# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Liu, Lei-Lei' 'Li, Hong-Xi' 'Wan, Li-Min' 'Ren, Zhi-Gang' 'Wang, Hui-Fang' 'Lang, Jian-Ping' _publ_contact_author_name 'Lang, Jian-Ping' _publ_contact_author_email jplang@suda.edu.cn _publ_section_title ; A Mn(III)-superoxo complex of a zwitterionic calix[4]arene with an unprecedented linear end-on Mn(III)-O2 arrangement and good catalytic performance for alkene epoxidation ; #===END #============================================================================== data_4 _database_code_depnum_ccdc_archive 'CCDC 783612' #TrackingRef 'JPLangCIF.CIF' #============================================================================== _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C40 H52 Mn N4 O7, 2(F6 P), 2(C O)' _chemical_formula_sum 'C42 H52 F12 Mn N4 O9 P2' _chemical_formula_weight 1101.76 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 '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 tetragonal _symmetry_space_group_name_H-M 'I 4 m m' _symmetry_space_group_name_HALL 'I 4 -2' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-y, x, z' 'y, -x, z' 'x, -y, z' '-x, y, z' '-y, -x, z' 'y, x, z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, z+1/2' '-y+1/2, -x+1/2, z+1/2' 'y+1/2, x+1/2, z+1/2' _cell_length_a 14.590(2) _cell_length_b 14.590(2) _cell_length_c 13.553(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2884.9(8) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 2971 _cell_measurement_theta_min 3.4610 _cell_measurement_theta_max 27.4778 _exptl_crystal_description Block _exptl_crystal_colour black _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.268 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1134 _exptl_absorpt_coefficient_mu 0.370 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8659 _exptl_absorpt_correction_T_max 0.9296 _exptl_absorpt_process_details 'Jacobson, R. (1998) Private communication to Rigaku Corp.' _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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_type 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 3187 _diffrn_reflns_av_R_equivalents 0.0223 _diffrn_reflns_av_sigmaI/netI 0.0253 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.47 _diffrn_reflns_theta_max 24.98 _reflns_number_total 1199 _reflns_number_gt 1112 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear, Ver. 1.30 (Rigaku/MSC, 2001)' _computing_cell_refinement 'CrystalClear, Ver. 1.30 (Rigaku/MSC, 2001)' _computing_data_reduction 'CrystalStructure, Ver. 3.60 (Rigaku/MSC, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics '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^)+(0.1600P)^2^+25.0000P] 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 constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.061(11) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.44(15) _refine_ls_number_reflns 1199 _refine_ls_number_parameters 125 _refine_ls_number_restraints 324 _refine_ls_R_factor_all 0.1376 _refine_ls_R_factor_gt 0.1331 _refine_ls_wR_factor_ref 0.3309 _refine_ls_wR_factor_gt 0.3268 _refine_ls_goodness_of_fit_ref 1.192 _refine_ls_restrained_S_all 1.082 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.0000 0.0000 0.9106(4) 0.0654(15) Uani 1 8 d SU . . O1 O 0.0911(3) -0.0911(3) 0.9068(6) 0.0343(16) Uani 1 2 d SU . . O1W O 0.0000 0.0000 1.087(2) 0.095(7) Uani 1 8 d SU . . O2 O 0.0000 0.0000 0.733(2) 0.083(6) Uani 1 8 d SU . . O3 O 0.0000 0.0000 0.644(3) 0.125(11) Uani 1 8 d SU . . O4 O 0.0000 -0.205(2) 0.3349(19) 0.097(8) Uani 0.50 2 d SPDU . . N1 N 0.2516(6) -0.2516(6) 0.5757(10) 0.066(3) Uani 1 2 d SD . . C1 C 0.1259(3) -0.1259(3) 0.8273(7) 0.0195(16) Uani 1 2 d SU . . C2 C 0.0865(4) -0.2057(4) 0.7825(6) 0.0233(14) Uani 1 1 d U . . C3 C 0.1277(4) -0.2439(4) 0.6997(6) 0.0333(17) Uani 1 1 d U . . H3A H 0.1024 -0.2963 0.6700 0.040 Uiso 1 1 calc R . . C4 C 0.2050(6) -0.2050(6) 0.6617(9) 0.042(3) Uani 1 2 d SU . . C5 C 0.0000 -0.2461(5) 0.8277(8) 0.0224(17) Uani 1 2 d SU . . H5A H 0.0000 -0.3126 0.8178 0.027 Uiso 1 2 calc SR . . H5B H 0.0000 -0.2343 0.8989 0.027 Uiso 1 2 calc SR . . C6 C 0.1872(12) -0.2660(14) 0.4924(13) 0.066(3) Uani 0.50 1 d PDU . . H6A H 0.2193 -0.2949 0.4381 0.099 Uiso 0.50 1 calc PR . . H6B H 0.1630 -0.2073 0.4711 0.099 Uiso 0.50 1 calc PR . . H6C H 0.1372 -0.3050 0.5137 0.099 Uiso 0.50 1 calc PR . . C7 C 0.2644(14) -0.3509(10) 0.6012(16) 0.066(3) Uani 0.50 1 d PDU . . H7A H 0.3078 -0.3563 0.6551 0.099 Uiso 0.50 1 calc PR . . H7B H 0.2877 -0.3835 0.5441 0.099 Uiso 0.50 1 calc PR . . H7C H 0.2060 -0.3770 0.6209 0.099 Uiso 0.50 1 calc PR . . C8 C 0.3391(13) -0.2064(14) 0.5435(17) 0.066(3) Uani 0.50 1 d PDU . . H8A H 0.3804 -0.2016 0.5993 0.099 Uiso 0.50 1 calc PR . . H8B H 0.3257 -0.1456 0.5183 0.099 Uiso 0.50 1 calc PR . . H8C H 0.3675 -0.2428 0.4920 0.099 Uiso 0.50 1 calc PR . . C9 C 0.0000 -0.208(4) 0.439(2) 0.115(13) Uani 0.50 2 d SPDU . . P1 P 0.0000 -0.5000 0.5568(6) 0.075(2) Uani 1 4 d SDU . . F1 F 0.0000 -0.3936(8) 0.5621(18) 0.106(6) Uani 0.76(2) 2 d SPDU A 1 F2 F -0.0770(15) -0.5000 0.4762(18) 0.117(7) Uani 0.76(2) 2 d SPDU A 1 F3 F -0.0759(17) -0.5000 0.6412(19) 0.155(8) Uani 0.76(2) 2 d SPDU A 1 F1A F 0.0000 -0.429(4) 0.644(4) 0.109(12) Uani 0.24(2) 