# Copyright The Royal Society of Chemistry, 1998 #******************************************** #Supplementary Data for Compound 1 #******************************************** data_mnmm23 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety '[Mn6O2(tma)10(thf)4].thf' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C70 H130 Mn6 O27' _chemical_formula_weight 1733.38 _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' 'O' 'O' 0.0106 0.0060 '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 Orthorhombic _symmetry_space_group_name_H-M Pbcn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 14.092(2) _cell_length_b 22.920(3) _cell_length_c 27.383(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8844(2) _cell_formula_units_Z 4 _cell_measurement_temperature 220(2) _cell_measurement_reflns_used 80 _cell_measurement_theta_min 12 _cell_measurement_theta_max 13 _exptl_crystal_description block _exptl_crystal_colour brown _exptl_crystal_size_max 0.47 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.27 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.302 _exptl_crystal_density_method ? _exptl_crystal_F_000 3664 _exptl_absorpt_coefficient_mu 0.899 _exptl_absorpt_correction_type Psi-scans _exptl_absorpt_correction_T_min 0.412 _exptl_absorpt_correction_T_max 0.428 _exptl_special_details ; ? ; _diffrn_ambient_temperature 220(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 ; Stoe Stadi-4 diffractometer with Oxford Cryosystems variable temperature device. ; _diffrn_measurement_method 'omega-theta with learnt profile' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 120 _diffrn_standards_decay_% ? _diffrn_reflns_number 7984 _diffrn_reflns_av_R_equivalents 0.0198 _diffrn_reflns_av_sigmaI/netI 0.0796 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 2.73 _diffrn_reflns_theta_max 24.97 _reflns_number_total 7725 _reflns_number_observed 5020 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Stoe DIF4' _computing_cell_refinement 'Stoe DIF4' _computing_data_reduction 'Stoe REDU4' _computing_structure_solution 'SHELXS-96 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-96 (Sheldrick, 1996)' _computing_molecular_graphics SHELXTL _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. 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^)+(0.0274P)^2^+18.0864P] 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 7725 _refine_ls_number_parameters 517 _refine_ls_number_restraints 90 _refine_ls_R_factor_all 0.1096 _refine_ls_R_factor_obs 0.0595 _refine_ls_wR_factor_all 0.1364 _refine_ls_wR_factor_obs 0.1055 _refine_ls_goodness_of_fit_all 1.100 _refine_ls_goodness_of_fit_obs 1.073 _refine_ls_restrained_S_all 1.095 _refine_ls_restrained_S_obs 1.065 _refine_ls_shift/esd_max 0.177 _refine_ls_shift/esd_mean 0.010 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 Mn1 Mn 0.5000 0.40467(4) 0.2500 0.0252(2) Uani 1 d S . Mn2 Mn 0.5000 0.28184(4) 0.2500 0.0240(2) Uani 1 d S . Mn3 Mn 0.42319(6) 0.36013(3) 0.35255(3) 0.0310(2) Uani 1 d . . Mn4 Mn 0.32924(5) 0.32720(3) 0.18420(3) 0.0302(2) Uani 1 d . . O1 O 0.5241(2) 0.34317(13) 0.29460(11) 0.0244(7) Uani 1 d . . O11 O 0.3163(3) 0.38261(17) 0.41266(14) 0.0508(11) Uani 1 d D . C21_a C 0.261(3) 0.3388(8) 0.4362(9) 0.102(14) Uani 0.57 d PD 1 H21A_a H 0.3016 0.3065 0.4469 0.123 Uiso 0.57 calc PR 1 H21B_a H 0.2131 0.3233 0.4137 0.123 Uiso 0.57 calc PR 1 C31_a C 0.2146(14) 0.3662(9) 0.4787(6) 0.122(9) Uani 0.57 d PD 1 H31A_a H 0.2013 0.3378 0.5046 0.146 Uiso 0.57 calc PR 1 H31B_a H 0.1558 0.3863 0.4695 0.146 Uiso 0.57 calc PR 1 C41_a C 0.2961(18) 0.4110(10) 0.4940(5) 0.119(13) Uani 0.57 d PD 1 H41A_a H 0.2714 0.4430 0.5140 0.143 Uiso 0.57 calc PR 1 H41B_a H 0.3482 0.3916 0.5113 0.143 Uiso 0.57 calc PR 1 C51_a C 0.3249(13) 0.4308(6) 0.4454(6) 0.076(11) Uani 0.57 d PD 1 H51A_a H 0.2841 0.4630 0.4347 0.091 Uiso 0.57 calc PR 1 H51B_a H 0.3907 0.4447 0.4461 0.091 Uiso 0.57 calc PR 1 C21'_b C 0.279(4) 0.3357(8) 0.4409(9) 0.075(11) Uani 0.43 d PD 2 H21C_b H 0.3217 0.3019 0.4388 0.090 Uiso 0.43 calc PR 2 H21D_b H 0.2168 0.3242 0.4284 0.090 Uiso 0.43 calc PR 2 C31'_b C 0.2710(15) 0.3550(10) 0.4918(6) 0.077(8) Uani 0.43 d PD 2 H31C_b H 0.3282 0.3458 0.5106 0.093 Uiso 0.43 calc PR 2 H31D_b H 0.2156 0.3377 0.5078 0.093 Uiso 0.43 calc PR 2 C41'_b C 0.259(2) 0.4237(10) 0.4845(7) 0.078(10) Uani 0.43 d PD 2 H41C_b H 0.1934 0.4341 0.4757 0.094 Uiso 0.43 calc PR 2 H41D_b H 0.2780 0.4456 0.5136 0.094 Uiso 0.43 calc PR 2 C51'_b C 0.325(3) 0.4323(8) 0.4438(8) 0.15(3) Uani 0.43 d PD 2 H51C_b H 0.3083 0.4679 0.4258 0.176 Uiso 0.43 calc PR 2 H51D_b H 0.3897 0.4359 0.4559 0.176 Uiso 0.43 calc PR 2 O12 O 0.1771(3) 0.30260(18) 0.16112(15) 0.0504(11) Uani 1 d . . C22 C 0.1492(6) 0.2493(3) 0.1394(3) 0.083(3) Uani 1 d . . H22A H 0.1342 0.2206 0.1647 0.100 Uiso 1 calc R . H22B H 0.2008 0.2339 0.1192 0.100 Uiso 1 calc R . C32 C 0.0656(6) 0.2604(5) 0.1092(3) 0.104(3) Uani 1 d . . H32A H 0.0111 0.2382 0.1215 0.125 Uiso 1 calc R . H32B H 0.0777 0.2486 0.0754 0.125 Uiso 1 calc R . C42 C 0.0462(6) 0.3232(5) 0.1118(3) 0.094(3) Uani 1 d . . H42A H -0.0210 0.3303 0.1189 0.113 Uiso 1 calc R . H42B H 0.0623 0.3422 0.0808 0.113 Uiso 1 calc R . C52 C 0.1069(5) 0.3456(4) 0.1519(3) 0.089(3) Uani 1 d . . H52A H 0.1367 0.3824 0.1423 0.107 Uiso 1 calc R . H52B H 0.0687 0.3524 0.1813 0.107 Uiso 1 calc R . O1A O 0.3561(2) 0.40832(15) 0.28521(12) 0.0319(8) Uani 1 d . . O2A O 0.2596(3) 0.39584(16) 0.22146(13) 0.0399(9) Uani 1 d . . C1A C 0.2798(4) 0.4183(2) 0.2620(2) 0.0354(13) Uani 1 d . . C2A C 0.2075(4) 0.4612(3) 0.2848(2) 0.0429(15) Uani 1 d . . C3A C 0.2601(5) 0.5073(3) 0.3144(3) 0.080(2) Uani 1 d . . H3A1 H 0.2977 0.4885 0.3395 0.119 Uiso 1 calc R . H3A2 H 0.2146 0.5335 0.3295 0.119 Uiso 1 calc R . H3A3 H 0.3015 0.5294 0.2930 0.119 Uiso 1 calc R . C4A C 0.1439(5) 0.4253(3) 0.3188(3) 0.086(3) Uani 1 d . . H4A1 H 0.1825 0.4069 0.3438 0.129 Uiso 1 calc R . H4A2 H 0.1113 0.3955 0.3001 0.129 Uiso 1 calc R . H4A3 H 0.0976 0.4507 0.3341 0.129 Uiso 1 calc R . C5A C 0.1481(5) 0.4902(3) 0.2458(3) 0.086(3) Uani 1 d . . H5A1 H 0.1143 0.4606 0.2274 0.130 Uiso 1 calc R . H5A2 H 0.1889 0.5122 0.2241 0.130 Uiso 1 calc R . H5A3 H 0.1027 0.5163 0.2611 0.130 Uiso 1 calc R . O1B O 0.3419(2) 0.27849(14) 0.25904(12) 0.0310(8) Uani 1 d . . O2B O 