# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'En-Qing Gao' _publ_contact_author_address ; Department of Chemistry East China Normal University Shanghai 200062 CHINA ; _publ_contact_author_email EQGAO@CHEM.ECNU.EDU.CN _publ_section_title ; Novel frustrated magnetic lattice based on triangular [Mn3(?3-X)] (X = F or OH) clusters with tetrazole ligands ; loop_ _publ_author_name 'En-Qing Gao' 'Ai-Ling Cheng' 'Song Gao' 'Na Liu' ## Crystallographic Data of Complex 1 data_1 _database_code_depnum_ccdc_archive 'CCDC 634263' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H30 F2 Mn7 N54 O12' _chemical_formula_weight 1545.48 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' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M P-3c1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, -z+1/2' 'x-y, -y, -z+1/2' '-x, -x+y, -z+1/2' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-y, -x, z-1/2' '-x+y, y, z-1/2' 'x, x-y, z-1/2' _cell_length_a 14.355(3) _cell_length_b 14.355(3) _cell_length_c 13.705(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 2445.7(12) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 7936 _cell_measurement_theta_min 2.838 _cell_measurement_theta_max 28.186 _exptl_crystal_description polyhedral _exptl_crystal_colour colorless _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.099 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1538 _exptl_absorpt_coefficient_mu 1.868 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9203 _exptl_absorpt_correction_T_max 0.9590 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 2.5 _diffrn_reflns_number 12451 _diffrn_reflns_av_R_equivalents 0.0272 _diffrn_reflns_av_sigmaI/netI 0.0186 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.64 _diffrn_reflns_theta_max 28.32 _reflns_number_total 1946 _reflns_number_gt 1805 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'Bruker SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0370P)^2^+1.1459P] 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 refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0049(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1946 _refine_ls_number_parameters 153 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0301 _refine_ls_R_factor_gt 0.0277 _refine_ls_wR_factor_ref 0.0669 _refine_ls_wR_factor_gt 0.0656 _refine_ls_goodness_of_fit_ref 1.091 _refine_ls_restrained_S_all 1.091 _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 0.498837(18) 0.798906(18) 0.350261(18) 0.01866(10) Uani 1 1 d . . . Mn2 