2 d SPDU A 2 F2A F -0.1075(12) -0.5000 0.551(6) 0.094(11) Uani 0.24(2) 2 d SPDU A 2 F3A F 0.0000 -0.419(4) 0.478(5) 0.120(14) Uani 0.24(2) 2 d SPDU A 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.0662(18) 0.0662(18) 0.064(3) 0.000 0.000 0.000 O1 0.032(2) 0.032(2) 0.040(4) -0.007(2) 0.007(2) -0.013(2) O1W 0.111(11) 0.111(11) 0.064(7) 0.000 0.000 0.000 O2 0.093(10) 0.093(10) 0.064(6) 0.000 0.000 0.000 O3 0.153(17) 0.153(17) 0.070(7) 0.000 0.000 0.000 O4 0.058(12) 0.15(2) 0.080(15) -0.036(17) 0.000 0.000 N1 0.066(3) 0.066(3) 0.068(6) -0.041(4) 0.041(4) -0.026(4) C1 0.019(2) 0.019(2) 0.020(4) 0.000(2) 0.000(2) 0.005(3) C2 0.024(3) 0.019(3) 0.028(3) 0.000(2) -0.003(2) 0.005(2) C3 0.031(3) 0.026(3) 0.043(4) -0.012(3) 0.002(3) -0.005(3) C4 0.043(4) 0.043(4) 0.041(7) -0.014(3) 0.014(3) -0.004(4) C5 0.030(4) 0.014(4) 0.023(4) 0.002(3) 0.000 0.000 C6 0.066(3) 0.066(3) 0.068(6) -0.041(4) 0.041(4) -0.026(4) C7 0.066(3) 0.066(3) 0.068(6) -0.041(4) 0.041(4) -0.026(4) C8 0.066(3) 0.066(3) 0.068(6) -0.041(4) 0.041(4) -0.026(4) C9 0.11(3) 0.15(3) 0.085(16) -0.04(2) 0.000 0.000 P1 0.043(3) 0.056(3) 0.126(6) 0.000 0.000 0.000 F1 0.086(9) 0.061(6) 0.170(19) -0.055(8) 0.000 0.000 F2 0.116(12) 0.084(9) 0.152(14) 0.000 -0.060(10) 0.000 F3 0.117(15) 0.200(17) 0.149(14) 0.000 0.062(11) 0.000 F1A 0.08(2) 0.09(3) 0.16(2) -0.037(17) 0.000 0.000 F2A 0.050(9) 0.07(2) 0.16(3) 0.000 -0.011(14) 0.000 F3A 0.09(2) 0.11(3) 0.17(2) 0.045(19) 0.000 0.000 _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 1.880(7) 3 ? Mn1 O1 1.880(7) 4 ? Mn1 O1 1.880(7) . ? Mn1 O1 1.880(7) 2 ? Mn1 O1W 2.39(3) . ? Mn1 O2 2.40(3) . ? O1 C1 1.296(12) . ? O2 O3 1.21(4) . ? O4 C9 1.406(18) . ? N1 C6 1.484(16) . ? N1 C6 1.484(16) 7 ? N1 C7 1.500(16) 7 ? N1 C7 1.500(16) . ? N1 C8 1.501(13) 7 ? N1 C8 1.501(13) . ? N1 C4 1.511(15) . ? C1 C2 1.433(7) . ? C1 C2 1.433(7) 7 ? C2 C3 1.390(10) . ? C2 C5 1.521(8) . ? C3 C4 1.363(9) . ? C3 H3A 0.9400 . ? C4 C3 1.363(9) 7 ? C5 C2 1.521(8) 6 ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C6 H6C 0.9700 . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C7 H7C 0.9700 . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C8 H8C 0.9700 . ? P1 F1 1.554(11) . ? P1 F1 1.554(11) 2_545 ? P1 F1A 1.566(18) . ? P1 F1A 1.566(18) 2_545 ? P1 F2 1.567(13) . ? P1 F2 1.567(13) 2_545 ? P1 F2A 1.570(17) 2_545 ? P1 F2A 1.570(17) . ? P1 F3 1.592(14) 2_545 ? P1 F3 1.592(14) . ? P1 F3A 1.595(18) 2_545 ? P1 F3A 1.595(18) . ? 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 176.9(6) 3 4 ? O1 Mn1 O1 89.957(16) 3 . ? O1 Mn1 O1 89.957(16) 4 . ? O1 Mn1 O1 89.957(16) 3 2 ? O1 Mn1 O1 89.957(16) 4 2 ? O1 Mn1 O1 176.9(6) . 