0.3271(3) 0.28996(16) 0.33968(12) 0.0379(9) Uani 1 d . . C1B C 0.3035(4) 0.2670(2) 0.30009(19) 0.0308(12) Uani 1 d . . C2B C 0.2210(4) 0.2227(3) 0.2998(2) 0.0414(14) Uani 1 d . . C3B C 0.2432(5) 0.1732(3) 0.2645(2) 0.0622(19) Uani 1 d . . H3B1 H 0.2546 0.1891 0.2322 0.093 Uiso 1 calc R . H3B2 H 0.1899 0.1465 0.2633 0.093 Uiso 1 calc R . H3B3 H 0.2993 0.1526 0.2756 0.093 Uiso 1 calc R . C4B C 0.1327(4) 0.2558(3) 0.2822(3) 0.068(2) Uani 1 d . . H4B1 H 0.1185 0.2872 0.3048 0.102 Uiso 1 calc R . H4B2 H 0.0792 0.2292 0.2806 0.102 Uiso 1 calc R . H4B3 H 0.1446 0.2719 0.2500 0.102 Uiso 1 calc R . C5B C 0.2021(5) 0.1991(3) 0.3509(2) 0.065(2) Uani 1 d . . H5B1 H 0.1877 0.2313 0.3727 0.098 Uiso 1 calc R . H5B2 H 0.2579 0.1787 0.3626 0.098 Uiso 1 calc R . H5B3 H 0.1487 0.1725 0.3499 0.098 Uiso 1 calc R . O1C O 0.5117(3) 0.32993(17) 0.41016(13) 0.0452(10) Uani 1 d . . O2C O 0.6560(3) 0.36035(17) 0.38757(13) 0.0438(10) Uani 1 d . . C1C C 0.5965(4) 0.3447(2) 0.4188(2) 0.0407(14) Uani 1 d . . C2C C 0.6295(5) 0.3443(3) 0.4726(2) 0.0542(17) Uani 1 d . . C3C C 0.5579(6) 0.3156(4) 0.5060(2) 0.097(3) Uani 1 d . . H3C1 H 0.5814 0.3164 0.5393 0.146 Uiso 1 calc R . H3C2 H 0.5482 0.2755 0.4959 0.146 Uiso 1 calc R . H3C3 H 0.4983 0.3366 0.5043 0.146 Uiso 1 calc R . C4C C 0.6415(7) 0.4072(4) 0.4886(3) 0.112(4) Uani 1 d . . H4C1 H 0.6884 0.4261 0.4680 0.168 Uiso 1 calc R . H4C2 H 0.6625 0.4083 0.5223 0.168 Uiso 1 calc R . H4C3 H 0.5813 0.4275 0.4856 0.168 Uiso 1 calc R . C5C C 0.7239(6) 0.3133(5) 0.4762(3) 0.127(4) Uani 1 d . . H5C1 H 0.7694 0.3321 0.4548 0.191 Uiso 1 calc R . H5C2 H 0.7163 0.2728 0.4665 0.191 Uiso 1 calc R . H5C3 H 0.7467 0.3149 0.5096 0.191 Uiso 1 calc R . O1D O 0.5442(2) 0.46642(14) 0.29378(13) 0.0345(9) Uani 1 d . . O2D O 0.4759(3) 0.44648(15) 0.36584(12) 0.0377(9) Uani 1 d . . C1D C 0.5236(4) 0.4780(2) 0.33816(19) 0.0350(13) Uani 1 d . . C2D C 0.5657(4) 0.5351(2) 0.35766(19) 0.0563(18) Uani 1 d D . C3D_a C 0.5723(18) 0.5807(12) 0.3171(10) 0.102(7) Uani 0.70 d PD 1 H3D1_a H 0.5989 0.6164 0.3302 0.153 Uiso 0.70 calc PR 1 H3D2_a H 0.5093 0.5884 0.3043 0.153 Uiso 0.70 calc PR 1 H3D3_a H 0.6126 0.5662 0.2912 0.153 Uiso 0.70 calc PR 1 C4D_a C 0.6653(6) 0.5174(15) 0.3747(13) 0.093(6) Uani 0.70 d PD 1 H4D1_a H 0.6971 0.5510 0.3888 0.139 Uiso 0.70 calc PR 1 H4D2_a H 0.7016 0.5032 0.3470 0.139 Uiso 0.70 calc PR 1 H4D3_a H 0.6603 0.4868 0.3991 0.139 Uiso 0.70 calc PR 1 C5D_a C 0.509(3) 0.5592(14) 0.4006(7) 0.086(6) Uani 0.70 d PD 1 H5D1_a H 0.5385 0.5949 0.4121 0.130 Uiso 0.70 calc PR 1 H5D2_a H 0.5081 0.5307 0.4268 0.130 Uiso 0.70 calc PR 1 H5D3_a H 0.4446 0.5674 0.3901 0.130 Uiso 0.70 calc PR 1 C6D_b C 0.519(6) 0.547(4) 0.4068(16) 0.086(6) Uani 0.30 d PD 2 H6D1_b H 0.5444 0.5833 0.4203 0.130 Uiso 0.30 calc PR 2 H6D2_b H 0.5316 0.5154 0.4290 0.130 Uiso 0.30 calc PR 2 H6D3_b H 0.4509 0.5515 0.4023 0.130 Uiso 0.30 calc PR 2 C7D_b C 0.542(5) 0.583(3) 0.321(2) 0.102(7) Uani 0.30 d PD 2 H7D1_b H 0.5685 0.6200 0.3325 0.153 Uiso 0.30 calc PR 2 H7D2_b H 0.4738 0.5869 0.3181 0.153 Uiso 0.30 calc PR 2 H7D3_b H 0.5692 0.5737 0.2896 0.153 Uiso 0.30 calc PR 2 C8D_b C 0.6730(11) 0.529(4) 0.364(3) 0.093(6) Uani 0.30 d PD 2 H8D1_b H 0.6988 0.5653 0.3764 0.139 Uiso 0.30 calc PR 2 H8D2_b H 0.7017 0.5205 0.3323 0.139 Uiso 0.30 calc PR 2 H8D3_b H 0.6867 0.4976 0.3864 0.139 Uiso 0.30 calc PR 2 O1E O 0.4939(3) 0.22040(14) 0.20068(12) 0.0318(8) Uani 1 d . . O2E O 0.3648(3) 0.24222(15) 0.15702(13) 0.0366(9) Uani 1 d . . C1E C 0.4340(4) 0.2105(2) 0.16700(18) 0.0328(12) Uani 1 d . . C2E C 0.4530(4) 0.1562(2) 0.13578(19) 0.0439(15) Uani 1 d D . C3E_a C 0.5054(8) 0.1090(3) 0.1645(3) 0.085(4) Uani 0.78 d PD 1 H3E1_a H 0.5167 0.0756 0.1435 0.128 Uiso 0.78 calc PR 1 H3E2_a H 0.4672 0.0972 0.1922 0.128 Uiso 0.78 calc PR 1 H3E3_a H 0.5656 0.1243 0.1759 0.128 Uiso 0.78 calc PR 1 C4E_a C 0.5153(7) 0.1770(4) 0.0934(3) 0.090(4) Uani 0.78 d PD 1 H4E1_a H 0.5296 0.1443 0.0722 0.136 Uiso 0.78 calc PR 1 H4E2_a H 0.5739 0.1931 0.1062 0.136 Uiso 0.78 calc PR 1 H4E3_a H 0.4818 0.2067 0.0750 0.136 Uiso 0.78 calc PR 1 C5E_a C 0.3597(6) 0.1322(5) 0.1161(4) 0.087(4) Uani 0.78 d PD 1 H5E1_a H 0.3722 0.0981 0.0961 0.130 Uiso 0.78 calc PR 1 H5E2_a H 0.3285 0.1618 0.0965 0.130 Uiso 0.78 calc PR 1 H5E3_a H 0.3190 0.1214 0.1432 0.130 Uiso 0.78 calc PR 1 C6E_b C 0.3849(19) 0.1526(17) 0.0926(9) 0.087(4) Uani 0.22 d PD 2 H6E1_b H 0.3991 0.1181 0.0735 0.130 Uiso 0.22 calc PR 2 H6E2_b H 0.3919 0.1871 0.0724 0.130 Uiso 0.22 calc PR 2 H6E3_b H 0.3202 0.1503 0.1046 0.130 Uiso 0.22 calc PR 2 C7E_b C 0.435(2) 0.1051(10) 0.1704(10) 0.085(4) Uani 0.22 d PD 2 H7E1_b H 0.4464 0.0687 0.1533 0.128 Uiso 0.22 calc PR 2 H7E2_b H 0.3696 0.1062 0.1816 0.128 Uiso 0.22 calc PR 2 H7E3_b H 0.4772 0.1079 0.1982 0.128 Uiso 0.22 calc PR 2 C8E_b C 0.5554(10) 0.1546(15) 0.1179(11) 0.090(4) Uani 0.22 d PD 2 H8E1_b H 0.5651 0.1199 0.0981 0.136 Uiso 0.22 calc PR 2 H8E2_b H 0.5980 0.1537 0.1457 0.136 Uiso 0.22 calc PR 2 H8E3_b H 0.5682 0.1890 0.0984 0.136 Uiso 0.22 calc PR 2 O1S O 0.464(3) 0.0158(15) 0.4607(12) 0.223(11) Uiso 0.50 d PD -1 C2S C 0.462(3) 0.0439(12) 0.5048(13) 0.154(11) Uiso 0.50 d PD -1 H2S1 H 0.4853 0.0835 0.4989 0.185 Uiso 0.50 calc PR -1 H2S2 H 0.3950 0.0476 0.5136 0.185 Uiso 0.50 calc PR -1 C3S C 0.506(4) 0.025(2) 0.5443(15) 0.26(2) Uiso 0.50 d PD -1 H3S1 H 0.4640 0.0046 0.5670 0.306 Uiso 0.50 calc PR -1 H3S2 H 0.5410 0.0560 0.5613 0.306 Uiso 0.50 calc PR -1 C4S C 0.584(3) -0.025(2) 0.510(3) 0.36(4) Uiso 0.50 d PD -1 H4S1 H 0.6519 -0.0166 0.5151 0.433 Uiso 0.50 calc PR -1 H4S2 H 0.5705 -0.0658 0.5158 0.433 Uiso 0.50 calc PR -1 C5S C 0.554(4) -0.006(2) 0.467(2) 0.27(2) Uiso 0.50 d PD -1 H5S1 H 0.5599 -0.0394 0.4443 0.324 Uiso 0.50 calc PR -1 H5S2 H 0.5984 0.0236 0.4556 0.324 Uiso 0.50 calc PR -1 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 0.0265(6) 0.0221(5) 0.0270(6) 0.000 0.0021(5) 0.000 Mn2 0.0261(6) 0.0222(5) 0.0235(5) 0.000 -0.0011(5) 0.000 Mn3 0.0325(4) 0.0323(4) 0.0282(4) -0.0020(4) 0.0062(4) -0.0046(4) Mn4 0.0266(4) 0.0343(4) 0.0299(4) -0.0001(4) -0.0022(4) 0.0016(4) O1 0.0251(18) 0.0251(17) 0.0229(17) 0.0001(14) -0.0001(14) 0.0013(15) O11 0.057(3) 0.055(3) 0.041(2) -0.006(2) 0.023(2) -0.005(2) C21_a 0.12(2) 0.12(3) 0.067(18) -0.031(17) 0.050(15) -0.039(17) C31_a 0.17(2) 0.092(14) 0.102(15) -0.020(13) 0.095(16) 