Mn 1.0000 1.0000 0.5000 0.01790(14) Uani 1 6 d S . . C1 C 0.64483(12) 0.68498(12) 0.37779(12) 0.0190(3) Uani 1 1 d . . . C2 C 0.75676(12) 0.87964(12) 0.38760(12) 0.0201(3) Uani 1 1 d . . . N1 N 0.54953(10) 0.67752(10) 0.36241(11) 0.0210(3) Uani 1 1 d . . . N2 N 0.47921(10) 0.56995(10) 0.35968(10) 0.0222(3) Uani 1 1 d . . . N3 N 0.53109(11) 0.51818(11) 0.37203(12) 0.0270(3) Uani 1 1 d . . . N4 N 0.63658(11) 0.58852(11) 0.38367(12) 0.0256(3) Uani 1 1 d . . . N5 N 0.74193(11) 0.77780(11) 0.38708(13) 0.0260(3) Uani 1 1 d . . . H5N H 0.7947(19) 0.770(2) 0.3956(18) 0.040(6) Uiso 1 1 d . . . N6 N 0.68202(10) 0.90666(10) 0.36844(11) 0.0220(3) Uani 1 1 d . . . N7 N 0.73707(11) 1.01645(11) 0.37269(12) 0.0262(3) Uani 1 1 d . . . N8 N 0.83721(11) 1.05059(11) 0.39380(12) 0.0249(3) Uani 1 1 d . . . N9 N 0.85341(10) 0.96591(10) 0.40585(11) 0.0224(3) Uani 1 1 d . . . O2 O 0.51634(10) 0.82929(11) 0.19364(10) 0.0260(3) Uani 1 1 d . . . H2WB H 0.580(2) 0.869(2) 0.1733(18) 0.043(7) Uiso 1 1 d . . . H2WA H 0.489(2) 0.865(2) 0.175(2) 0.055(8) Uiso 1 1 d . . . O3 O 0.45997(12) 0.77267(12) 0.50875(11) 0.0296(3) Uani 1 1 d . . . H3WB H 0.446(2) 0.720(3) 0.527(3) 0.069(10) Uiso 1 1 d . . . H3WA H 0.502(2) 0.818(2) 0.545(2) 0.041(7) Uiso 1 1 d . . . F F 0.3333 0.6667 0.33125(12) 0.0213(3) Uani 1 3 d S . . 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 0.01338(13) 0.01522(14) 0.02820(17) 0.00041(9) -0.00022(9) 0.00778(10) Mn2 0.01173(17) 0.01173(17) 0.0302(3) 0.000 0.000 0.00587(8) C1 0.0162(7) 0.0167(7) 0.0251(8) -0.0027(6) -0.0022(6) 0.0091(6) C2 0.0132(7) 0.0173(7) 0.0281(8) 0.0004(6) -0.0006(6) 0.0062(6) N1 0.0135(6) 0.0155(6) 0.0329(8) -0.0021(5) -0.0012(5) 0.0065(5) N2 0.0166(6) 0.0158(6) 0.0326(8) -0.0026(5) -0.0023(5) 0.0069(5) N3 0.0206(7) 0.0172(6) 0.0426(9) -0.0035(6) -0.0061(6) 0.0091(5) N4 0.0192(6) 0.0166(6) 0.0419(9) -0.0034(6) -0.0062(6) 0.0096(5) N5 0.0123(6) 0.0168(6) 0.0500(10) -0.0033(6) -0.0051(6) 0.0080(5) N6 0.0155(6) 0.0152(6) 0.0338(8) 0.0018(5) -0.0032(5) 0.0066(5) N7 0.0195(7) 0.0163(6) 0.0407(9) 0.0023(6) -0.0053(6) 0.0074(5) N8 0.0175(6) 0.0163(6) 0.0388(9) 0.0035(6) -0.0037(6) 0.0070(5) N9 0.0143(6) 0.0155(6) 0.0354(8) 0.0009(5) -0.0027(5) 0.0060(5) O2 0.0215(6) 0.0272(6) 0.0317(7) 0.0037(5) 0.0030(5) 0.0139(5) O3 0.0348(7) 0.0214(6) 0.0294(7) -0.0022(6) -0.0035(6) 0.0117(6) F 0.0156(5) 0.0156(5) 0.0327(9) 0.000 0.000 0.0078(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn1 O2 2.1798(16) . ? Mn1 F 2.1922(5) . ? Mn1 N1 2.2049(14) . ? Mn1 O3 2.2273(17) . ? Mn1 N2 