7290(8) -0.0631(8) 0.0411(13) Uani 1 1 d . . . H4 H 0.012(3) 0.703(10) -0.069(10) 0.07(2) Uiso 1 1 d . . . C5 C 0.0624(2) 0.9024(8) -0.0758(9) 0.0451(14) Uani 1 1 d . . . H5 H 0.041(2) 0.990(8) -0.094(8) 0.042(16) Uiso 1 1 d . . . C6 C 0.11154(19) 0.9385(7) -0.1001(8) 0.0352(11) Uani 1 1 d . . . H6 H 0.125(2) 1.050(8) -0.117(8) 0.037(15) Uiso 1 1 d . . . C7 C 0.19850(15) 0.8608(6) -0.1377(6) 0.0223(8) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Zn1 0.0229(3) 0.0262(3) 0.0192(3) 0.0027(2) 0.00182(18) 0.0005(2) S1 0.0253(5) 0.0221(5) 0.0202(5) 0.0001(4) 0.0007(4) -0.0010(4) O1 0.0213(14) 0.0274(16) 0.0250(16) -0.0035(13) 0.0024(12) -0.0008(12) O2 0.0245(15) 0.0212(15) 0.0328(18) -0.0031(13) 0.0025(13) -0.0018(12) C1 0.0206(19) 0.025(2) 0.020(2) 0.0036(17) 0.0001(16) 0.0001(16) C2 0.023(2) 0.028(2) 0.018(2) -0.0001(17) -0.0016(16) 0.0009(18) C3 0.026(2) 0.032(3) 0.035(3) 0.002(2) 0.0036(19) -0.0040(19) C4 0.021(2) 0.049(3) 0.053(3) 0.004(3) 0.006(2) 0.000(2) C5 0.029(3) 0.040(3) 0.067(4) -0.002(3) 0.010(3) 0.009(2) C6 0.031(2) 0.030(3) 0.045(3) 0.000(2) 0.007(2) 0.001(2) C7 0.026(2) 0.021(2) 0.020(2) 0.0052(17) -0.0004(16) 0.0008(17) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zn1 O1 1.996(3) 6_566 ? Zn1 O2 1.997(3) 7_565 ? Zn1 S1 2.3314(13) . ? Zn1 S1 2.3328(13) 6_566 ? Zn1 O1 2.481(3) 7_565 ? Zn1 C7 2.594(4) 7_565 ? S1 C2 1.792(4) . ? S1 Zn1 2.3328(13) 6_565 ? O1 C7 1.256(5) . ? O1 Zn1 1.996(3) 6_565 ? O1 Zn1 2.481(3) 7_565 ? O2 C7 1.268(5) . ? O2 Zn1 1.997(3) 7_565 ? C1 C6 1.401(6) . ? C1 C2 1.408(6) . ? C1 C7 1.505(6) . ? C2 C3 1.399(6) . ? C3 C4 1.371(7) . ? C4 C5 1.383(8) . ? C5 C6 1.379(7) . ? C7 Zn1 2.594(4) 7_565 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Zn1 O2 94.54(12) 6_566 7_565 ? O1 Zn1 S1 111.72(9) 6_566 . ? O2 Zn1 S1 109.23(10) 7_565 . ? O1 Zn1 S1 92.05(9) 6_566 6_566 ? O2 Zn1 S1 139.92(10) 7_565 6_566 ? S1 Zn1 S1 104.76(4) . 6_566 ? O1 Zn1 O1 125.14(4) 6_566 7_565 ? O2 Zn1 O1 57.01(11) 7_565 7_565 ? S1 Zn1 O1 121.39(8) . 7_565 ? S1 Zn1 O1 87.33(8) 6_566 7_565 ? O1 Zn1 C7 111.43(12) 6_566 7_565 ? O2 Zn1 C7 28.46(13) 7_565 7_565 ? S1 Zn1 C7 119.41(10) . 7_565 ? S1 Zn1 C7 114.00(10) 6_566 7_565 ? O1 Zn1 C7 28.56(11) 7_565 7_565 ? C2 S1 Zn1 101.03(14) . . ? C2 S1 Zn1 97.69(15) . 6_565 ? Zn1 S1 Zn1 100.78(4) . 6_565 ? C7 O1 Zn1 128.0(3) . 6_565 ? C7 O1 Zn1 80.7(2) . 7_565 ? Zn1 O1 Zn1 149.48(15) 6_565 7_565 ? C7 O2 Zn1 102.9(3) . 