2 ? O1 Mn1 O1W 91.6(3) 3 . ? O1 Mn1 O1W 91.6(3) 4 . ? O1 Mn1 O1W 91.6(3) . . ? O1 Mn1 O1W 91.6(3) 2 . ? O1 Mn1 O2 88.4(3) 3 . ? O1 Mn1 O2 88.4(3) 4 . ? O1 Mn1 O2 88.4(3) . . ? O1 Mn1 O2 88.4(3) 2 . ? O1W Mn1 O2 180.000(7) . . ? C1 O1 Mn1 125.3(7) . . ? O3 O2 Mn1 180.000(5) . . ? C6 N1 C6 66.4(16) . 7 ? C6 N1 C7 140.3(12) . 7 ? C6 N1 C7 96.8(12) 7 7 ? C6 N1 C7 96.8(12) . . ? C6 N1 C7 140.3(12) 7 . ? C7 N1 C7 73.0(17) 7 . ? C6 N1 C8 51.7(12) . 7 ? C6 N1 C8 112.3(15) 7 7 ? C7 N1 C8 112.7(14) 7 7 ? C7 N1 C8 45.7(12) . 7 ? C6 N1 C8 112.3(15) . . ? C6 N1 C8 51.7(12) 7 . ? C7 N1 C8 45.7(12) 7 . ? C7 N1 C8 112.7(14) . . ? C8 N1 C8 131.5(15) 7 . ? C6 N1 C4 111.4(10) . . ? C6 N1 C4 111.4(10) 7 . ? C7 N1 C4 108.2(11) 7 . ? C7 N1 C4 108.2(11) . . ? C8 N1 C4 114.2(8) 7 . ? C8 N1 C4 114.1(8) . . ? O1 C1 C2 120.9(4) . . ? O1 C1 C2 120.9(4) . 7 ? C2 C1 C2 118.2(8) . 7 ? C3 C2 C1 119.6(6) . . ? C3 C2 C5 121.9(6) . . ? C1 C2 C5 118.5(6) . . ? C4 C3 C2 119.8(6) . . ? C4 C3 H3A 120.1 . . ? C2 C3 H3A 120.1 . . ? C3 C4 C3 123.0(10) 7 . ? C3 C4 N1 118.5(5) 7 . ? C3 C4 N1 118.5(5) . . ? C2 C5 C2 112.1(7) 6 . ? C2 C5 H5A 109.2 6 . ? C2 C5 H5A 109.2 . . ? C2 C5 H5B 109.2 6 . ? C2 C5 H5B 109.2 . . ? H5A C5 H5B 107.9 . . ? N1 C6 H6A 109.5 . . ? N1 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? N1 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? N1 C7 H7A 109.5 . . ? N1 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? N1 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? N1 C8 H8A 109.5 . . ? N1 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? N1 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? F1 P1 F1 175(2) . 2_545 ? F1 P1 F1A 46(3) . . ? F1 P1 F1A 129(3) 2_545 . ? F1 P1 F1A 129(3) . 2_545 ? F1 P1 F1A 46(3) 2_545 2_545 ? F1A P1 F1A 82(6) . 2_545 ? F1 P1 F2 91.8(7) . . ? F1 P1 F2 91.8(7) 2_545 . ? F1A P1 F2 121.7(17) . . ? F1A P1 F2 121.7(17) 2_545 . ? F1 P1 F2 91.8(7) . 2_545 ? F1 P1 F2 91.8(7) 2_545 2_545 ? F1A P1 F2 121.7(17) . 2_545 ? F1A P1 F2 121.7(17) 2_545 2_545 ? F2 P1 F2 92(2) . 2_545 ? F1 P1 F2A 90.13(15) . 2_545 ? F1 P1 F2A 90.13(15) 2_545 2_545 ? F1A P1 F2A 92(2) . 2_545 ? F1A P1 F2A 92(2) 2_545 2_545 ? F2 P1 F2A 133(4) . 2_545 ? F2 P1 F2A 42(3) 2_545 2_545 ? F1 P1 F2A 90.13(15) . . ? F1 P1 F2A 90.13(15) 2_545 . ? F1A P1 F2A 92(2) . . ? F1A P1 F2A 92(2) 2_545 . ? F2 P1 F2A 42(3) . . ? F2 P1 F2A 133(4) 2_545 . ? F2A P1 F2A 175(6) 2_545 . ? F1 P1 F3 88.1(7) . 2_545 ? F1 P1 F3 88.1(7) 2_545 2_545 ? F1A P1 F3 57.3(17) . 2_545 ? F1A P1 F3 57.3(17) 2_545 2_545 ? F2 P1 F3 178.3(19) . 2_545 ? F2 P1 F3 90.2(14) 2_545 2_545 ? F2A P1 F3 49(3) 2_545 2_545 ? F2A P1 F3 137(4) . 