2.2506(14) 2_665 ? Mn1 N6 2.3025(14) . ? Mn2 N9 2.3028(14) 7_776 ? Mn2 N9 2.3028(14) . ? Mn2 N9 2.3028(14) 2_765 ? Mn2 N9 2.3028(14) 8_566 ? Mn2 N9 2.3028(14) 3_675 ? Mn2 N9 2.3028(14) 9_656 ? C1 N4 1.332(2) . ? C1 N1 1.3344(19) . ? C1 N5 1.370(2) . ? C2 N6 1.3367(19) . ? C2 N9 1.3427(19) . ? C2 N5 1.368(2) . ? N1 N2 1.3586(18) . ? N2 N3 1.2997(19) . ? N2 Mn1 2.2506(14) 3_565 ? N3 N4 1.3450(19) . ? N5 H5N 0.83(2) . ? N6 N7 1.3660(18) . ? N7 N8 1.2983(19) . ? N8 N9 1.3570(19) . ? O2 H2WB 0.84(3) . ? O2 H2WA 0.83(3) . ? O3 H3WB 0.73(4) . ? O3 H3WA 0.80(3) . ? F Mn1 2.1922(5) 2_665 ? F Mn1 2.1922(5) 3_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 O2 Mn1 F 91.31(6) . . ? O2 Mn1 N1 100.48(5) . . ? F Mn1 N1 88.15(3) . . ? O2 Mn1 O3 171.20(5) . . ? F Mn1 O3 84.15(6) . . ? N1 Mn1 O3 86.93(5) . . ? O2 Mn1 N2 87.87(5) . 2_665 ? F Mn1 N2 87.10(4) . 2_665 ? N1 Mn1 N2 170.48(5) . 2_665 ? O3 Mn1 N2 84.38(5) . 2_665 ? O2 Mn1 N6 89.63(5) . . ? F Mn1 N6 166.84(3) . . ? N1 Mn1 N6 78.78(5) . . ? O3 Mn1 N6 96.51(6) . . ? N2 Mn1 N6 106.05(5) 2_665 . ? N9 Mn2 N9 180.0 7_776 . ? N9 Mn2 N9 88.34(6) 7_776 2_765 ? N9 Mn2 N9 91.66(6) . 2_765 ? N9 Mn2 N9 91.66(6) 7_776 8_566 ? N9 Mn2 N9 88.34(6) . 8_566 ? N9 Mn2 N9 180.00(6) 2_765 8_566 ? N9 Mn2 N9 88.34(6) 7_776 3_675 ? N9 Mn2 N9 91.66(6) . 3_675 ? N9 Mn2 N9 91.66(6) 2_765 3_675 ? N9 Mn2 N9 88.34(6) 8_566 3_675 ? N9 Mn2 N9 91.66(6) 7_776 9_656 ? N9 Mn2 N9 88.34(6) . 9_656 ? N9 Mn2 N9 88.34(6) 2_765 9_656 ? N9 Mn2 N9 91.66(6) 8_566 9_656 ? N9 Mn2 N9 180.0 3_675 9_656 ? N4 C1 N1 111.80(13) . . ? N4 C1 N5 121.59(14) . . ? N1 C1 N5 126.61(14) . . ? N6 C2 N9 112.22(14) . . ? N6 C2 N5 126.19(14) . . ? N9 C2 N5 121.57(14) . . ? C1 N1 N2 104.18(12) . . ? C1 N1 Mn1 132.74(10) . . ? N2 N1 Mn1 123.01(10) . . ? N3 N2 N1 109.50(12) . . ? N3 N2 Mn1 127.75(10) . 3_565 ? N1 N2 Mn1 122.47(10) . 3_565 ? N2 N3 N4 109.75(13) . . ? C1 N4 N3 104.77(13) . . ? C2 N5 C1 125.37(13) . . ? C2 N5 H5N 118.8(17) . . ? C1 N5 H5N 115.8(17) . . ? C2 N6 N7 103.95(12) . . ? C2 N6 Mn1 129.72(10) . . ? N7 N6 Mn1 125.96(10) . . ? N8 N7 N6 109.74(12) . . ? N7 N8 N9 110.01(12) . . ? C2 N9 N8 104.04(12) . . ? C2 N9 Mn2 135.51(11) . . ? N8 N9 Mn2 115.18(10) . . ? Mn1 O2 H2WB 115.9(17) . . ? Mn1 O2 H2WA 112.8(19) . . ? H2WB O2 H2WA 100(2) . . ? Mn1 O3 H3WB 116(3) . . ? Mn1 O3 H3WA 116.8(19) . . ? H3WB O3 H3WA 109(3) . . ? Mn1 F Mn1 118.608(18) 2_665 . ? Mn1 F Mn1 118.608(18) 2_665 3_565 ? Mn1 F Mn1 118.608(18) . 3_565 ? 