7_565 ? C6 C1 C2 119.0(4) . . ? C6 C1 C7 115.3(4) . . ? C2 C1 C7 125.7(4) . . ? C3 C2 C1 118.6(4) . . ? C3 C2 S1 115.3(3) . . ? C1 C2 S1 126.1(3) . . ? C4 C3 C2 121.4(5) . . ? C3 C4 C5 120.1(5) . . ? C6 C5 C4 119.8(5) . . ? C5 C6 C1 121.1(5) . . ? O1 C7 O2 119.3(4) . . ? O1 C7 C1 123.1(4) . . ? O2 C7 C1 117.5(4) . . ? O1 C7 Zn1 70.7(2) . 7_565 ? O2 C7 Zn1 48.7(2) . 7_565 ? C1 C7 Zn1 166.0(3) . 7_565 ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 27.94 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.873 _refine_diff_density_min -0.580 _refine_diff_density_rms 0.143 data_pw0327 _database_code_depnum_ccdc_archive 'CCDC 231142' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C24 H20 Mn2 N4 O12 S4, 4(H2 O)' _chemical_formula_sum 'C24 H28 Mn2 N4 O16 S4' _chemical_formula_weight 866.62 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.2801(2) _cell_length_b 10.5377(2) _cell_length_c 16.8864(4) _cell_angle_alpha 95.1726(11) _cell_angle_beta 97.8935(11) _cell_angle_gamma 102.7070(9) _cell_volume 1583.20(6) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 8085 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 26.02 _exptl_crystal_description rod _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.818 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 884 _exptl_absorpt_coefficient_mu 1.145 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.903 _exptl_absorpt_correction_T_max 0.988 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_reflns_number 16800 _diffrn_reflns_av_R_equivalents 0.0427 _diffrn_reflns_av_sigmaI/netI 0.0483 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 3.53 _diffrn_reflns_theta_max 26.07 _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 26.07 _diffrn_measured_fraction_theta_full 0.990 _reflns_number_total 6212 _reflns_number_gt 3960 _reflns_threshold_expression >2sigma(I) _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0399P)^2^+1.0185P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6212 _refine_ls_number_parameters 561 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0728 _refine_ls_R_factor_gt 0.0420 _refine_ls_wR_factor_ref 0.1102 _refine_ls_wR_factor_gt 0.0954 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.052 _refine_ls_shift/su_max 0.016 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.352 _refine_diff_density_min -0.411 _refine_diff_density_rms 0.079 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 1.25103(5) 0.50059(4) -0.00021(3) 0.02076(14) Uani 1 1 d . . . Mn2 Mn 0.75644(5) 0.00856(4) 0.50111(3) 0.01754(13) Uani 1 1 d . . . S1 S 1.14834(8) 