2_545 ? F1 P1 F3 88.1(7) . . ? F1 P1 F3 88.1(7) 2_545 . ? F1A P1 F3 57.3(17) . . ? F1A P1 F3 57.3(17) 2_545 . ? F2 P1 F3 90.2(14) . . ? F2 P1 F3 178.3(19) 2_545 . ? F2A P1 F3 137(4) 2_545 . ? F2A P1 F3 49(3) . . ? F3 P1 F3 88(2) 2_545 . ? F1 P1 F3A 141(4) . 2_545 ? F1 P1 F3A 45(3) 2_545 2_545 ? F1A P1 F3A 173(5) . 2_545 ? F1A P1 F3A 91(4) 2_545 2_545 ? F2 P1 F3A 62.2(19) . 2_545 ? F2 P1 F3A 62.2(19) 2_545 2_545 ? F2A P1 F3A 88(2) 2_545 2_545 ? F2A P1 F3A 88(2) . 2_545 ? F3 P1 F3A 119(2) 2_545 2_545 ? F3 P1 F3A 119(2) . 2_545 ? F1 P1 F3A 45(3) . . ? F1 P1 F3A 141(4) 2_545 . ? F1A P1 F3A 91(4) . . ? F1A P1 F3A 173(5) 2_545 . ? F2 P1 F3A 62.2(19) . . ? F2 P1 F3A 62.2(19) 2_545 . ? F2A P1 F3A 88(2) 2_545 . ? F2A P1 F3A 88(2) . . ? F3 P1 F3A 119(2) 2_545 . ? F3 P1 F3A 119(2) . . ? F3A P1 F3A 96(6) 2_545 . ? 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 O1 Mn1 O1 C1 -88.4(3) 3 . . . ? O1 Mn1 O1 C1 88.4(3) 4 . . . ? O1 Mn1 O1 C1 0.00(3) 2 . . . ? O1W Mn1 O1 C1 180.000(2) . . . . ? O2 Mn1 O1 C1 0.000(2) . . . . ? O1 Mn1 O2 O3 0(100) 3 . . . ? O1 Mn1 O2 O3 0(100) 4 . . . ? O1 Mn1 O2 O3 0(100) . . . . ? O1 Mn1 O2 O3 0(100) 2 . . . ? O1W Mn1 O2 O3 0(100) . . . . ? Mn1 O1 C1 C2 -90.4(7) . . . . ? Mn1 O1 C1 C2 90.4(7) . . . 7 ? O1 C1 C2 C3 -177.3(7) . . . . ? C2 C1 C2 C3 1.9(12) 7 . . . ? O1 C1 C2 C5 2.8(11) . . . . ? C2 C1 C2 C5 -178.0(5) 7 . . . ? C1 C2 C3 C4 -0.2(12) . . . . ? C5 C2 C3 C4 179.7(9) . . . . ? C2 C3 C4 C3 -1.7(18) . . . 7 ? C2 C3 C4 N1 176.1(10) . . . . ? C6 N1 C4 C3 -127.1(12) . . . 7 ? C6 N1 C4 C3 -55.0(16) 7 . . 7 ? C7 N1 C4 C3 50.2(16) 7 . . 7 ? C7 N1 C4 C3 127.7(13) . . . 7 ? C8 N1 C4 C3 176.5(15) 7 . . 7 ? C8 N1 C4 C3 1(2) . . . 7 ? C6 N1 C4 C3 55.0(16) . . . . ? C6 N1 C4 C3 127.1(12) 7 . . . ? C7 N1 C4 C3 -127.7(13) 7 . . . ? C7 N1 C4 C3 -50.2(16) . . . . ? C8 N1 C4 C3 -1(2) 7 . . . ? C8 N1 C4 C3 -176.5(15) . . . . ? C3 C2 C5 C2 -89.3(8) . . . 6 ? C1 C2 C5 C2 90.7(9) . . . 6 ? 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 C3 H3A F1 0.94 2.53 3.424(15) 159.6 . C7 H7B O1 0.97 2.59 3.480(19) 151.8 10_544 _diffrn_measured_fraction_theta_max 0.973 _diffrn_reflns_theta_full 24.98 _diffrn_measured_fraction_theta_full 0.973 _refine_diff_density_max 1.117 _refine_diff_density_min -1.114 _refine_diff_density_rms 0.168 #===END # Attachment '- JPLangCIF (revised).CIF' data_2 _database_code_depnum_ccdc_archive 'CCDC 834982' #TrackingRef '- JPLangCIF (revised).CIF' #============================================================================== _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C40 H54.08 Mn N4 O7, 