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 N4 C1 N1 N2 0.56(19) . . . . ? N5 C1 N1 N2 -179.43(17) . . . . ? N4 C1 N1 Mn1 177.38(12) . . . . ? N5 C1 N1 Mn1 -2.6(3) . . . . ? O2 Mn1 N1 C1 90.41(16) . . . . ? F Mn1 N1 C1 -178.61(16) . . . . ? O3 Mn1 N1 C1 -94.37(16) . . . . ? N2 Mn1 N1 C1 -118.5(3) 2_665 . . . ? N6 Mn1 N1 C1 2.90(15) . . . . ? O2 Mn1 N1 N2 -93.27(13) . . . . ? F Mn1 N1 N2 -2.28(13) . . . . ? O3 Mn1 N1 N2 81.96(13) . . . . ? N2 Mn1 N1 N2 57.8(3) 2_665 . . . ? N6 Mn1 N1 N2 179.22(14) . . . . ? C1 N1 N2 N3 -0.47(18) . . . . ? Mn1 N1 N2 N3 -177.69(11) . . . . ? C1 N1 N2 Mn1 173.91(11) . . . 3_565 ? Mn1 N1 N2 Mn1 -3.30(18) . . . 3_565 ? N1 N2 N3 N4 0.2(2) . . . . ? Mn1 N2 N3 N4 -173.78(11) 3_565 . . . ? N1 C1 N4 N3 -0.4(2) . . . . ? N5 C1 N4 N3 179.56(16) . . . . ? N2 N3 N4 C1 0.1(2) . . . . ? N6 C2 N5 C1 -8.0(3) . . . . ? N9 C2 N5 C1 173.89(17) . . . . ? N4 C1 N5 C2 -176.03(17) . . . . ? N1 C1 N5 C2 3.9(3) . . . . ? N9 C2 N6 N7 1.66(19) . . . . ? N5 C2 N6 N7 -176.61(17) . . . . ? N9 C2 N6 Mn1 -171.60(12) . . . . ? N5 C2 N6 Mn1 10.1(3) . . . . ? O2 Mn1 N6 C2 -107.15(15) . . . . ? F Mn1 N6 C2 -13.0(4) . . . . ? N1 Mn1 N6 C2 -6.38(15) . . . . ? O3 Mn1 N6 C2 79.17(15) . . . . ? N2 Mn1 N6 C2 165.18(14) 2_665 . . . ? O2 Mn1 N6 N7 80.95(14) . . . . ? F Mn1 N6 N7 175.1(2) . . . . ? N1 Mn1 N6 N7 -178.29(15) . . . . ? O3 Mn1 N6 N7 -92.74(14) . . . . ? N2 Mn1 N6 N7 -6.73(15) 2_665 . . . ? C2 N6 N7 N8 -0.50(19) . . . . ? Mn1 N6 N7 N8 173.10(12) . . . . ? N6 N7 N8 N9 -0.8(2) . . . . ? N6 C2 N9 N8 -2.1(2) . . . . ? N5 C2 N9 N8 176.25(16) . . . . ? N6 C2 N9 Mn2 149.58(13) . . . . ? N5 C2 N9 Mn2 -32.1(3) . . . . ? N7 N8 N9 C2 1.7(2) . . . . ? N7 N8 N9 Mn2 -156.72(12) . . . . ? N9 Mn2 N9 C2 -91(100) 7_776 . . . ? N9 Mn2 N9 C2 65.7(2) 2_765 . . . ? N9 Mn2 N9 C2 -114.3(2) 8_566 . . . ? N9 Mn2 N9 C2 157.44(15) 3_675 . . . ? N9 Mn2 N9 C2 -22.56(15) 9_656 . . . ? N9 Mn2 N9 N8 59(100) 7_776 . . . ? N9 Mn2 N9 N8 -144.82(10) 2_765 . . . ? N9 Mn2 N9 N8 35.18(10) 8_566 . . . ? N9 Mn2 N9 N8 -53.11(14) 3_675 . . . ? N9 Mn2 N9 N8 126.89(14) 9_656 . . . ? O2 Mn1 F Mn1 -95.77(8) . . . 2_665 ? N1 Mn1 F Mn1 163.78(8) . . . 2_665 ? O3 Mn1 F Mn1 76.68(8) . . . 2_665 ? N2 Mn1 F Mn1 -7.97(8) 2_665 . . 2_665 ? N6 Mn1 F Mn1 170.3(2) . . . 2_665 ? O2 Mn1 F Mn1 107.49(8) . . . 3_565 ? N1 Mn1 F Mn1 7.04(8) . . . 3_565 ? O3 Mn1 F Mn1 -80.06(8) . . . 3_565 ? N2 Mn1 F Mn1 -164.70(8) 2_665 . . 3_565 ? N6 Mn1 F Mn1 13.5(3) . . . 