0.31917(7) 0.20883(4) 0.01784(18) Uani 1 1 d . . . S2 S 1.13482(8) 0.18268(7) 0.28761(4) 0.01731(18) Uani 1 1 d . . . S3 S 0.36881(8) -0.18104(7) 0.70851(4) 0.01763(18) Uani 1 1 d . . . S4 S 0.35365(8) -0.31717(7) 0.78787(4) 0.01754(18) Uani 1 1 d . . . N1 N 1.0380(3) 0.4308(2) 0.32898(15) 0.0199(6) Uani 1 1 d . . . N2 N 0.9046(3) 0.0713(2) 0.16961(15) 0.0203(6) Uani 1 1 d . . . N3 N 0.5953(3) -0.0691(2) 0.82835(15) 0.0205(6) Uani 1 1 d . . . N4 N 0.4699(3) -0.4289(2) 0.67021(15) 0.0196(6) Uani 1 1 d . . . O1 O 1.1466(2) 0.4932(2) 0.10351(12) 0.0214(5) Uani 1 1 d . . . O2 O 0.9641(2) 0.5975(2) 0.07671(12) 0.0225(5) Uani 1 1 d . . . O3 O 0.8785(2) -0.08994(19) 0.42335(12) 0.0210(5) Uani 1 1 d . . . O4 O 1.0996(2) 0.01081(19) 0.39475(12) 0.0207(5) Uani 1 1 d . . . O5 O 0.6225(2) 0.10396(19) 0.57714(12) 0.0199(5) Uani 1 1 d . . . O6 O 0.4026(2) -0.0066(2) 0.60317(12) 0.0212(5) Uani 1 1 d . . . O7 O 0.3542(2) -0.4894(2) 0.89541(12) 0.0207(5) Uani 1 1 d . . . O8 O 0.5345(2) -0.5963(2) 0.92257(12) 0.0220(5) Uani 1 1 d . . . O9 O 1.2904(3) 0.3055(3) 0.01963(19) 0.0383(7) Uani 1 1 d . . . H9B H 1.330(6) 0.280(5) 0.004(3) 0.057 Uiso 1 1 d . . . H9A H 1.346(5) 0.288(4) 0.084(3) 0.057 Uiso 1 1 d . . . O10 O 1.2104(4) 0.6959(3) -0.0205(2) 0.0405(8) Uani 1 1 d . . . H10B H 1.159(5) 0.714(4) -0.085(3) 0.061 Uiso 1 1 d . . . H10A H 1.171(7) 0.712(6) -0.008(4) 0.061 Uiso 1 1 d . . . O11 O 0.6142(3) -0.1889(2) 0.52269(17) 0.0317(6) Uani 1 1 d . . . H11B H 0.600(4) -0.202(4) 0.569(3) 0.048 Uiso 1 1 d . . . H11A H 0.544(5) -0.202(4) 0.492(3) 0.048 Uiso 1 1 d . . . O12 O 0.8710(3) 0.2014(2) 0.48371(19) 0.0370(7) Uani 1 1 d . . . H12B H 0.829(5) 0.252(4) 0.484(3) 0.056 Uiso 1 1 d . . . H12A H 0.956(5) 0.228(4) 0.491(3) 0.056 Uiso 1 1 d . . . O13 O 1.1637(3) 0.3531(3) 0.47437(16) 0.0319(6) Uani 1 1 d . . . H13A H 1.145(6) 0.352(5) 0.418(4) 0.035(5) Uiso 0.67 1 d P . . H13B H 1.209(6) 0.291(6) 0.482(3) 0.035(5) Uiso 0.67 1 d P . . H13C H 1.227(7) 0.418(6) 0.482(4) 0.035(5) Uiso 0.67 1 d P . . O14 O 1.0078(3) 0.1351(3) 0.02464(15) 0.0446(7) Uani 1 1 d D . . H14C H 0.997(5) 0.134(5) 0.0746(15) 0.035(5) Uiso 0.67 1 d PD . . H14B H 1.003(7) 0.050(4) 0.007(4) 0.035(5) Uiso 0.67 1 d P . . H14A H 1.087(4) 0.184(4) 0.016(3) 0.035(5) Uiso 0.67 1 d PD . . O15 O 0.3054(3) -0.3786(2) 0.52588(15) 0.0337(6) Uani 1 1 d D . . H15C H 0.348(6) -0.387(4) 0.584(3) 0.035(5) Uiso 0.67 1 d PD . . H15B H 0.270(6) -0.461(2) 0.508(3) 0.035(5) Uiso 0.67 1 d PD . . H15A H 0.368(5) -0.314(4) 0.517(3) 0.035(5) Uiso 