0.008(17) C41_a 0.14(3) 0.15(2) 0.068(13) -0.036(15) -0.013(14) 0.041(18) C51_a 0.052(10) 0.11(2) 0.07(2) -0.046(17) 0.026(11) 0.003(12) C21'_b 0.11(2) 0.05(2) 0.06(2) 0.013(16) 0.058(18) -0.020(15) C31'_b 0.064(14) 0.097(19) 0.071(14) 0.028(13) 0.028(11) -0.010(14) C41'_b 0.08(2) 0.100(19) 0.050(12) -0.026(13) 0.021(15) -0.024(17) C51'_b 0.29(5) 0.07(2) 0.08(3) -0.05(2) 0.12(3) -0.09(3) O12 0.035(2) 0.050(3) 0.066(3) -0.005(2) -0.014(2) -0.004(2) C22 0.075(5) 0.069(5) 0.104(7) -0.006(5) -0.040(5) -0.015(4) C32 0.054(5) 0.147(9) 0.112(8) -0.052(7) -0.016(5) -0.019(6) C42 0.059(5) 0.151(9) 0.073(6) 0.009(6) -0.022(4) 0.008(6) C52 0.052(5) 0.089(6) 0.127(7) -0.009(6) -0.037(5) 0.020(4) O1A 0.0238(19) 0.036(2) 0.036(2) 0.0022(17) 0.0031(16) 0.0042(16) O2A 0.029(2) 0.049(2) 0.042(2) -0.0040(19) 0.0002(18) 0.0086(18) C1A 0.027(3) 0.032(3) 0.048(4) 0.005(3) 0.012(3) 0.003(2) C2A 0.035(3) 0.045(3) 0.048(4) -0.007(3) 0.006(3) 0.016(3) C3A 0.065(5) 0.062(5) 0.111(6) -0.033(5) 0.001(5) 0.028(4) C4A 0.071(5) 0.086(6) 0.102(6) 0.009(5) 0.053(5) 0.014(4) C5A 0.081(6) 0.098(6) 0.081(5) -0.002(5) 0.000(5) 0.063(5) O1B 0.0253(19) 0.0347(19) 0.033(2) 0.0038(16) -0.0012(16) -0.0003(16) O2B 0.037(2) 0.042(2) 0.035(2) 0.0000(18) 0.0081(18) -0.0116(19) C1B 0.029(3) 0.029(3) 0.034(3) 0.001(2) 0.000(2) -0.001(2) C2B 0.039(3) 0.043(3) 0.042(3) 0.006(3) -0.002(3) -0.017(3) C3B 0.065(5) 0.056(4) 0.065(4) -0.010(3) 0.002(4) -0.029(4) C4B 0.037(4) 0.077(5) 0.091(6) 0.020(4) -0.004(4) -0.014(4) C5B 0.064(5) 0.073(5) 0.060(4) 0.010(4) 0.008(4) -0.034(4) O1C 0.043(2) 0.055(3) 0.038(2) 0.0034(19) -0.0040(19) -0.002(2) O2C 0.046(2) 0.053(2) 0.032(2) -0.0042(19) 0.0031(19) -0.011(2) C1C 0.050(4) 0.042(3) 0.031(3) -0.003(3) -0.003(3) -0.002(3) C2C 0.054(4) 0.077(5) 0.031(3) 0.004(3) -0.001(3) -0.004(4) C3C 0.106(7) 0.154(9) 0.032(4) 0.024(5) -0.006(4) -0.033(6) C4C 0.184(11) 0.104(7) 0.049(5) -0.021(5) -0.017(6) -0.033(7) C5C 0.091(7) 0.234(13) 0.057(5) 0.003(7) -0.019(5) 0.068(8) O1D 0.037(2) 0.029(2) 0.037(2) -0.0065(16) 0.0070(17) -0.0069(17) O2D 0.043(2) 0.033(2) 0.037(2) -0.0052(17) 0.0052(18) -0.0081(18) C1D 0.038(3) 0.032(3) 0.035(3) -0.009(3) 0.004(3) 0.003(3) C2D 0.078(5) 0.038(3) 0.053(4) -0.019(3) 0.014(4) -0.021(4) C3D_a 0.18(2) 0.041(5) 0.085(8) -0.014(5) 0.041(11) -0.031(10) C4D_a 0.078(6) 0.109(16) 0.092(17) -0.029(9) 0.009(7) -0.060(7) C5D_a 0.128(11) 0.050(15) 0.081(7) -0.042(8) 0.045(8) -0.027(8) C6D_b 0.128(11) 0.050(15) 0.081(7) -0.042(8) 0.045(8) -0.027(8) C7D_b 0.18(2) 0.041(5) 0.085(8) -0.014(5) 0.041(11) -0.031(10) C8D_b 0.078(6) 0.109(16) 0.092(17) -0.029(9) 0.009(7) -0.060(7) O1E 0.039(2) 0.0267(18) 0.0300(19) -0.0057(15) -0.0043(18) 0.0018(18) O2E 0.034(2) 0.033(2) 0.043(2) -0.0054(17) -0.0073(18) 0.0006(17) C1E 0.038(3) 0.029(3) 0.032(3) 0.001(2) 0.005(3) -0.004(3) C2E 0.047(3) 0.036(3) 0.049(4) -0.011(3) -0.006(3) -0.004(3) C3E_a 0.131(11) 0.039(4) 0.086(6) -0.023(4) -0.042(8) 0.034(7) C4E_a 0.132(10) 0.065(7) 0.075(8) -0.031(6) 0.041(7) -0.006(7) C5E_a 0.072(7) 0.071(9) 0.118(10) -0.058(7) -0.029(7) -0.004(5) C6E_b 0.072(7) 0.071(9) 0.118(10) -0.058(7) -0.029(7) -0.004(5) C7E_b 0.131(11) 0.039(4) 0.086(6) -0.023(4) -0.042(8) 0.034(7) C8E_b 0.132(10) 0.065(7) 0.075(8) -0.031(6) 0.041(7) -0.006(7) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn1 O1 1.896(3) 3_655 ? Mn1 O1 1.896(3) . ? Mn1 O1D 1.957(3) 3_655 ? Mn1 O1D 1.957(3) . ? Mn1 O1A 2.247(3) . ? Mn1 O1A 2.247(3) 3_655 ? Mn1 Mn2 2.8154(15) . ? Mn1 Mn3 3.1779(9) 3_655 ? Mn1 Mn3 3.1780(9) . ? Mn2 O1 1.893(3) 3_655 ? Mn2 O1 1.893(3) . ? Mn2 O1E 1.953(3) . ? Mn2 O1E 1.953(3) 3_655 ? Mn2 O1B 2.243(3) . ? Mn2 O1B 2.243(3) 3_655 ? Mn2 Mn4 3.1808(9) . ? Mn2 Mn4 3.1808(9) 3_655 ? Mn3 O1C 2.127(4) . ? Mn3 O2B 2.132(4) . ? Mn3 O2D 2.145(3) . ? Mn3 O1 2.166(3) . ? Mn3 O11 2.290(4) . ? Mn3 O1A 2.348(3) . ? Mn4 O2A 2.117(4) . ? Mn4 O2C 2.117(4) 3_655 ? Mn4 O2E 2.144(4) . ? Mn4 O1 2.177(3) 3_655 ? Mn4 O12 2.305(4) . ? Mn4 O1B 2.340(3) . ? O1 Mn4 2.177(3) 3_655 ? O11 C21'_b 1.424(8) . ? O11 C51'_b 1.427(8) . ? O11 C21_a 1.426(8) . ? O11 C51_a 1.428(7) . ? C21_a C31_a 1.473(13) . ? C31_a C41_a 1.597(19) . ? C41_a C51_a 1.463(12) . ? C21'_b C31'_b 1.467(13) . ? C31'_b C41'_b 1.596(19) . ? C41'_b C51'_b 1.465(13) . ? O12 C22 1.414(8) . ? O12 C52 1.419(7) . ? C22 C32 1.461(10) . ? C32 C42 1.467(11) . ? C42 C52 1.483(10) . ? O1A C1A 1.270(6) . ? O2A C1A 1.256(6) . ? C1A C2A 1.546(7) . ? C2A C5A 1.510(8) . ? C2A C3A 1.524(8) . ? C2A C4A 1.534(8) . ? O1B C1B 1.275(6) . ? O2B C1B 1.250(6) . ? C1B C2B 1.543(7) . ? C2B C3B 1.522(8) . ? C2B C5B 1.524(8) . ? C2B C4B 1.535(8) . ? O1C C1C 1.264(6) . ? O2C C1C 1.251(6) . ? O2C Mn4 2.117(4) 3_655 ? C1C C2C 1.545(7) . ? C2C C3C 1.511(9) . ? C2C C5C 1.512(10) . ? C2C C4C 1.518(10) . ? O1D C1D 1.277(6) . ? O2D C1D 1.245(6) . ? C1D C2D 1.532(7) . ? C2D C5D_a 1.524(8) . ? C2D C6D_b 1.525(9) . ? C2D C7D_b 1.526(9) . ? C2D C3D_a 1.527(8) . ? C2D C8D_b 1.528(9) . ? C2D C4D_a 1.534(8) . ? O1E C1E 1.270(6) . ? O2E C1E 1.247(6) . ? C1E C2E 1.533(7) . ? C2E C8E_b 1.524(9) . ? C2E C5E_a 1.524(7) . ? C2E C6E_b 1.525(9) . ? C2E C3E_a 1.528(7) . ? C2E C7E_b 1.529(9) . ? C2E C4E_a 1.530(7) . ? O1S C5S 1.37(3) . ? O1S C2S 1.37(3) . ? C2S C3S 1.32(3) . ? C2S C5S 2.02(5) . ? C3S C4S 1.84(8) . ? C4S C5S 1.32(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 O1 Mn1 O1 83.94(18) 3_655 . ? O1 Mn1 O1D 94.93(14) 3_655 3_655 ? O1 Mn1 O1D 171.76(14) . 3_655 ? O1 Mn1 O1D 171.76(14) 3_655 . ? O1 Mn1 O1D 94.93(14) . . ? O1D Mn1 O1D 87.3(2) 3_655 . ? O1 Mn1 O1A 98.17(13) 3_655 . ? O1 Mn1 O1A 85.02(13) . . ? O1D Mn1 O1A 87.06(13) 3_655 . ? O1D Mn1 O1A 89.85(13) . . ? O1 Mn1 O1A 85.02(13) 3_655 3_655 ? O1 Mn1 O1A 98.17(13) . 3_655 ? O1D Mn1 O1A 89.85(14) 3_655 3_655 ? O1D Mn1 O1A 87.06(13) . 3_655 ? O1A Mn1 O1A 175.74(18) . 3_655 ? O1 Mn1 Mn2 41.97(9) 3_655 . ? O1 Mn1 Mn2 41.97(9) . . ? O1D Mn1 Mn2 136.33(11) 3_655 . ? O1D Mn1 Mn2 136.33(11) . . ? O1A Mn1 Mn2 92.13(9) . . ? O1A Mn1 Mn2 92.13(9) 3_655 . ? O1 Mn1 Mn3 41.68(9) 3_655 3_655 ? O1 Mn1 Mn3 105.62(10) . 3_655 ? O1D Mn1 Mn3 78.42(10) 3_655 3_655 ? O1D Mn1 Mn3 131.71(10) . 3_655 ? O1A Mn1 Mn3 134.30(9) . 3_655 ? O1A Mn1 Mn3 47.58(9) 3_655 3_655 ? Mn2 Mn1 Mn3 71.26(2) . 