3_565 ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N5 H5N N8 0.83(2) 2.11(2) 2.9186(19) 165(2) 2_765 O2 H2WB N7 0.84(3) 1.97(3) 2.7993(19) 169(2) 5_675 O2 H2WA N3 0.83(3) 2.02(3) 2.819(2) 162(3) 6_665 O3 H3WB O3 0.73(4) 2.33(3) 2.926(3) 140(3) 3_565 O3 H3WA N4 0.80(3) 1.95(3) 2.730(2) 163(3) 8_566 _diffrn_measured_fraction_theta_max 0.952 _diffrn_reflns_theta_full 28.32 _diffrn_measured_fraction_theta_full 0.952 _refine_diff_density_max 0.449 _refine_diff_density_min -0.353 _refine_diff_density_rms 0.114 # Attachment '2.cif' ## Crystallographic Data of Complex 2 data_2 _database_code_depnum_ccdc_archive 'CCDC 634264' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H32 Mn7 N54 O14' _chemical_formula_weight 1541.50 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' Mn Mn 0.3368 0.7283 '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-3c1 ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, -z+1/2' 'x-y, -y, -z+1/2' '-x, -x+y, -z+1/2' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-y, -x, z-1/2' '-x+y, y, z-1/2' 'x, x-y, z-1/2' _cell_length_a 14.289(3) _cell_length_b 14.289(3) _cell_length_c 13.738(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 2429.1(11) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 766 _cell_measurement_theta_min 2.851 _cell_measurement_theta_max 21.577 _exptl_crystal_description polyhedral _exptl_crystal_colour colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.108 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1538 _exptl_absorpt_coefficient_mu 1.878 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6027 _exptl_absorpt_correction_T_max 0.7051 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 4.53 _diffrn_reflns_number 11645 _diffrn_reflns_av_R_equivalents 0.0867 _diffrn_reflns_av_sigmaI/netI 0.0701 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 1.65 _diffrn_reflns_theta_max 27.12 _reflns_number_total 1805 _reflns_number_gt 1151 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'Bruker SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0060P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1805 _refine_ls_number_parameters 154 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0573 _refine_ls_R_factor_gt 0.0304 _refine_ls_wR_factor_ref 0.0438 _refine_ls_wR_factor_gt 0.0413 _refine_ls_goodness_of_fit_ref 0.801 _refine_ls_restrained_S_all 0.801 _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 0.49789(3) 0.79755(3) 0.35027(3) 0.02290(12) Uani 1 1 d . . . Mn2 Mn 1.0000 1.0000 0.5000 0.0219(2) Uani 1 6 d S . . C1 C 0.6452(2) 0.6839(2) 0.37832(19) 0.0221(6) Uani 1 1 d . . . C2 C 0.75705(19) 0.8791(2) 0.38827(18) 0.0227(6) Uani 