0.67 1 d PD . . O16 O 0.4919(3) -0.1342(3) 0.97341(17) 0.0430(8) Uani 1 1 d . . . H16C H 0.496(6) -0.129(5) 0.922(4) 0.035(5) Uiso 0.67 1 d P . . H16B H 0.508(7) -0.040(5) 0.992(4) 0.035(5) Uiso 0.67 1 d P . . H16A H 0.438(7) -0.179(6) 0.981(4) 0.035(5) Uiso 0.67 1 d P . . C1 C 1.0572(3) 0.4360(3) 0.25212(17) 0.0147(6) Uani 1 1 d . . . C2 C 1.0102(3) 0.5285(3) 0.20641(17) 0.0158(6) Uani 1 1 d . . . C3 C 0.9362(3) 0.6134(3) 0.24210(19) 0.0184(7) Uani 1 1 d . . . H3 H 0.899(4) 0.679(3) 0.210(2) 0.028(9) Uiso 1 1 d . . . C4 C 0.9163(4) 0.6095(3) 0.32140(19) 0.0212(7) Uani 1 1 d . . . H4 H 0.870(3) 0.669(3) 0.3468(18) 0.015(8) Uiso 1 1 d . . . C5 C 0.9705(3) 0.5174(3) 0.36208(19) 0.0212(7) Uani 1 1 d . . . H5 H 0.967(3) 0.516(3) 0.418(2) 0.019(8) Uiso 1 1 d . . . C6 C 1.0409(3) 0.5397(3) 0.12190(17) 0.0148(6) Uani 1 1 d . . . C7 C 0.9620(3) 0.0656(3) 0.24590(17) 0.0153(6) Uani 1 1 d . . . C8 C 0.8932(3) -0.0247(3) 0.29267(17) 0.0154(6) Uani 1 1 d . . . C9 C 0.7586(3) -0.1111(3) 0.25754(18) 0.0183(7) Uani 1 1 d . . . H9 H 0.703(4) -0.174(3) 0.289(2) 0.033(9) Uiso 1 1 d . . . C10 C 0.6995(4) -0.1077(3) 0.1787(2) 0.0228(7) Uani 1 1 d . . . H10 H 0.609(4) -0.164(3) 0.1545(19) 0.019(8) Uiso 1 1 d . . . C11 C 0.7764(4) -0.0160(3) 0.1372(2) 0.0229(7) Uani 1 1 d . . . H11 H 0.745(4) -0.013(3) 0.084(2) 0.032(10) Uiso 1 1 d . . . C12 C 0.9611(3) -0.0349(3) 0.37759(17) 0.0160(6) Uani 1 1 d . . . C13 C 0.5401(3) -0.0632(3) 0.75203(17) 0.0160(6) Uani 1 1 d . . . C14 C 0.6081(3) 0.0302(3) 0.70609(17) 0.0161(6) Uani 1 1 d . . . C15 C 0.7433(3) 0.1156(3) 0.74179(18) 0.0179(7) Uani 1 1 d . . . H15 H 0.801(4) 0.181(3) 0.7106(19) 0.028(9) Uiso 1 1 d . . . C16 C 0.8014(3) 0.1104(3) 0.82052(19) 0.0214(7) Uani 1 1 d . . . H16 H 0.893(4) 0.167(3) 0.8495(19) 0.025(9) Uiso 1 1 d . . . C17 C 0.7235(4) 0.0174(3) 0.8615(2) 0.0235(7) Uani 1 1 d . . . H17 H 0.757(4) 0.016(3) 0.919(2) 0.029(9) Uiso 1 1 d . . . C18 C 0.5403(3) 0.0430(3) 0.62250(17) 0.0163(6) Uani 1 1 d . . . C19 C 0.4463(3) -0.4336(3) 0.74630(17) 0.0154(6) Uani 1 1 d . . . C20 C 0.4910(3) -0.5269(3) 0.79283(17) 0.0159(6) Uani 1 1 d . . . C21 C 0.5648(3) -0.6127(3) 0.75798(19) 0.0182(7) Uani 1 1 d . . . H21 H 0.602(4) -0.679(3) 0.788(2) 0.027(9) Uiso 1 1 d . . . C22 C 0.5898(4) -0.6089(3) 0.67942(19) 0.0210(7) Uani 1 1 d . . . H22 H 0.633(4) -0.668(3) 0.655(2) 0.029(9) Uiso 1 1 d . . . C23 C 0.5386(4) -0.5158(3) 0.6384(2) 0.0228(7) Uani 1 1 d . . . H23 H 0.548(4) -0.513(3) 0.585(2) 0.025(9) Uiso 1 1 d . . . C24 C 