3_655 ? O1 Mn1 Mn3 105.62(10) 3_655 . ? O1 Mn1 Mn3 41.67(9) . . ? O1D Mn1 Mn3 131.71(10) 3_655 . ? O1D Mn1 Mn3 78.42(10) . . ? O1A Mn1 Mn3 47.58(9) . . ? O1A Mn1 Mn3 134.30(9) 3_655 . ? Mn2 Mn1 Mn3 71.26(2) . . ? Mn3 Mn1 Mn3 142.53(4) 3_655 . ? O1 Mn2 O1 84.09(18) 3_655 . ? O1 Mn2 O1E 94.66(13) 3_655 . ? O1 Mn2 O1E 171.70(14) . . ? O1 Mn2 O1E 171.70(14) 3_655 3_655 ? O1 Mn2 O1E 94.66(13) . 3_655 ? O1E Mn2 O1E 87.7(2) . 3_655 ? O1 Mn2 O1B 85.30(12) 3_655 . ? O1 Mn2 O1B 97.63(13) . . ? O1E Mn2 O1B 90.43(14) . . ? O1E Mn2 O1B 86.74(14) 3_655 . ? O1 Mn2 O1B 97.63(13) 3_655 3_655 ? O1 Mn2 O1B 85.30(12) . 3_655 ? O1E Mn2 O1B 86.74(14) . 3_655 ? O1E Mn2 O1B 90.43(14) 3_655 3_655 ? O1B Mn2 O1B 176.08(18) . 3_655 ? O1 Mn2 Mn1 42.04(9) 3_655 . ? O1 Mn2 Mn1 42.04(9) . . ? O1E Mn2 Mn1 136.14(10) . . ? O1E Mn2 Mn1 136.14(10) 3_655 . ? O1B Mn2 Mn1 91.96(9) . . ? O1B Mn2 Mn1 91.96(9) 3_655 . ? O1 Mn2 Mn4 41.92(9) 3_655 . ? O1 Mn2 Mn4 104.99(10) . . ? O1E Mn2 Mn4 79.07(10) . . ? O1E Mn2 Mn4 131.37(11) 3_655 . ? O1B Mn2 Mn4 47.33(8) . . ? O1B Mn2 Mn4 134.44(9) 3_655 . ? Mn1 Mn2 Mn4 70.92(2) . . ? O1 Mn2 Mn4 104.99(10) 3_655 3_655 ? O1 Mn2 Mn4 41.92(9) . 3_655 ? O1E Mn2 Mn4 131.37(11) . 3_655 ? O1E Mn2 Mn4 79.07(10) 3_655 3_655 ? O1B Mn2 Mn4 134.44(9) . 3_655 ? O1B Mn2 Mn4 47.33(8) 3_655 3_655 ? Mn1 Mn2 Mn4 70.92(2) . 3_655 ? Mn4 Mn2 Mn4 141.84(4) . 3_655 ? O1C Mn3 O2B 104.45(15) . . ? O1C Mn3 O2D 88.36(15) . . ? O2B Mn3 O2D 160.75(15) . . ? O1C Mn3 O1 95.71(13) . . ? O2B Mn3 O1 99.24(13) . . ? O2D Mn3 O1 93.58(13) . . ? O1C Mn3 O11 85.75(15) . . ? O2B Mn3 O11 82.58(14) . . ? O2D Mn3 O11 84.16(14) . . ? O1 Mn3 O11 177.28(13) . . ? O1C Mn3 O1A 166.33(14) . . ? O2B Mn3 O1A 88.23(13) . . ? O2D Mn3 O1A 80.72(13) . . ? O1 Mn3 O1A 76.92(11) . . ? O11 Mn3 O1A 101.17(14) . . ? O1C Mn3 Mn1 124.06(11) . . ? O2B Mn3 Mn1 108.22(10) . . ? O2D Mn3 Mn1 74.67(10) . . ? O1 Mn3 Mn1 35.58(8) . . ? O11 Mn3 Mn1 141.91(11) . . ? O1A Mn3 Mn1 44.95(8) . . ? O2A Mn4 O2C 103.07(15) . 3_655 ? O2A Mn4 O2E 161.94(15) . . ? O2C Mn4 O2E 88.90(14) 3_655 . ? O2A Mn4 O1 100.76(13) . 3_655 ? O2C Mn4 O1 95.39(13) 3_655 3_655 ? O2E Mn4 O1 91.36(13) . 3_655 ? O2A Mn4 O12 83.25(15) . . ? O2C Mn4 O12 85.67(15) 3_655 . ? O2E Mn4 O12 84.26(14) . . ? O1 Mn4 O12 175.47(13) 3_655 . ? O2A Mn4 O1B 88.16(13) . . ? O2C Mn4 O1B 167.53(13) 3_655 . ? O2E Mn4 O1B 81.54(13) . . ? O1 Mn4 O1B 76.96(11) 3_655 . ? O12 Mn4 O1B 101.21(13) . . ? O2A Mn4 Mn2 108.72(10) . . ? O2C Mn4 Mn2 124.66(11) 3_655 . ? O2E Mn4 Mn2 73.92(10) . . ? O1 Mn4 Mn2 35.51(8) 3_655 . ? O12 Mn4 Mn2 141.17(11) . . ? O1B Mn4 Mn2 44.79(8) . . ? Mn2 O1 Mn1 95.99(14) . . ? Mn2 O1 Mn3 119.20(15) . . ? Mn1 O1 Mn3 102.74(13) . . ? Mn2 O1 Mn4 102.57(13) . 3_655 ? Mn1 O1 Mn4 117.85(15) . 3_655 ? Mn3 O1 Mn4 117.27(14) . 3_655 ? C21'_b O11 C51'_b 108.0(8) . . ? C21_a O11 C51_a 107.9(7) . . ? C21'_b O11 Mn3 117.5(13) . . ? C51'_b O11 Mn3 123.7(10) . . ? C21_a O11 Mn3 121.8(9) . . ? C51_a O11 Mn3 124.7(6) . . ? O11 C21_a C31_a 107.4(9) . . ? C21_a C31_a C41_a 99.4(12) . . ? C51_a C41_a C31_a 99.2(10) . . ? O11 C51_a C41_a 107.9(8) . . ? O11 C21'_b C31'_b 108.4(9) . . ? C21'_b C31'_b C41'_b 100.9(12) . . ? C51'_b C41'_b C31'_b 99.2(12) . . ? O11 C51'_b C41'_b 107.2(9) . . ? C22 O12 C52 109.3(5) . . ? C22 O12 Mn4 125.8(4) . . ? C52 O12 Mn4 121.9(4) . . ? O12 C22 C32 108.3(7) . . ? C22 C32 C42 107.0(7) . . ? C32 C42 C52 105.6(7) . . ? O12 C52 C42 107.1(7) . . ? C1A O1A Mn1 123.8(3) . . ? C1A O1A Mn3 145.0(3) . . ? Mn1 O1A Mn3 87.47(12) . . ? C1A O2A Mn4 128.7(3) . . ? O2A C1A O1A 124.1(5) . . ? O2A C1A C2A 117.9(5) . . ? O1A C1A C2A 118.0(5) . . ? C5A C2A C3A 109.9(6) . . ? C5A C2A C4A 109.9(6) . . ? C3A C2A C4A 109.5(6) . . ? C5A C2A C1A 111.1(5) . . ? C3A C2A C1A 109.6(5) . . ? C4A C2A C1A 106.8(5) . . ? C1B O1B Mn2 121.7(3) . . ? C1B O1B Mn4 146.9(3) . . ? Mn2 O1B Mn4 87.87(12) . . ? C1B O2B Mn3 129.1(3) . . ? O2B C1B O1B 124.4(5) . . ? O2B C1B C2B 118.8(5) . . ? O1B C1B C2B 116.8(5) . . ? C3B C2B C5B 110.8(5) . . ? C3B C2B C4B 109.6(5) . . ? C5B C2B C4B 108.8(5) . . ? C3B C2B C1B 109.8(5) . . ? C5B C2B C1B 111.1(5) . . ? C4B C2B C1B 106.7(5) . . ? C1C O1C Mn3 127.4(4) . . ? C1C O2C Mn4 126.7(4) . 3_655 ? O2C C1C O1C 125.6(5) . . ? O2C C1C C2C 116.9(5) . . ? O1C C1C C2C 117.5(5) . . ? C3C C2C C5C 110.1(7) . . ? C3C C2C C4C 108.3(6) . . ? C5C C2C C4C 109.3(7) . . ? C3C C2C C1C 112.3(5) . . ? C5C C2C C1C 109.2(5) . . ? C4C C2C C1C 107.6(6) . . ? C1D O1D Mn1 131.4(3) . . ? C1D O2D Mn3 128.3(3) . . ? O2D C1D O1D 125.5(5) . . ? O2D C1D C2D 119.5(4) . . ? O1D C1D C2D 114.9(5) . . ? C6D_b C2D C7D_b 110.5(11) . . ? C5D_a C2D C3D_a 110.1(7) . . ? C6D_b C2D C8D_b 110.4(11) . . ? C7D_b C2D C8D_b 110.6(11) . . ? C5D_a C2D C1D 112.1(17) . . ? C6D_b C2D C1D 107(4) . . ? C7D_b C2D C1D 108(4) . . ? C3D_a C2D C1D 110.8(15) . . ? C8D_b C2D C1D 110(4) . . ? C5D_a C2D C4D_a 109.9(7) . . ? C3D_a C2D C4D_a 110.3(7) . . ? C1D C2D C4D_a 103.6(15) . . ? C1E O1E Mn2 131.3(3) . . ? C1E O2E Mn4 129.5(3) . . ? O2E C1E O1E 125.0(5) . . ? O2E C1E C2E 119.2(5) . . ? O1E C1E C2E 115.7(5) . . ? C8E_b C2E C6E_b 110.2(10) . . ? C5E_a C2E C3E_a 110.0(6) . . ? C8E_b C2E C7E_b 109.8(10) . . ? C6E_b C2E C7E_b 109.5(10) . . ? C5E_a C2E C4E_a 109.8(6) . . ? C3E_a C2E C4E_a 109.5(6) . . ? C8E_b C2E C1E 111.4(14) . . ? C5E_a C2E C1E 109.8(6) . . ? C6E_b C2E C1E 111.5(17) . . ? C3E_a C2E C1E 111.9(5) . . ? C7E_b C2E C1E 104.3(13) . . ? C4E_a C2E C1E 105.7(5) . . ? C5S O1S C2S 95(4) . . ? C3S C2S O1S 124(3) . . ? C3S C2S C5S 86(3) . . ? O1S C2S C5S 42.5(18) . . ? C2S C3S C4S 94(3) . . ? C5S C4S C3S 94(3) . . ? C4S C5S O1S 122(3) . . ? C4S C5S C2S 86(3) . . ? O1S C5S C2S 42.5(18) . . ? _refine_diff_density_max 0.481 _refine_diff_density_min -0.358 _refine_diff_density_rms 0.082 #=END #******************************************** #Supplementary Data for Compound 2 #******************************************** data_mnmm86 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety [Mn9K2O7(tma)15(Htma)2] _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C85 H155 K2 Mn9 O41' _chemical_formula_weight 2405.75 _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' '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' 'K' 'K' 0.3868 1.0657 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'P 32 2 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z+2/3' '-x+y, -x, z+1/3' 