2(F6 P), 2(H2 O), 4(H O0.50)' _chemical_formula_sum 'C40 H62 F12 Mn N4 O11 P2' _chemical_formula_weight 1119.82 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'I 4 m m' _symmetry_space_group_name_HALL 'I 4 -2' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x, z' '-x, -y, z' 'y, -x, z' '-x, y, z' '-y, -x, z' 'x, -y, z' 'y, x, z' 'x+1/2, y+1/2, z+1/2' '-y+1/2, x+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' '-x+1/2, y+1/2, z+1/2' '-y+1/2, -x+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' 'y+1/2, x+1/2, z+1/2' _cell_length_a 14.6070(10) _cell_length_b 14.6070(10) _cell_length_c 13.5758(12) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2896.6(4) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 3745 _cell_measurement_theta_min 2.11 _cell_measurement_theta_max 24.32 _exptl_crystal_description Block _exptl_crystal_colour purple _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.284 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1162 _exptl_absorpt_coefficient_mu 0.372 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9029 _exptl_absorpt_correction_T_max 0.9226 _exptl_absorpt_process_details 'Jacobson, R. (1998) Private communication to Rigaku Corp.' _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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_type 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 4756 _diffrn_reflns_av_R_equivalents 0.0500 _diffrn_reflns_av_sigmaI/netI 0.0509 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.00 _diffrn_reflns_theta_max 26.00 _reflns_number_total 1424 _reflns_number_gt 1199 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear, Ver. 1.30 (Rigaku/MSC, 2001)' _computing_cell_refinement 'CrystalClear, Ver. 1.30 (Rigaku/MSC, 2001)' _computing_data_reduction 'CrystalStructure, Ver. 3.60 (Rigaku/MSC, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics '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^)+(0.0900P)^2^+1.9900P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.05(6) _refine_ls_number_reflns 1424 _refine_ls_number_parameters 112 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0690 _refine_ls_R_factor_gt 0.0602 _refine_ls_wR_factor_ref 0.1514 _refine_ls_wR_factor_gt 0.1486 _refine_ls_goodness_of_fit_ref 1.059 _refine_ls_restrained_S_all 1.058 _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 C1 C 0.6259(2) 0.3741(2) 0.4055(3) 0.0166(9) Uani 1 2 d S . . C2 C 0.7054(2) 0.4139(2) 0.4490(3) 0.0165(7) Uani 1 1 d . . . C3 C 0.7435(2) 0.3723(2) 0.5301(3) 0.0262(8) Uani 1 1 d . . . H3 H 0.7960 0.3979 0.5591 0.031 Uiso 1 1 calc R . . C4 C 0.7062(3) 