1 1 d . . . N1 N 0.55005(15) 0.67657(16) 0.36329(14) 0.0233(5) Uani 1 1 d . . . N2 N 0.47950(17) 0.56801(17) 0.36012(15) 0.0260(6) Uani 1 1 d . . . N3 N 0.53173(17) 0.51668(16) 0.37199(16) 0.0301(6) Uani 1 1 d . . . N4 N 0.63827(17) 0.58739(17) 0.38341(16) 0.0300(6) Uani 1 1 d . . . N5 N 0.74132(18) 0.77640(19) 0.38761(18) 0.0304(6) Uani 1 1 d . . . H5N H 0.7905(17) 0.7705(17) 0.3910(17) 0.009(7) Uiso 1 1 d . . . N9 N 0.85331(15) 0.96500(16) 0.40639(14) 0.0243(5) Uani 1 1 d . . . N8 N 0.83654(17) 1.04978(17) 0.39432(16) 0.0294(6) Uani 1 1 d . . . N7 N 0.73631(17) 1.01551(17) 0.37288(16) 0.0305(6) Uani 1 1 d . . . N6 N 0.68128(16) 0.90491(16) 0.36867(15) 0.0250(6) Uani 1 1 d . . . O1 O 0.3333 0.6667 0.3188(3) 0.0212(8) Uani 1 3 d S . . H1W H 0.3333 0.6667 0.265(3) 0.017(15) Uiso 1 3 d S . . O2 O 0.5161(2) 0.82909(17) 0.19318(16) 0.0328(6) Uani 1 1 d . . . H2WB H 0.571(2) 0.854(2) 0.182(2) 0.046(13) Uiso 1 1 d . . . H2WA H 0.497(3) 0.875(3) 0.175(2) 0.100(17) Uiso 1 1 d . . . O3 O 0.45902(17) 0.7717(2) 0.50790(15) 0.0349(6) Uani 1 1 d . . . H3WB H 0.4451(19) 0.714(2) 0.5215(18) 0.026(9) Uiso 1 1 d . . . H3WA H 0.508(2) 0.825(2) 0.540(2) 0.055(11) Uiso 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 0.0161(2) 0.0186(2) 0.0347(3) 0.00034(19) -0.00043(19) 0.00918(19) Mn2 0.0151(3) 0.0151(3) 0.0354(7) 0.000 0.000 0.00757(16) C1 0.0167(15) 0.0194(15) 0.0278(17) -0.0038(12) -0.0037(12) 0.0074(13) C2 0.0193(14) 0.0191(15) 0.0286(17) 0.0005(13) -0.0008(12) 0.0088(13) N1 0.0148(12) 0.0182(13) 0.0354(15) -0.0039(11) -0.0042(10) 0.0072(11) N2 0.0192(13) 0.0200(13) 0.0373(15) -0.0010(11) -0.0022(10) 0.0085(11) N3 0.0238(14) 0.0211(13) 0.0461(17) -0.0051(11) -0.0063(11) 0.0118(12) N4 0.0224(13) 0.0201(13) 0.0487(16) -0.0060(12) -0.0096(12) 0.0116(11) N5 0.0115(13) 0.0228(14) 0.0598(19) -0.0050(12) -0.0072(12) 0.0108(12) N9 0.0159(12) 0.0150(12) 0.0392(15) 0.0019(11) -0.0022(10) 0.0057(10) N8 0.0202(13) 0.0205(13) 0.0439(16) 0.0040(11) -0.0044(11) 0.0075(11) N7 0.0225(14) 0.0205(13) 0.0463(17) 0.0045(11) -0.0059(11) 0.0090(12) N6 0.0172(13) 0.0166(12) 0.0395(16) 0.0022(10) -0.0033(10) 0.0072(10) O1 0.0194(12) 0.0194(12) 0.025(2) 0.000 0.000 0.0097(6) O2 0.0253(14) 0.0338(13) 0.0402(15) 0.0050(10) 0.0036(12) 0.0155(12) O3 0.0380(14) 0.0226(13) 0.0395(14) -0.0024(12) -0.0033(10) 0.0116(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 O2 2.193(2) . ? Mn1 O1 2.1946(9) . ? Mn1 N1 2.205(2) . ? Mn1 O3 2.220(2) . ? Mn1 N2 2.256(2) 2_665 ? Mn1 N6 2.294(2) . ? Mn2 N9 2.291(2) 7_776 ? Mn2 N9 2.2910(19) 2_765 ? Mn2 N9 2.291(2) . ? Mn2 N9 2.291(2) 3_675 ? Mn2 N9 2.291(2) 9_656 ? Mn2 N9 2.2910(19) 8_566 ? C1 N1 1.327(3) . ? C1 N4 1.333(3) . ? C1 N5 1.354(3) . ? C2 N9 1.331(3) . ? C2 N6 1.334(3) . ? C2 N5 1.369(3) . ? N1 N2 1.364(3) . ? N2 N3 1.292(3) . ? N2 Mn1 2.256(2) 3_565 ? N3 N4 1.351(3) . ? N5 H5N 0.75(2) . ? N9 N8 1.358(3) . ? N8 N7 1.295(3) . ? N7 N6 1.370(3) . ? O1 Mn1 2.1946(9) 2_665 ? O1 Mn1 2.1946(9) 3_565 ? O1 H1W 0.74(4) . ? O2 H2WB 0.69(3) . ? O2 H2WA 0.86(4) . ? O3 H3WB 0.77(2) . ? O3 H3WA 0.85(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 O2 Mn1 O1 86.99(11) . . ? O2 Mn1 N1 100.90(9) . . ? O1 Mn1 N1 89.20(5) . . ? O2 Mn1 O3 171.09(9) . . ? O1 Mn1 O3 88.76(11) . . ? N1 Mn1 O3 86.85(8) . . ? O2 Mn1 N2 87.71(9) . 2_665 ? O1 Mn1 N2 88.33(5) . 2_665 ? N1 Mn1 N2 170.90(7) . 2_665 ? O3 Mn1 N2 84.34(8) . 2_665 ? O2 Mn1 N6 89.58(9) . . ? O1 Mn1 N6 166.02(6) . . ? N1 Mn1 N6 78.15(7) . . ? O3 Mn1 N6 96.36(8) . . ? N2 Mn1 N6 105.08(7) 2_665 . ? N9 Mn2 N9 88.43(7) 7_776 2_765 ? N9 Mn2 N9 180.000(1) 7_776 . ? N9 Mn2 N9 91.57(7) 2_765 . ? N9 Mn2 N9 88.43(7) 7_776 3_675 ? N9 Mn2 N9 91.57(7) 2_765 3_675 ? N9 Mn2 N9 91.57(7) . 3_675 ? N9 Mn2 N9 91.57(7) 7_776 9_656 ? N9 Mn2 N9 88.43(7) 2_765 9_656 ? N9 Mn2 N9 88.43(7) . 9_656 ? N9 Mn2 N9 180.0 3_675 9_656 ? N9 Mn2 N9 91.57(7) 7_776 8_566 ? N9 Mn2 N9 180.00(8) 2_765 8_566 ? N9 Mn2 N9 88.43(7) . 8_566 ? N9 Mn2 N9 88.43(7) 3_675 8_566 ? N9 Mn2 N9 91.57(7) 9_656 8_566 ? N1 C1 N4 112.5(2) . . ? N1 C1 N5 126.2(2) . . ? N4 C1 N5 121.3(2) . . ? N9 C2 N6 113.0(2) . . ? N9 C2 N5 122.0(2) . . ? N6 C2 N5 125.0(2) . . ? C1 N1 N2 103.9(2) . . ? C1 N1 Mn1 133.30(17) . . ? N2 N1 Mn1 122.79(15) . . ? N3 N2 N1 109.5(2) . . ? N3 N2 Mn1 129.16(16) . 3_565 ? N1 N2 Mn1 121.10(15) . 3_565 ? N2 N3 N4 110.2(2) . . ? C1 N4 N3 103.9(2) . . ? C1 N5 C2 126.2(2) . . ? C1 N5 H5N 116.5(18) . . ? C2 N5 H5N 117.3(18) . . ? C2 N9 N8 103.76(19) . . ? C2 N9 Mn2 135.81(17) . . ? N8 N9 Mn2 115.10(15) . . ? N7 N8 N9 110.2(2) . . ? N8 N7 N6 109.5(2) . . ? C2 N6 N7 103.5(2) . . ? C2 N6 Mn1 130.60(17) . . ? N7 N6 Mn1 125.52(15) . . ? Mn1 O1 Mn1 116.21(6) 2_665 . ? Mn1 O1 Mn1 116.21(6) 2_665 3_565 ? Mn1 O1 Mn1 116.21(6) . 