0.4589(3) -0.5376(3) 0.87741(17) 0.0163(6) 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 Mn1 0.0132(2) 0.0335(3) 0.0155(2) 0.0084(2) 0.00339(17) 0.00241(19) Mn2 0.0154(2) 0.0251(3) 0.0153(2) 0.00662(19) 0.00379(17) 0.00893(18) S1 0.0182(4) 0.0153(4) 0.0209(4) 0.0018(3) 0.0074(3) 0.0035(3) S2 0.0146(4) 0.0158(3) 0.0205(4) 0.0022(3) 0.0007(3) 0.0028(3) S3 0.0152(4) 0.0158(3) 0.0203(4) 0.0015(3) -0.0001(3) 0.0023(3) S4 0.0174(4) 0.0157(4) 0.0208(4) 0.0023(3) 0.0067(3) 0.0044(3) N1 0.0239(14) 0.0210(13) 0.0155(13) 0.0032(11) 0.0046(11) 0.0057(11) N2 0.0181(14) 0.0235(13) 0.0184(14) 0.0047(11) 0.0018(11) 0.0032(11) N3 0.0196(14) 0.0214(13) 0.0196(14) 0.0026(11) 0.0025(11) 0.0033(11) N4 0.0224(14) 0.0218(13) 0.0154(13) 0.0016(11) 0.0020(11) 0.0078(11) O1 0.0202(12) 0.0310(12) 0.0177(11) 0.0083(9) 0.0080(9) 0.0109(9) O2 0.0196(12) 0.0298(11) 0.0190(11) 0.0057(10) 0.0010(9) 0.0077(9) O3 0.0206(12) 0.0254(11) 0.0201(11) 0.0070(9) 0.0081(9) 0.0070(9) O4 0.0148(11) 0.0281(11) 0.0194(12) 0.0065(9) 0.0010(9) 0.0049(9) O5 0.0199(11) 0.0228(11) 0.0184(11) 0.0061(9) 0.0062(9) 0.0046(9) O6 0.0161(11) 0.0301(11) 0.0171(11) 0.0070(9) 0.0012(9) 0.0039(9) O7 0.0176(11) 0.0286(11) 0.0209(11) 0.0084(9) 0.0088(9) 0.0106(9) O8 0.0182(11) 0.0286(11) 0.0203(12) 0.0064(10) 0.0021(9) 0.0074(9) O9 0.049(2) 0.0293(14) 0.0494(19) 0.0152(13) 0.0204(14) 0.0232(12) O10 0.054(2) 0.0312(14) 0.0515(19) 0.0176(13) 0.0258(15) 0.0257(13) O11 0.0273(14) 0.0297(13) 0.0345(16) 0.0084(12) 0.0010(11) 0.0001(11) O12 0.0234(14) 0.0276(13) 0.0596(18) 0.0200(13) 0.0037(14) 0.0008(11) O13 0.0410(17) 0.0332(14) 0.0256(14) 0.0047(12) 0.0066(12) 0.0164(12) O14 0.0415(16) 0.0535(17) 0.0236(14) 0.0037(13) 0.0055(12) -0.0211(14) O15 0.0432(17) 0.0317(14) 0.0290(14) 0.0038(12) 0.0032(12) 0.0162(12) O16 0.0401(17) 0.0514(18) 0.0241(14) 0.0067(13) 0.0034(12) -0.0176(13) C1 0.0097(14) 0.0140(13) 0.0183(16) -0.0010(12) 0.0024(12) -0.0007(11) C2 0.0109(15) 0.0172(14) 0.0164(16) 0.0021(12) 0.0013(12) -0.0022(12) C3 0.0158(16) 0.0150(14) 0.0243(17) 0.0008(13) 0.0041(13) 0.0035(12) C4 0.0222(18) 0.0209(16) 0.0214(17) -0.0023(14) 0.0069(14) 0.0064(13) C5 0.0244(18) 0.0256(16) 0.0153(17) 0.0027(14) 0.0055(14) 0.0076(14) C6 0.0094(14) 0.0162(14) 0.0156(16) 0.0008(12) 0.0009(12) -0.0025(12) C7 0.0138(15) 0.0141(13) 0.0186(16) 0.0017(12) 0.0014(12) 0.0056(12) C8 0.0128(15) 0.0162(14) 0.0192(16) 0.0019(12) 0.0019(12) 0.0084(12) C9 0.0180(16) 0.0162(14) 0.0209(17) 0.0032(13) 0.0042(14) 0.0036(12) C10 0.0212(18) 0.0183(15) 