'y, x, -z' 'x-y, -y, -z+1/3' '-x, -x+y, -z+2/3' _cell_length_a 25.392(5) _cell_length_b 25.392(5) _cell_length_c 16.080(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 8978.3(30) _cell_formula_units_Z 3 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 67 _cell_measurement_theta_min 40 _cell_measurement_theta_max 44 _exptl_crystal_description 'needle (roughly axial mount)' _exptl_crystal_colour 'Very dark red' _exptl_crystal_size_max 0.58 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.335 _exptl_crystal_density_method ? _exptl_crystal_F_000 3768 _exptl_absorpt_coefficient_mu 8.701 _exptl_absorpt_correction_type Psi-scans _exptl_absorpt_correction_T_min 0.275 _exptl_absorpt_correction_T_max 0.337 _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 1.54184 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device ; ? ; _diffrn_measurement_method Omega-theta _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 8 _diffrn_reflns_number 6369 _diffrn_reflns_av_R_equivalents 0.2400 _diffrn_reflns_av_sigmaI/netI 0.2395 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.41 _diffrn_reflns_theta_max 50.08 _reflns_number_total 6027 _reflns_number_observed 3073 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Stoe DIF4' _computing_cell_refinement 'Stoe DIF4' _computing_data_reduction 'Stoe REDU4' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics SHELXTL _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 7 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^)+(0.1112P)^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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.01(2) _refine_ls_number_reflns 6020 _refine_ls_number_parameters 321 _refine_ls_number_restraints 954 _refine_ls_R_factor_all 0.2070 _refine_ls_R_factor_obs 0.0988 _refine_ls_wR_factor_all 0.2558 _refine_ls_wR_factor_obs 0.2008 _refine_ls_goodness_of_fit_all 0.991 _refine_ls_goodness_of_fit_obs 1.101 _refine_ls_restrained_S_all 0.942 _refine_ls_restrained_S_obs 0.985 _refine_ls_shift/esd_max -0.098 _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 Mn1 Mn 0.19952(15) 0.9635(2) 0.0751(2) 0.0383(10) Uani 1 d . . Mn2 Mn 0.30313(14) 0.97697(15) -0.0325(2) 0.0311(9) Uani 1 d . . Mn3 Mn 0.24082(14) 0.86055(15) 0.1052(2) 0.0314(9) Uani 1 d . . Mn4 Mn 0.42083(14) 1.09235(14) 0.0572(2) 0.0262(8) Uani 1 d . . Mn5 Mn 0.3328(2) 1.0000 0.1667 0.0268(11) Uani 1 d S . K1 K 0.4088(2) 0.9337(2) 0.0660(3) 0.0430(14) Uani 1 d . . O1 O 0.2507(6) 1.0000 0.1667 0.024(4) Uiso 1 d S . O2 O 0.2452(5) 0.9270(5) 0.0473(7) 0.030(3) Uiso 1 d . . O3 O 0.3096(5) 0.9142(5) 0.1633(7) 0.024(3) Uiso 1 d . . O4 O 0.3633(5) 1.0111(5) 0.0521(6) 0.022(3) Uiso 1 d . . O1A O 0.5140(7) 1.0197(6) 0.0132(9) 0.077(6) Uiso 1 d D . O2A O 0.4896(5) 1.0719(6) 0.1001(7) 0.039(4) Uiso 1 d D . C1A C 0.5279(6) 1.0637(8) 0.0625(12) 0.061(8) Uiso 1 d D . C2A C 0.5954(6) 1.1089(7) 0.0727(9) 0.056(7) Uiso 1 d D . C3A C 0.6048(10) 1.1644(8) 0.1218(13) 0.100(10) Uiso 1 d D . H3A1 H 0.6484(10) 1.1930(8) 0.1281(13) 0.150 Uiso 1 calc R . H3A2 H 0.5861(10) 1.1516(8) 0.1769(13) 0.150 Uiso 1 calc R . H3A3 H 0.5858(10) 1.1843(8) 0.0920(13) 0.150 Uiso 1 calc R . C4A C 0.6264(9) 1.0794(10) 0.1199(13) 0.091(10) Uiso 1 d D . H4A1 H 0.6698(9) 1.1089(10) 0.1262(13) 0.137 Uiso 1 calc R . H4A2 H 0.6214(9) 1.0441(10) 0.0887(13) 0.137 Uiso 1 calc R . H4A3 H 0.6077(9) 1.0664(10) 0.1749(13) 0.137 Uiso 1 calc R . C5A C 0.6255(10) 1.1299(11) -0.0123(11) 0.123(12) Uiso 1 d D . H5A1 H 0.6690(10) 1.1589(11) -0.0050(11) 0.185 Uiso 1 calc R . H5A2 H 0.6065(10) 1.1495(11) -0.0425(11) 0.185 Uiso 1 calc R . H5A3 H 0.6205(10) 1.0947(11) -0.0441(11) 0.185 Uiso 1 calc R . O1B O 0.5573(7) 0.9554(6) -0.0482(10) 0.087(6) Uiso 1 d D . H1B H 0.5454(7) 0.9783(6) -0.0284(10) 0.130 Uiso 1 calc R . O2B O 0.4643(6) 0.8817(7) -0.0105(9) 0.069(5) Uiso 1 d D . C1B C 0.5159(8) 0.8996(7) -0.0373(13) 0.079(9) Uiso 1 d D . C2B C 0.5340(7) 0.8544(7) -0.0717(10) 0.066(8) Uiso 1 d D . C3B C 0.5903(8) 0.8634(10) -0.0259(13) 0.093(10) Uiso 1 d D . H3B1 H 0.6233(8) 0.9055(10) -0.0329(13) 0.140 Uiso 1 calc R . H3B2 H 0.6030(8) 0.8356(10) -0.0487(13) 0.140 Uiso 1 calc R . H3B3 H 0.5811(8) 0.8549(10) 0.0334(13) 0.140 Uiso 1 calc R . C4B C 0.4825(9) 0.7895(8) -0.0618(16) 0.129(13) Uiso 1 d D . H4B1 H 0.4465(9) 0.7843(8) -0.0915(16) 0.194 Uiso 1 calc R . H4B2 H 0.4729(9) 0.7806(8) -0.0027(16) 0.194 Uiso 1 calc R . H4B3 H 0.4949(9) 0.7616(8) -0.0849(16) 0.194 Uiso 1 calc R . C5B C 0.5492(12) 0.8681(12) -0.1643(10) 0.128(13) Uiso 1 d D . H5B1 H 0.5825(12) 0.9100(12) -0.1709(10) 0.192 Uiso 1 calc R . H5B2 H 0.5132(12) 0.8628(12) -0.1942(10) 0.192 Uiso 1 calc R . H5B3 H 0.5616(12) 0.8401(12) -0.1870(10) 0.192 Uiso 1 calc R . O1C O 0.3275(6) 0.9118(5) -0.0728(7) 0.048(4) Uiso 1 d D . O2C O 0.2782(6) 0.8325(5) 0.0125(7) 0.049(4) Uiso 1 d D . C1C C 0.3075(9) 0.8570(6) -0.0529(9) 0.049(6) Uiso 1 d D . C2C C 0.3069(7) 0.8148(6) -0.1220(8) 0.045(6) Uiso 1 d D . C3C C 0.3135(9) 0.7636(7) -0.0834(11) 0.056(7) Uiso 1 d D . H3C1 H 0.3523(9) 0.7808(7) -0.0538(11) 0.084 Uiso 1 calc R . H3C2 H 0.3123(9) 0.7363(7) -0.1274(11) 0.084 Uiso 1 calc R . H3C3 H 0.2800(9) 0.7407(7) -0.0443(11) 0.084 Uiso 1 calc R . C4C C 0.2465(7) 0.7886(9) -0.1683(12) 0.083(9) Uiso 1 d D . H4C1 H 0.2426(7) 0.8219(9) -0.1928(12) 0.124 Uiso 1 calc R . H4C2 H 0.2130(7) 0.7658(9) -0.1294(12) 0.124 Uiso 1 calc R . H4C3 H 0.2452(7) 0.7614(9) -0.2125(12) 0.124 Uiso 1 calc R . C5C C 0.3589(8) 0.8500(9) -0.1831(11) 0.080(9) Uiso 1 d D . H5C1 H 0.3548(8) 0.8831(9) -0.2079(11) 0.120 Uiso 1 calc R . H5C2 H 0.3574(8) 0.8225(9) -0.2270(11) 0.120 Uiso 1 calc R . H5C3 H 0.3978(8) 0.8671(9) -0.1536(11) 0.120 Uiso 1 calc R . O1D O 0.1563(5) 0.8073(5) 0.0734(7) 0.037(4) Uiso 1 d D . O2D O 0.1294(5) 0.8727(5) 0.1236(8) 0.038(4) Uiso 1 d D . C1D C 0.1182(6) 0.8239(6) 0.0900(11) 0.032(6) Uiso 1 d D . C2D C 0.0514(6) 0.7762(6) 0.0735(9) 0.048(7) Uiso 1 d D . C3D C 0.0471(9) 0.7436(9) -0.0087(10) 0.078(9) Uiso 1 d D . H3D1 H 0.0625(9) 0.7733(9) -0.0541(10) 0.117 Uiso 1 calc R . H3D2 H 0.0046(9) 0.7130(9) -0.0195(10) 0.117 Uiso 1 calc R . H3D3 H 0.0716(9) 0.7237(9) -0.0049(10) 0.117 Uiso 1 calc R . C4D C 0.0276(9) 0.7296(8) 0.1433(11) 0.089(10) Uiso 1 d D . H4D1 H 0.0525(9) 0.7101(8) 0.1472(11) 0.133 Uiso 1 calc R . H4D2 H -0.0146(9) 0.6987(8) 0.1317(11) 0.133 Uiso 1 calc R . H4D3 H 0.0297(9) 0.7499(8) 0.1960(11) 0.133 Uiso 1 calc R . C5D C 0.0129(8) 0.8064(9) 0.0675(13) 0.084(9) Uiso 1 d D . H5D1 H 0.0283(8) 0.8365(9) 0.0225(13) 0.127 Uiso 1 calc R . H5D2 H 0.0149(8) 0.8267(9) 0.1202(13) 0.127 Uiso 1 calc R . H5D3 H -0.0294(8) 0.7755(9) 0.0559(13) 0.127 Uiso 1 calc R . O1E O 0.2364(5) 0.9459(6) -0.1156(7) 0.039(4) Uiso 1 d D . O2E O 0.1594(6) 0.9370(6) -0.0371(7) 0.046(4) Uiso 1 d D . C1E C 0.1826(7) 0.9337(9) -0.1040(8) 0.046(6) Uiso 1 d D . C2E C 0.1426(6) 0.9158(8) -0.1824(8) 0.054(7) Uiso 1 d D . C3E C 0.1809(13) 0.9199(19) -0.2582(12) 0.036(13) Uiso 0.43 d PD 1 H3E1 H 0.1973(13) 0.8926(19) -0.2506(12) 0.055 Uiso 0.43 calc PR 1 H3E2 H 0.2144(13) 0.9617(19) -0.2645(12) 0.055 Uiso 0.43 calc PR 1 H3E3 H 0.1553(13) 0.9079(19) -0.3082(12) 0.055 Uiso 0.43 calc PR 1 C4E C 0.0901(14) 0.8508(12) -0.1744(23) 0.126(30) Uiso 0.43 d PD 1 H4E1 H 0.1062(14) 0.8232(12) -0.1668(23) 0.189 Uiso 0.43 calc PR 1 H4E2 H 0.0652(14) 0.8395(12) -0.2249(23) 0.189 Uiso 0.43 calc PR 1 H4E3 H 0.0650(14) 0.8478(12) -0.1263(23) 0.189 Uiso 0.43 calc PR 1 C5E C 0.1178(19) 0.9587(18) -0.1942(21) 0.071(19) Uiso 0.43 d PD 1 H5E1 H 0.1516(19) 1.0005(18) -0.1992(21) 0.106 Uiso 0.43 calc PR 1 H5E2 H 0.0927(19) 0.9557(18) -0.1461(21) 0.106 Uiso 0.43 calc PR 1 H5E3 H 0.0930(19) 0.9475(18) -0.2448(21) 0.106 Uiso 0.43 calc PR 1 C6E C 0.0788(9) 0.9044(15) -0.1634(19) 0.038(10) Uiso 0.57 d PD 2 H6E1 H 0.0817(9) 0.9408(15) -0.1381(19) 0.057 Uiso 0.57 calc PR 2 H6E2 H 0.0585(9) 0.8701(15) -0.1248(19) 0.057 Uiso 0.57 calc PR 2 H6E3 H 0.0554(9) 0.8949(15) -0.2151(19) 0.057 Uiso 0.57 calc PR 2 C7E C 0.1755(15) 0.9704(12) -0.2388(22) 0.085(16) Uiso 0.57 d PD 2 H7E1 H 0.1775(15) 1.0061(12) -0.2121(22) 0.128 Uiso 0.57 calc PR 2 H7E2 H 0.1536(15) 0.9624(12) -0.2917(22) 0.128 Uiso 0.57 calc PR 2 H7E3 H 0.2169(15) 0.9783(12) -0.2492(22) 0.128 Uiso 0.57 calc PR 2 C8E C 0.1391(16) 0.8599(12) -0.2210(23) 0.067(14) Uiso 0.57 d PD 2 H8E1 H 0.1177(16) 0.8253(12) -0.1832(23) 0.101 Uiso 0.57 calc PR 2 H8E2 H 0.1803(16) 0.8672(12) -0.2311(23) 0.101 Uiso 0.57 calc PR 2 H8E3 H 0.1170(16) 0.8509(12) -0.2739(23) 0.101 Uiso 0.57 calc PR 2 O1F O 0.2689(5) 1.0417(4) -0.0063(7) 0.032(4) Uiso 1 d D . O2F O 0.3594(5) 1.1241(5) 0.0195(8) 0.038(4) Uiso 1 d D . C1F C 0.3048(6) 1.0988(6) -0.0023(10) 0.039(6) Uiso 1 d D . C2F C 0.2820(6) 1.1384(6) -0.0427(8) 0.030(6) Uiso 1 d D . C3F C 0.2172(6) 1.1175(9) -0.0163(12) 0.069(8) Uiso 1 d D . H3F1 H 0.1909(6) 1.0750(9) -0.0330(12) 0.103 Uiso 1 calc R . H3F2 H 0.2032(6) 1.1429(9) -0.0432(12) 0.103 Uiso 1 calc R . H3F3 H 0.2156(6) 1.1209(9) 0.0442(12) 0.103 Uiso 1 calc R . C4F C 0.3227(8) 1.2046(6) -0.0167(12) 0.072(8) Uiso 1 d D . H4F1 H 0.3647(8) 1.2183(6) -0.0336(12) 0.108 Uiso 1 calc R . H4F2 H 0.3210(8) 1.2080(6) 0.0438(12) 0.108 Uiso 1 calc R . H4F3 H 0.3087(8) 1.2299(6) -0.0436(12) 0.108 Uiso 1 calc R . C5F C 0.2855(10) 1.1339(10) -0.1371(8) 0.085(9) Uiso 1 d D . H5F1 H 0.3275(10) 1.1475(10) -0.1535(8) 0.127 Uiso 1 calc R . H5F2 H 0.2718(10) 1.1596(10) -0.1639(8) 0.127 Uiso 1 calc R . H5F3 H 0.2593(10) 1.0915(10) -0.1545(8) 0.127 Uiso 1 calc R . O1G O 0.3572(4) 1.0305(5) -0.1172(6) 0.028(3) Uiso 1 d D . O2G O 0.4463(5) 1.0954(5) -0.0572(6) 0.037(4) Uiso 1 d D . C1G C 0.4121(6) 1.0709(7) -0.1180(8) 0.037(6) Uiso 1 d D . C2G C 0.4434(6) 1.0854(6) -0.2037(7) 0.037(5) Uiso 1 d D . C3G C 0.4635(9) 1.0389(8) -0.2218(12) 0.080(8) Uiso 1 d D . H3G1 H 0.4920(9) 1.0415(8) -0.1787(12) 0.120 Uiso 1 calc R . H3G2 H 0.4835(9) 1.0476(8) -0.2762(12) 0.120 Uiso 1 calc R . H3G3 H 0.4279(9) 0.9979(8) -0.2222(12) 0.120 Uiso 1 calc R . C4G C 0.4998(7) 1.1486(7) -0.2017(12) 0.073(8) Uiso 1 d D . H4G1 H 0.5278(7) 1.1498(7) -0.1587(12) 0.109 Uiso 1 calc R . H4G2 H 0.4878(7) 1.1789(7) -0.1891(12) 0.109 Uiso 1 calc R . H4G3 H 0.5201(7) 1.1576(7) -0.2559(12) 0.109 Uiso 1 calc R . C5G C 0.3991(8) 1.0821(10) -0.2692(10) 0.089(9) Uiso 1 d D . H5G1 H 0.3632(8) 1.0413(10) -0.2695(10) 0.134 Uiso 1 calc R . H5G2 H 0.4187(8) 1.0908(10) -0.3239(10) 0.134 Uiso 1 calc R . H5G3 H 0.3867(8) 1.1121(10) -0.2567(10) 0.134 Uiso 1 calc R . O1H O 0.4368(6) 1.2087(5) 0.1613(8) 0.046(4) Uiso 1 d D . O2H O 0.4808(5) 1.1775(5) 0.0675(7) 0.031(4) Uiso 1 d D . C1H C 0.4769(7) 1.2180(6) 0.1064(10) 0.048(6) Uiso 1 d D . C2H C 0.5239(6) 1.2850(6) 0.0928(9) 0.045(6) Uiso 1 d D . C3H C 0.4926(9) 1.3231(8) 0.0920(12) 0.073(8) Uiso 1 d D . H3H1 H 0.4625(9) 1.3090(8) 0.0471(12) 0.109 Uiso 1 calc R . H3H2 H 0.5230(9) 1.3660(8) 0.0829(12) 0.109 Uiso 1 calc R . H3H3 H 0.4723(9) 1.3189(8) 0.1454(12) 0.109 Uiso 1 calc R . C4H C 0.5707(8) 1.3071(9) 0.1627(11) 0.068(8) Uiso 1 d D . H4H1 H 0.6010(8) 1.3500(9) 0.1537(11) 0.102 Uiso 1 calc R . H4H2 H 0.5911(8) 1.2829(9) 0.1631(11) 0.102 Uiso 1 calc R . H4H3 H 0.5503(8) 1.3026(9) 0.2161(11) 0.102 Uiso 1 calc R . C5H C 0.5564(9) 1.2934(10) 0.0094(10) 0.095(10) Uiso 1 d D . H5H1 H 0.5265(9) 1.2793(10) -0.0358(10) 0.142 Uiso 1 calc R . H5H2 H 0.5772(9) 1.2697(10) 0.0094(10) 0.142 Uiso 1 calc R . H5H3 H 0.5861(9) 1.3365(10) 0.0012(10) 0.142 Uiso 1 calc R . O1I O 0.1437(6) 0.9919(6) 0.0984(8) 0.037(4) Uiso 1 d . . C1I C 0.1232(15) 1.0000 0.1667 0.068(11) Uiso 1 d S . C2I C 0.0617(15) 1.0000 0.1667 0.071(12) Uiso 1 d S . C3I C 0.0754(20) 1.0580(19) 0.1150(29) 0.051(14) Uiso 0.50 d P -1 H3I1 H 0.1061(20) 1.0944(19) 0.1440(29) 0.076 Uiso 0.50 calc PR -1 H3I2 H 0.0380(20) 1.0598(19) 0.1088(29) 0.076 Uiso 0.50 calc PR -1 H3I3 H 0.0908(20) 1.0558(19) 0.0599(29) 0.076 Uiso 0.50 calc PR -1 C4I C 0.0201(38) 0.9512(38) 0.1205(56) 0.154(37) Uiso 0.50 d P -1 H4I1 H -0.0188(38) 0.9506(38) 0.1199(56) 0.231 Uiso 0.50 calc PR -1 H4I2 H 0.0144(38) 0.9134(38) 0.1452(56) 0.231 Uiso 0.50 calc PR -1 H4I3 H 0.0351(38) 0.9549(38) 0.0634(56) 0.231 Uiso 0.50 calc PR -1 C5I C 0.0520(33) 1.0242(34) 0.2558(41) 0.111(27) Uiso 0.50 d P -1 H5I1 H 0.0900(33) 1.0603(34) 0.2728(41) 0.166 Uiso 0.50 calc PR -1 H5I2 H 0.0402(33) 0.9922(34) 0.2977(41) 0.166 Uiso 0.50 calc PR -1 H5I3 H 0.0199(33) 1.0348(34) 0.2507(41) 0.166 Uiso 0.50 calc PR -1 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 0.031(2) 0.054(3) 0.026(2) 0.012(2) -0.003(2) 0.019(2) Mn2 0.031(2) 0.035(2) 0.021(2) 0.002(2) 0.001(2) 0.012(2) Mn3 0.030(2) 0.032(2) 