3_565 ? Mn1 O1 H1W 101.37(9) 2_665 . ? Mn1 O1 H1W 101.37(9) . . ? Mn1 O1 H1W 101.37(9) 3_565 . ? Mn1 O2 H2WB 108(3) . . ? Mn1 O2 H2WA 113(2) . . ? H2WB O2 H2WA 105(3) . . ? Mn1 O3 H3WB 108.9(19) . . ? Mn1 O3 H3WA 109(2) . . ? H3WB O3 H3WA 119(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 N4 C1 N1 N2 0.8(3) . . . . ? N5 C1 N1 N2 -179.5(2) . . . . ? N4 C1 N1 Mn1 178.42(17) . . . . ? N5 C1 N1 Mn1 -1.8(4) . . . . ? O2 Mn1 N1 C1 89.7(2) . . . . ? O1 Mn1 N1 C1 176.4(3) . . . . ? O3 Mn1 N1 C1 -94.8(2) . . . . ? N2 Mn1 N1 C1 -109.3(5) 2_665 . . . ? N6 Mn1 N1 C1 2.4(2) . . . . ? O2 Mn1 N1 N2 -93.06(18) . . . . ? O1 Mn1 N1 N2 -6.3(2) . . . . ? O3 Mn1 N1 N2 82.51(18) . . . . ? N2 Mn1 N1 N2 68.0(5) 2_665 . . . ? N6 Mn1 N1 N2 179.69(19) . . . . ? C1 N1 N2 N3 -0.4(3) . . . . ? Mn1 N1 N2 N3 -178.38(16) . . . . ? C1 N1 N2 Mn1 174.15(16) . . . 3_565 ? Mn1 N1 N2 Mn1 -3.8(2) . . . 3_565 ? N1 N2 N3 N4 -0.1(3) . . . . ? Mn1 N2 N3 N4 -174.06(16) 3_565 . . . ? N1 C1 N4 N3 -0.8(3) . . . . ? N5 C1 N4 N3 179.4(2) . . . . ? N2 N3 N4 C1 0.5(3) . . . . ? N1 C1 N5 C2 3.6(5) . . . . ? N4 C1 N5 C2 -176.6(3) . . . . ? N9 C2 N5 C1 173.9(2) . . . . ? N6 C2 N5 C1 -8.1(5) . . . . ? N6 C2 N9 N8 -1.9(3) . . . . ? N5 C2 N9 N8 176.3(2) . . . . ? N6 C2 N9 Mn2 149.59(18) . . . . ? N5 C2 N9 Mn2 -32.2(4) . . . . ? N9 Mn2 N9 C2 -115(100) 7_776 . . . ? N9 Mn2 N9 C2 66.1(3) 2_765 . . . ? N9 Mn2 N9 C2 157.7(2) 3_675 . . . ? N9 Mn2 N9 C2 -22.3(2) 9_656 . . . ? N9 Mn2 N9 C2 -113.9(3) 8_566 . . . ? N9 Mn2 N9 N8 34(100) 7_776 . . . ? N9 Mn2 N9 N8 -144.71(14) 2_765 . . . ? N9 Mn2 N9 N8 -53.10(19) 3_675 . . . ? N9 Mn2 N9 N8 126.90(19) 9_656 . . . ? N9 Mn2 N9 N8 35.29(14) 8_566 . . . ? C2 N9 N8 N7 1.5(3) . . . . ? Mn2 N9 N8 N7 -156.94(16) . . . . ? N9 N8 N7 N6 -0.6(3) . . . . ? N9 C2 N6 N7 1.5(3) . . . . ? N5 C2 N6 N7 -176.6(2) . . . . ? N9 C2 N6 Mn1 -171.47(15) . . . . ? N5 C2 N6 Mn1 10.4(4) . . . . ? N8 N7 N6 C2 -0.5(3) . . . . ? N8 N7 N6 Mn1 172.95(16) . . . . ? O2 Mn1 N6 C2 -107.7(2) . . . . ? O1 Mn1 N6 C2 -32.0(5) . . . . ? N1 Mn1 N6 C2 -6.5(2) . . . . ? O3 Mn1 N6 C2 78.9(2) . . . . ? N2 Mn1 N6 C2 164.8(2) 2_665 . . . ? O2 Mn1 N6 N7 80.67(19) . . . . ? O1 Mn1 N6 N7 156.4(4) . . . . ? N1 Mn1 N6 N7 -178.1(2) . . . . ? O3 Mn1 N6 N7 -92.68(19) . . . . ? N2 Mn1 N6 N7 -6.9(2) 2_665 . . . ? O2 Mn1 O1 Mn1 -102.81(15) . . . 2_665 ? N1 Mn1 O1 Mn1 156.23(15) . . . 2_665 ? O3 Mn1 O1 Mn1 69.37(15) . . . 2_665 ? N2 Mn1 O1 Mn1 -15.01(14) 2_665 . . 2_665 ? N6 Mn1 O1 Mn1 -178.8(3) . . . 2_665 ? O2 Mn1 O1 Mn1 114.91(15) . . . 3_565 ? N1 Mn1 O1 Mn1 13.95(15) . . . 3_565 ? O3 Mn1 O1 Mn1 -72.91(15) . . . 3_565 ? N2 Mn1 O1 Mn1 -157.29(15) 2_665 . . 3_565 ? N6 Mn1 O1 Mn1 38.9(5) . . . 3_565 ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.12 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.475 _refine_diff_density_min -0.378 _refine_diff_density_rms 0.067