0.0263(19) 0.0006(14) -0.0002(15) 0.0025(14) C11 0.0231(18) 0.0258(16) 0.0166(17) 0.0022(14) -0.0037(14) 0.0034(14) C12 0.0162(16) 0.0153(14) 0.0179(16) 0.0003(13) 0.0031(13) 0.0074(12) C13 0.0161(15) 0.0157(14) 0.0177(16) 0.0000(12) 0.0050(13) 0.0064(12) C14 0.0141(15) 0.0169(14) 0.0185(16) 0.0024(12) 0.0034(12) 0.0060(12) C15 0.0152(16) 0.0152(14) 0.0237(17) 0.0016(13) 0.0035(13) 0.0047(12) C16 0.0166(17) 0.0199(15) 0.0246(18) -0.0012(14) -0.0012(14) 0.0024(13) C17 0.0250(18) 0.0252(16) 0.0169(17) 0.0007(14) -0.0010(14) 0.0026(14) C18 0.0166(16) 0.0156(14) 0.0191(16) 0.0012(13) 0.0036(13) 0.0089(12) C19 0.0109(15) 0.0150(14) 0.0179(16) -0.0008(12) 0.0017(12) -0.0007(11) C20 0.0103(15) 0.0181(14) 0.0175(16) 0.0003(12) 0.0021(12) 0.0005(12) C21 0.0149(16) 0.0150(14) 0.0246(18) 0.0028(13) 0.0040(13) 0.0028(12) C22 0.0225(18) 0.0202(15) 0.0216(17) 0.0003(14) 0.0063(14) 0.0072(13) C23 0.0266(18) 0.0276(17) 0.0163(17) 0.0002(14) 0.0084(14) 0.0091(14) C24 0.0139(15) 0.0169(14) 0.0153(16) -0.0007(13) 0.0009(13) -0.0003(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 Mn1 O1 2.114(2) . ? Mn1 O7 2.118(2) 1_664 ? Mn1 O8 2.204(2) 2_756 ? Mn1 O2 2.206(2) 2_765 ? Mn1 O9 2.212(2) . ? Mn1 O10 2.220(3) . ? Mn2 O4 2.112(2) 2_756 ? Mn2 O6 2.132(2) 2_656 ? Mn2 O12 2.142(2) . ? Mn2 O3 2.183(2) . ? Mn2 O5 2.227(2) . ? Mn2 O11 2.295(2) . ? S1 C1 1.797(3) . ? S1 S2 2.0409(10) . ? S2 C7 1.803(3) . ? S3 C13 1.804(3) . ? S3 S4 2.0451(10) . ? S4 C19 1.792(3) . ? N1 C1 1.338(4) . ? N1 C5 1.339(4) . ? N2 C7 1.337(4) . ? N2 C11 1.346(4) . ? N3 C13 1.332(4) . ? N3 C17 1.345(4) . ? N4 C19 1.336(4) . ? N4 C23 1.340(4) . ? O1 C6 1.252(3) . ? O2 C6 1.260(4) . ? O2 Mn1 2.206(2) 2_765 ? O3 C12 1.252(3) . ? O4 C12 1.252(3) . ? O4 Mn2 2.112(2) 2_756 ? O5 C18 1.271(3) . ? O6 C18 1.255(3) . ? O6 Mn2 2.132(2) 2_656 ? O7 C24 1.252(3) . ? O7 Mn1 2.118(2) 1_446 ? O8 C24 1.259(4) . ? O8 Mn1 2.204(2) 2_756 ? C1 C2 1.402(4) . ? C2 C3 1.387(4) . ? C2 C6 1.503(4) . ? C3 C4 1.380(4) . ? C4 C5 1.380(4) . ? C7 C8 1.395(4) . ? C8 C9 1.393(4) . ? C8 C12 1.508(4) . ? C9 C10 1.375(4) . ? C10 C11 1.375(4) . ? C13 C14 1.403(4) . ? C14 C15 1.395(4) . ? C14 C18 1.495(4) . ? C15 C16 1.375(4) . ? C16 C17 1.382(4) . ? C19 C20 1.409(4) . ? C20 C21 1.386(4) . ? C20 C24 1.507(4) . ? C21 C22 1.380(4) . ? C22 C23 1.380(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Mn1 O7 179.08(8) . 1_664 ? O1 Mn1 O8 88.97(8) . 2_756 ? O7 Mn1 O8 91.24(8) 1_664 2_756 ? O1 Mn1 O2 90.48(8) . 