0.023(2) 0.002(2) 0.000(2) 0.009(2) Mn4 0.030(2) 0.027(2) 0.017(2) 0.005(2) 0.003(2) 0.012(2) Mn5 0.034(2) 0.026(3) 0.018(2) 0.004(2) 0.0018(11) 0.0130(14) K1 0.040(3) 0.056(4) 0.029(3) 0.002(3) -0.001(2) 0.021(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn1 O2 1.864(13) . ? Mn1 O1 1.873(8) . ? Mn1 O1I 1.922(13) . ? Mn1 O2E 2.015(12) . ? Mn1 O2D 2.232(12) . ? Mn1 O1F 2.295(11) . ? Mn1 Mn2 3.022(4) . ? Mn2 O2 1.886(12) . ? Mn2 O4 1.901(11) . ? Mn2 O1G 1.929(11) . ? Mn2 O1E 1.985(11) . ? Mn2 O1C 2.136(12) . ? Mn2 O1F 2.250(12) . ? Mn2 K1 3.723(6) . ? Mn3 O3 1.844(12) . ? Mn3 O2 1.880(12) . ? Mn3 O1H 1.945(12) 5_675 ? Mn3 O1D 1.948(12) . ? Mn3 O2C 2.075(12) . ? Mn3 K1 3.757(6) . ? Mn4 O4 1.840(12) . ? Mn4 O3 1.906(11) 5_675 ? Mn4 O2H 1.931(11) . ? Mn4 O2G 1.938(11) . ? Mn4 O2F 2.168(12) . ? Mn4 O2A 2.169(12) . ? Mn4 Mn5 2.891(3) . ? Mn4 K1 3.830(5) 5_675 ? Mn4 K1 3.887(6) . ? Mn5 O3 1.953(12) 5_675 ? Mn5 O3 1.953(12) . ? Mn5 O4 1.964(10) 5_675 ? Mn5 O4 1.964(10) . ? Mn5 O1 2.09(2) . ? Mn5 Mn4 2.891(3) 5_675 ? Mn5 K1 3.525(6) 5_675 ? Mn5 K1 3.525(6) . ? K1 O1A 2.61(2) . ? K1 O2B 2.666(13) . ? K1 O2A 2.707(12) 5_675 ? K1 O4 2.741(12) . ? K1 O3 2.790(12) . ? K1 O1C 2.900(14) . ? K1 C1C 3.01(2) . ? K1 O2A 3.101(13) . ? K1 O2C 3.135(14) . ? K1 C1A 3.17(2) . ? O1 Mn1 1.873(8) 5_675 ? O3 Mn4 1.906(12) 5_675 ? O1A C1A 1.269(13) . ? O2A C1A 1.247(12) . ? O2A K1 2.707(12) 5_675 ? C1A C2A 1.522(14) . ? C2A C5A 1.527(12) . ? C2A C3A 1.528(12) . ? C2A C4A 1.529(12) . ? O1B C1B 1.287(13) . ? O2B C1B 1.231(13) . ? C1B C2B 1.534(14) . ? C2B C4B 1.515(12) . ? C2B C3B 1.523(12) . ? C2B C5B 1.534(12) . ? O1C C1C 1.261(12) . ? O2C C1C 1.260(12) . ? C1C C2C 1.537(14) . ? C2C C3C 1.524(12) . ? C2C C4C 1.525(12) . ? C2C C5C 1.525(12) . ? O1D C1D 1.262(12) . ? O2D C1D 1.247(12) . ? C1D C2D 1.535(13) . ? C2D C4D 1.519(12) . ? C2D C5D 1.520(12) . ? C2D C3D 1.533(12) . ? O1E C1E 1.257(12) . ? O2E C1E 1.250(12) . ? C1E C2E 1.538(14) . ? C2E C8E 1.511(13) . ? C2E C7E 1.512(13) . ? C2E C5E 1.519(12) . ? C2E C4E 1.523(13) . ? C2E C6E 1.526(13) . ? C2E C3E 1.530(12) . ? O1F C1F 1.271(12) . ? O2F C1F 1.253(12) . ? C1F C2F 1.533(13) . ? C2F C3F 1.515(12) . ? C2F C4F 1.525(12) . ? C2F C5F 1.528(12) . ? O1G C1G 1.251(12) . ? O2G C1G 1.247(12) . ? C1G C2G 1.540(13) . ? C2G C5G 1.513(12) . ? C2G C4G 1.526(12) . ? C2G C3G 1.529(12) . ? O1H C1H 1.276(12) . ? O1H Mn3 1.945(12) 5_675 ? O2H C1H 1.251(12) . ? C1H C2H 1.529(14) . ? C2H C4H 1.525(12) . ? C2H C3H 1.529(12) . ? C2H C5H 1.532(12) . ? O1I C1I 1.28(2) . ? C1I O1I 1.28(2) 5_675 ? C1I C2I 1.56(5) . ? C2I C4I 1.38(8) 5_675 ? C2I C4I 1.38(8) . ? C2I C3I 1.57(4) 5_675 ? C2I C3I 1.57(4) . ? C2I C5I 1.63(7) . ? C2I C5I 1.63(7) 5_675 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Mn1 O1 89.2(6) . . ? O2 Mn1 O1I 172.7(6) . . ? O1 Mn1 O1I 96.9(6) . . ? O2 Mn1 O2E 87.5(5) . . ? O1 Mn1 O2E 168.1(5) . . ? O1I Mn1 O2E 87.4(5) . . ? O2 Mn1 O2D 86.8(5) . . ? O1 Mn1 O2D 103.5(3) . . ? O1I Mn1 O2D 87.9(5) . . ? O2E Mn1 O2D 87.7(5) . . ? O2 Mn1 O1F 84.0(5) . . ? O1 Mn1 O1F 88.7(3) . . ? O1I Mn1 O1F 100.2(5) . . ? O2E Mn1 O1F 79.6(5) . . ? O2D Mn1 O1F 164.5(4) . . ? O2 Mn1 Mn2 36.6(4) . . ? O1 Mn1 Mn2 92.6(4) . . ? O1I Mn1 Mn2 146.3(4) . . ? O2E Mn1 Mn2 78.0(3) . . ? O2D Mn1 Mn2 121.1(3) . . ? O1F Mn1 Mn2 47.7(3) . . ? O2 Mn2 O4 89.9(5) . . ? O2 Mn2 O1G 174.8(5) . . ? O4 Mn2 O1G 93.3(4) . . ? O2 Mn2 O1E 88.1(5) . . ? O4 Mn2 O1E 174.2(5) . . ? O1G Mn2 O1E 88.3(5) . . ? O2 Mn2 O1C 96.6(5) . . ? O4 Mn2 O1C 95.3(5) . . ? O1G Mn2 O1C 87.2(5) . . ? O1E Mn2 O1C 90.4(5) . . ? O2 Mn2 O1F 84.7(5) . . ? O4 Mn2 O1F 92.8(5) . . ? O1G Mn2 O1F 91.0(4) . . ? O1E Mn2 O1F 81.5(5) . . ? O1C Mn2 O1F 171.8(5) . . ? O2 Mn2 Mn1 36.1(4) . . ? O4 Mn2 Mn1 95.6(3) . . ? O1G Mn2 Mn1 139.2(4) . . ? O1E Mn2 Mn1 79.6(3) . . ? O1C Mn2 Mn1 131.2(3) . . ? O1F Mn2 Mn1 49.0(3) . . ? O2 Mn2 K1 86.9(4) . . ? O4 Mn2 K1 45.3(4) . . ? O1G Mn2 K1 98.3(3) . . ? O1E Mn2 K1 140.0(4) . . ? O1C Mn2 K1 51.0(4) . . ? O1F Mn2 K1 137.2(3) . . ? Mn1 Mn2 K1 115.95(12) . . ? O3 Mn3 O2 88.8(5) . . ? O3 Mn3 O1H 93.2(5) . 5_675 ? O2 Mn3 O1H 173.2(6) . 5_675 ? O3 Mn3 O1D 162.5(5) . . ? O2 Mn3 O1D 92.4(5) . . ? O1H Mn3 O1D 83.7(5) 5_675 . ? O3 Mn3 O2C 101.0(5) . . ? O2 Mn3 O2C 96.9(5) . . ? O1H Mn3 O2C 89.1(5) 5_675 . ? O1D Mn3 O2C 96.2(5) . . ? O3 Mn3 K1 45.4(4) . . ? O2 Mn3 K1 86.0(4) . . ? O1H Mn3 K1 100.0(4) 5_675 . ? O1D Mn3 K1 152.1(4) . . ? O2C Mn3 K1 56.5(4) . . ? O4 Mn4 O3 84.3(5) . 5_675 ? O4 Mn4 O2H 177.6(5) . . ? O3 Mn4 O2H 93.4(5) 5_675 . ? O4 Mn4 O2G 93.7(5) . . ? O3 Mn4 O2G 177.4(5) 5_675 . ? O2H Mn4 O2G 88.6(5) . . ? O4 Mn4 O2F 95.1(5) . . ? O3 Mn4 O2F 91.4(5) 5_675 . ? O2H Mn4 O2F 85.4(5) . . ? O2G Mn4 O2F 90.4(5) . . ? O4 Mn4 O2A 91.6(5) . . ? O3 Mn4 O2A 87.3(5) 5_675 . ? O2H Mn4 O2A 87.8(5) . . ? O2G Mn4 O2A 91.1(5) . . ? O2F Mn4 O2A 173.0(5) . . ? O4 Mn4 Mn5 42.2(3) . . ? O3 Mn4 Mn5 42.1(4) 5_675 . ? O2H Mn4 Mn5 135.5(4) . . ? O2G Mn4 Mn5 135.9(4) . . ? O2F Mn4 Mn5 93.6(3) . . ? O2A Mn4 Mn5 90.0(3) . . ? O4 Mn4 K1 89.9(3) . 5_675 ? O3 Mn4 K1 43.9(3) 5_675 5_675 ? O2H Mn4 K1 88.1(4) . 5_675 ? O2G Mn4 K1 134.6(4) . 5_675 ? O2F Mn4 K1 134.3(4) . 5_675 ? O2A Mn4 K1 43.5(3) . 5_675 ? Mn5 Mn4 K1 61.40(11) . 5_675 ? O4 Mn4 K1 39.8(4) . . ? O3 Mn4 K1 91.5(4) 5_675 . ? O2H Mn4 K1 140.0(4) . . ? O2G Mn4 K1 85.9(4) . . ? O2F Mn4 K1 134.2(3) . . ? O2A Mn4 K1 52.8(3) . . ? Mn5 Mn4 K1 60.58(11) . . ? K1 Mn4 K1 68.72(13) 5_675 . ? O3 Mn5 O3 150.3(7) 5_675 . ? O3 Mn5 O4 90.6(5) 5_675 5_675 ? O3 Mn5 O4 79.8(5) . 5_675 ? O3 Mn5 O4 79.8(5) 5_675 . ? O3 Mn5 O4 90.6(5) . . ? O4 Mn5 O4 142.3(7) 5_675 . ? O3 Mn5 O1 104.9(4) 5_675 . ? O3 Mn5 O1 104.9(4) . . ? O4 Mn5 O1 108.9(3) 5_675 . ? O4 Mn5 O1 108.9(3) . . ? O3 Mn5 Mn4 124.6(4) 5_675 5_675 ? O3 Mn5 Mn4 40.9(3) . 5_675 ? O4 Mn5 Mn4 39.0(3) 5_675 5_675 ? O4 Mn5 Mn4 122.7(4) . 5_675 ? O1 Mn5 Mn4 111.58(11) . 5_675 ? O3 Mn5 Mn4 40.9(3) 5_675 . ? O3 Mn5 Mn4 124.6(4) . . ? O4 Mn5 Mn4 122.7(4) 5_675 . ? O4 Mn5 Mn4 39.0(3) . . ? O1 Mn5 Mn4 111.58(11) . . ? Mn4 Mn5 Mn4 136.8(2) 5_675 . ? O3 Mn5 K1 52.1(3) 5_675 5_675 ? O3 Mn5 K1 102.2(4) . 5_675 ? O4 Mn5 K1 50.7(3) 5_675 5_675 ? O4 Mn5 K1 97.2(4) . 5_675 ? O1 Mn5 K1 141.85(9) . 5_675 ? Mn4 Mn5 K1 73.83(13) 5_675 5_675 ? Mn4 Mn5 K1 72.54(12) . 