2_765 ? O7 Mn1 O2 89.32(8) 1_664 2_765 ? O8 Mn1 O2 179.14(7) 2_756 2_765 ? O1 Mn1 O9 86.99(9) . . ? O7 Mn1 O9 93.91(9) 1_664 . ? O8 Mn1 O9 90.39(10) 2_756 . ? O2 Mn1 O9 88.91(10) 2_765 . ? O1 Mn1 O10 92.99(9) . . ? O7 Mn1 O10 86.11(9) 1_664 . ? O8 Mn1 O10 89.91(12) 2_756 . ? O2 Mn1 O10 90.78(12) 2_765 . ? O9 Mn1 O10 179.69(15) . . ? O4 Mn2 O6 173.63(7) 2_756 2_656 ? O4 Mn2 O12 97.50(9) 2_756 . ? O6 Mn2 O12 88.87(9) 2_656 . ? O4 Mn2 O3 91.48(8) 2_756 . ? O6 Mn2 O3 87.90(8) 2_656 . ? O12 Mn2 O3 94.06(10) . . ? O4 Mn2 O5 90.38(8) 2_756 . ? O6 Mn2 O5 90.07(8) 2_656 . ? O12 Mn2 O5 87.38(10) . . ? O3 Mn2 O5 177.47(8) . . ? O4 Mn2 O11 84.77(9) 2_756 . ? O6 Mn2 O11 88.91(9) 2_656 . ? O12 Mn2 O11 174.22(11) . . ? O3 Mn2 O11 91.19(9) . . ? O5 Mn2 O11 87.28(9) . . ? C1 S1 S2 102.77(9) . . ? C7 S2 S1 103.11(10) . . ? C13 S3 S4 102.74(10) . . ? C19 S4 S3 102.89(10) . . ? C1 N1 C5 117.9(3) . . ? C7 N2 C11 117.7(2) . . ? C13 N3 C17 117.8(3) . . ? C19 N4 C23 118.2(3) . . ? C6 O1 Mn1 131.28(18) . . ? C6 O2 Mn1 123.86(17) . 2_765 ? C12 O3 Mn2 124.97(18) . . ? C12 O4 Mn2 127.51(18) . 2_756 ? C18 O5 Mn2 123.19(18) . . ? C18 O6 Mn2 133.39(18) . 2_656 ? C24 O7 Mn1 129.73(18) . 1_446 ? C24 O8 Mn1 124.13(18) . 2_756 ? N1 C1 C2 122.3(3) . . ? N1 C1 S1 117.2(2) . . ? C2 C1 S1 120.5(2) . . ? C3 C2 C1 118.0(3) . . ? C3 C2 C6 119.9(3) . . ? C1 C2 C6 122.1(3) . . ? C4 C3 C2 120.2(3) . . ? C3 C4 C5 117.4(3) . . ? N1 C5 C4 124.2(3) . . ? O1 C6 O2 125.4(3) . . ? O1 C6 C2 115.7(3) . . ? O2 C6 C2 118.9(3) . . ? N2 C7 C8 122.7(3) . . ? N2 C7 S2 116.9(2) . . ? C8 C7 S2 120.4(2) . . ? C9 C8 C7 117.7(3) . . ? C9 C8 C12 119.5(2) . . ? C7 C8 C12 122.7(3) . . ? C10 C9 C8 120.1(3) . . ? C11 C10 C9 117.9(3) . . ? N2 C11 C10 123.8(3) . . ? O4 C12 O3 125.9(3) . . ? O4 C12 C8 115.1(2) . . ? O3 C12 C8 119.0(3) . . ? N3 C13 C14 122.9(3) . . ? N3 C13 S3 117.1(2) . . ? C14 C13 S3 120.0(2) . . ? C15 C14 C13 117.5(3) . . ? C15 C14 C18 119.6(2) . . ? C13 C14 C18 122.9(3) . . ? C16 C15 C14 120.0(3) . . ? C15 C16 C17 118.0(3) . . ? N3 C17 C16 123.7(3) . . ? O6 C18 O5 124.8(3) . . ? O6 C18 C14 116.0(2) . . ? O5 C18 C14 119.2(3) . . ? N4 C19 C20 121.8(3) . . ? N4 C19 S4 117.7(2) . . ? C20 C19 S4 120.5(2) . . ? C21 C20 C19 117.9(3) . . ? C21 C20 C24 119.6(3) . . ? C19 C20 C24 122.5(3) . . ? C22 C21 C20 120.8(3) . . ? C21 C22 C23 116.8(3) . . ? N4 C23 C22 124.4(3) . . ? O7 C24 O8 125.7(3) . . ? O7 C24 C20 115.6(3) . . ? O8 C24 C20 118.6(3) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C1 S1 S2 C7 91.32(13) . . . . ? C13 S3 S4 C19 -91.74(13) . . . . ?