5_675 ? O3 Mn5 K1 102.2(4) 5_675 . ? O3 Mn5 K1 52.1(3) . . ? O4 Mn5 K1 97.2(4) 5_675 . ? O4 Mn5 K1 50.7(3) . . ? O1 Mn5 K1 141.85(9) . . ? Mn4 Mn5 K1 72.54(12) 5_675 . ? Mn4 Mn5 K1 73.83(13) . . ? K1 Mn5 K1 76.3(2) 5_675 . ? O1A K1 O2B 71.9(4) . . ? O1A K1 O2A 106.9(4) . 5_675 ? O2B K1 O2A 110.7(4) . 5_675 ? O1A K1 O4 89.8(4) . . ? O2B K1 O4 146.5(4) . . ? O2A K1 O4 101.2(3) 5_675 . ? O1A K1 O3 142.0(4) . . ? O2B K1 O3 145.5(4) . . ? O2A K1 O3 61.7(3) 5_675 . ? O4 K1 O3 60.4(3) . . ? O1A K1 O1C 104.1(4) . . ? O2B K1 O1C 93.0(4) . . ? O2A K1 O1C 145.5(4) 5_675 . ? O4 K1 O1C 63.9(3) . . ? O3 K1 O1C 84.5(4) . . ? O1A K1 C1C 121.4(4) . . ? O2B K1 C1C 83.0(4) . . ? O2A K1 C1C 131.6(4) 5_675 . ? O4 K1 C1C 83.2(4) . . ? O3 K1 C1C 80.7(4) . . ? O1C K1 C1C 24.6(3) . . ? O1A K1 O2A 44.7(3) . . ? O2B K1 O2A 115.3(4) . . ? O2A K1 O2A 81.9(4) 5_675 . ? O4 K1 O2A 58.8(3) . . ? O3 K1 O2A 97.5(3) . . ? O1C K1 O2A 111.0(3) . . ? C1C K1 O2A 135.4(4) . . ? O1A K1 O2C 145.0(4) . . ? O2B K1 O2C 94.1(4) . . ? O2A K1 O2C 108.2(4) 5_675 . ? O4 K1 O2C 85.0(3) . . ? O3 K1 O2C 61.1(3) . . ? O1C K1 O2C 43.2(3) . . ? C1C K1 O2C 23.5(2) . . ? O2A K1 O2C 143.7(4) . . ? O1A K1 C1A 22.8(3) . . ? O2B K1 C1A 92.4(4) . . ? O2A K1 C1A 90.7(4) 5_675 . ? O4 K1 C1A 77.1(4) . . ? O3 K1 C1A 120.1(4) . . ? O1C K1 C1A 113.7(4) . . ? C1C K1 C1A 136.3(5) . . ? O2A K1 C1A 22.9(2) . . ? O2C K1 C1A 156.3(5) . . ? O1A K1 Mn5 109.1(3) . . ? O2B K1 Mn5 178.9(4) . . ? O2A K1 Mn5 69.5(3) 5_675 . ? O4 K1 Mn5 33.7(2) . . ? O3 K1 Mn5 33.5(2) . . ? O1C K1 Mn5 86.4(3) . . ? C1C K1 Mn5 96.1(3) . . ? O2A K1 Mn5 65.7(2) . . ? O2C K1 Mn5 84.8(3) . . ? C1A K1 Mn5 88.6(3) . . ? O1A K1 Mn2 101.7(4) . . ? O2B K1 Mn2 126.0(4) . . ? O2A K1 Mn2 122.0(3) 5_675 . ? O4 K1 Mn2 29.5(2) . . ? O3 K1 Mn2 64.6(3) . . ? O1C K1 Mn2 34.9(2) . . ? C1C K1 Mn2 54.0(3) . . ? O2A K1 Mn2 84.7(3) . . ? O2C K1 Mn2 60.1(2) . . ? C1A K1 Mn2 97.9(4) . . ? Mn5 K1 Mn2 53.64(9) . . ? Mn1 O1 Mn1 127.1(9) 5_675 . ? Mn1 O1 Mn5 116.4(4) 5_675 . ? Mn1 O1 Mn5 116.4(4) . . ? Mn1 O2 Mn3 123.7(6) . . ? Mn1 O2 Mn2 107.4(6) . . ? Mn3 O2 Mn2 128.1(7) . . ? Mn3 O3 Mn4 127.2(6) . 5_675 ? Mn3 O3 Mn5 119.0(6) . . ? Mn4 O3 Mn5 97.0(5) 5_675 . ? Mn3 O3 K1 106.6(5) . . ? Mn4 O3 K1 107.8(5) 5_675 . ? Mn5 O3 K1 94.4(4) . . ? Mn4 O4 Mn2 123.3(6) . . ? Mn4 O4 Mn5 98.9(5) . . ? Mn2 O4 Mn5 115.9(6) . . ? Mn4 O4 K1 114.7(5) . . ? Mn2 O4 K1 105.2(5) . . ? Mn5 O4 K1 95.6(4) . . ? C1A O1A K1 104.6(10) . . ? C1A O2A Mn4 132.3(13) . . ? C1A O2A K1 124.8(13) . 5_675 ? Mn4 O2A K1 103.0(4) . 5_675 ? C1A O2A K1 81.8(9) . . ? Mn4 O2A K1 93.4(4) . . ? K1 O2A K1 96.9(4) 5_675 . ? O2A C1A O1A 123.6(12) . . ? O2A C1A C2A 120.1(11) . . ? O1A C1A C2A 116.3(11) . . ? O2A C1A K1 75.3(8) . . ? O1A C1A K1 52.7(9) . . ? C2A C1A K1 155.6(11) . . ? C1A C2A C5A 110.2(11) . . ? C1A C2A C3A 110.3(10) . . ? C5A C2A C3A 108.7(10) . . ? C1A C2A C4A 110.3(11) . . ? C5A C2A C4A 109.0(10) . . ? C3A C2A C4A 108.3(10) . . ? C1B O2B K1 135.1(11) . . ? O2B C1B O1B 125.9(13) . . ? O2B C1B C2B 120.7(12) . . ? O1B C1B C2B 113.0(11) . . ? C4B C2B C3B 110.2(10) . . ? C4B C2B C5B 109.3(10) . . ? C3B C2B C5B 108.9(10) . . ? C4B C2B C1B 111.0(11) . . ? C3B C2B C1B 108.8(11) . . ? C5B C2B C1B 108.5(11) . . ? C1C O1C Mn2 131.8(10) . . ? C1C O1C K1 82.6(11) . . ? Mn2 O1C K1 94.1(4) . . ? C1C O2C Mn3 133.6(10) . . ? C1C O2C K1 72.7(10) . . ? Mn3 O2C K1 89.9(4) . . ? O2C C1C O1C 124.7(12) . . ? O2C C1C C2C 117.5(11) . . ? O1C C1C C2C 116.4(10) . . ? O2C C1C K1 83.8(10) . . ? O1C C1C K1 72.9(10) . . ? C2C C1C K1 128.2(10) . . ? C3C C2C C4C 110.0(10) . . ? C3C C2C C5C 109.3(10) . . ? C4C C2C C5C 109.1(10) . . ? C3C C2C C1C 109.5(10) . . ? C4C C2C C1C 108.4(10) . . ? C5C C2C C1C 110.6(10) . . ? C1D O1D Mn3 118.4(9) . . ? C1D O2D Mn1 122.9(11) . . ? O2D C1D O1D 126.2(12) . . ? O2D C1D C2D 118.3(10) . . ? O1D C1D C2D 115.3(10) . . ? C4D C2D C5D 109.5(10) . . ? C4D C2D C3D 108.9(10) . . ? C5D C2D C3D 109.1(10) . . ? C4D C2D C1D 109.8(11) . . ? C5D C2D C1D 110.3(10) . . ? C3D C2D C1D 109.2(10) . . ? C1E O1E Mn2 127.2(9) . . ? C1E O2E Mn1 128.0(10) . . ? O2E C1E O1E 127.1(12) . . ? O2E C1E C2E 117.5(11) . . ? O1E C1E C2E 115.3(10) . . ? C8E C2E C7E 111.2(12) . . ? C5E C2E C4E 109.6(11) . . ? C8E C2E C6E 110.2(11) . . ? C7E C2E C6E 110.0(12) . . ? C5E C2E C3E 109.2(11) . . ? C4E C2E C3E 108.8(11) . . ? C8E C2E C1E 109.5(18) . . ? C7E C2E C1E 103.9(19) . . ? C5E C2E C1E 109.9(11) . . ? C4E C2E C1E 110.0(12) . . ? C6E C2E C1E 111.9(15) . . ? C3E C2E C1E 109.3(11) . . ? C1F O1F Mn2 121.6(9) . . ? C1F O1F Mn1 139.5(12) . . ? Mn2 O1F Mn1 83.3(4) . . ? C1F O2F Mn4 134.9(10) . . ? O2F C1F O1F 125.3(12) . . ? O2F C1F C2F 117.8(10) . . ? O1F C1F C2F 115.9(10) . . ? C3F C2F C4F 109.2(10) . . ? C3F C2F C5F 110.1(10) . . ? C4F C2F C5F 108.8(10) . . ? C3F C2F C1F 110.5(10) . . ? C4F C2F C1F 109.7(10) . . ? C5F C2F C1F 108.4(10) . . ? C1G O1G Mn2 134.0(9) . . ? C1G O2G Mn4 126.1(9) . . ? O2G C1G O1G 127.7(12) . . ? O2G C1G C2G 115.8(10) . . ? O1G C1G C2G 115.8(10) . . ? C5G C2G C4G 110.7(10) . . ? C5G C2G C3G 110.5(10) . . ? C4G C2G C3G 108.3(10) . . ? C5G C2G C1G 109.3(10) . . ? C4G C2G C1G 109.4(10) . . ? C3G C2G C1G 108.5(10) . . ? C1H O1H Mn3 135.2(10) . 5_675 ? C1H O2H Mn4 128.4(9) . . ? O2H C1H O1H 125.3(12) . . ? O2H C1H C2H 120.3(11) . . ? O1H C1H C2H 114.4(10) . . ? C4H C2H C1H 109.6(10) . . ? C4H C2H C3H 109.3(10) . . ? C1H C2H C3H 110.0(10) . . ? C4H C2H C5H 109.1(10) . . ? C1H C2H C5H 110.3(10) . . ? C3H C2H C5H 108.6(10) . . ? C1I O1I Mn1 131.7(18) . . ? O1I C1I O1I 121.4(33) 5_675 . ? O1I C1I C2I 119.3(16) 5_675 . ? O1I C1I C2I 119.3(16) . . ? C4I C2I C4I 143.0(83) 5_675 . ? C4I C2I C1I 108.5(42) 5_675 . ? C4I C2I C1I 108.5(41) . . ? C4I C2I C3I 105.6(39) 5_675 5_675 ? C4I C2I C3I 64.8(36) . 5_675 ? C1I C2I C3I 104.3(22) . 5_675 ? C4I C2I C3I 64.8(36) 5_675 . ? C4I C2I C3I 105.6(39) . . ? C1I C2I C3I 104.3(22) . . ? C3I C2I C3I 151.4(43) 5_675 . ? C4I C2I C5I 32.9(41) 5_675 . ? C4I C2I C5I 128.6(42) . . ? C1I C2I C5I 109.9(28) . . ? C3I C2I C5I 73.5(28) 5_675 . ? C3I C2I C5I 96.7(30) . . ? C4I C2I C5I 128.6(42) 5_675 5_675 ? C4I C2I C5I 32.9(41) . 5_675 ? C1I C2I C5I 109.9(28) . 5_675 ? C3I C2I C5I 96.7(30) 5_675 5_675 ? C3I C2I C5I 73.5(28) . 5_675 ? C5I C2I C5I 140.2(57) . 5_675 ? _refine_diff_density_max 0.583 _refine_diff_density_min -0.851 _refine_diff_density_rms 0.116