0.2938(3) 0.5698(5) 0.0383(15) Uani 1 2 d S . . C5 C 0.7457(3) 0.5000 0.4056(4) 0.0193(10) Uani 1 2 d S . . H5A H 0.8120 0.5000 0.4167 0.023 Uiso 1 2 calc SR . . H5B H 0.7353 0.5000 0.3343 0.023 Uiso 1 2 calc SR . . C6 C 0.7164(3) 0.2836(3) 0.7428(5) 0.0482(18) Uani 1 2 d S . . H6B H 0.6505 0.2757 0.7437 0.072 Uiso 0.50 1 calc PR . . H6C H 0.7310 0.3482 0.7474 0.072 Uiso 0.50 1 calc PR . . H6A H 0.7433 0.2514 0.7982 0.072 Uiso 0.50 1 calc PR . . C7 C 0.7420(3) 0.1547(3) 0.6597(4) 0.0484(14) Uani 1 1 d . . . H7A H 0.7712 0.1315 0.7187 0.073 Uiso 1 1 calc R . . H7B H 0.7707 0.1278 0.6021 0.073 Uiso 1 1 calc R . . H7C H 0.6775 0.1388 0.6606 0.073 Uiso 1 1 calc R . . Mn1 Mn 0.5000 0.5000 0.32017(15) 0.0433(5) Uani 1 8 d S . . N1 N 0.7512(3) 0.2488(3) 0.6561(4) 0.0402(13) Uani 1 2 d S . . O1 O 0.59133(18) 0.40867(18) 0.3237(3) 0.0296(8) Uani 1 2 d S . . O2 O 0.5000 0.5000 0.5002(7) 0.045(2) Uani 1 8 d S . . O3 O 0.5000 0.5000 0.5922(8) 0.052(2) Uani 1 8 d S . . O1W O 0.5000 0.5000 0.1574(7) 0.043(2) Uani 1 8 d S . . H1X H 0.5599 0.4840 0.1338 0.052 Uiso 0.13 1 d PR . . H1Y H 0.4840 0.5599 0.1338 0.052 Uiso 0.13 1 d PR . . P1 P 0.5000 0.0000 0.6730(2) 0.0461(6) Uani 1 4 d S . . F1 F 0.5000 -0.1054(3) 0.6647(4) 0.0641(12) Uani 1 2 d S . . F2 F 0.5815(3) 0.0000 0.5921(4) 0.0697(14) Uani 1 2 d S . . F3 F 0.5829(3) 0.0000 0.7325(4) 0.0598(12) Uani 1 2 d S . . O3W O 0.6665(6) 0.5000 0.7244(8) 0.050(2) Uani 0.50 2 d SP . . H3X H 0.6553 0.5537 0.7033 0.060 Uiso 0.25 1 d PR . . H3Y H 0.6698 0.4633 0.6759 0.060 Uiso 0.25 1 d PR . . O2W O 0.7098(5) 0.5000 0.9029(7) 0.046(2) Uani 0.50 2 d SP . . H2X H 0.7412 0.5475 0.9157 0.055 Uiso 0.25 1 d PR . . H2Y H 0.7412 0.4525 0.9157 0.055 Uiso 0.25 1 d PR . . 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 C1 0.0163(12) 0.0163(12) 0.017(2) -0.0087(14) 0.0087(14) -0.0063(16) C2 0.0120(15) 0.0148(15) 0.0227(17) 0.0011(12) -0.0030(13) 0.0026(11) C3 0.0219(18) 0.0220(16) 0.035(2) 0.0055(15) -0.0120(16) -0.0045(15) C4 0.036(2) 0.036(2) 0.043(3) 0.017(2) -0.017(2) -0.018(2) C5 0.018(2) 0.017(2) 0.023(3) 0.000 0.003(2) 0.000 C6 0.052(3) 0.052(3) 0.041(4) 0.014(2) -0.014(2) 0.020(3) C7 0.055(3) 0.048(3) 0.043(3) 0.029(2) -0.029(2) -0.028(2) Mn1 0.0452(7) 0.0452(7) 0.0394(11) 0.000 0.000 0.000 N1 0.0419(18) 0.0419(18) 0.037(3) 0.0153(19) -0.0153(19) -0.015(2) O1 0.0291(11) 0.0291(11) 0.0305(19) -0.0012(14) 0.0012(14) -0.0130(15) O2 0.047(3) 0.047(3) 0.040(6) 0.000 0.000 0.000 O3 0.051(4) 0.051(4) 0.055(7) 0.000 0.000 0.000 O1W 0.046(3) 0.046(3) 0.038(5) 0.000 0.000 0.000 P1 0.0357(12) 0.0457(14) 0.0569(16) 0.000 0.000 0.000 F1 0.073(3) 0.052(2) 0.067(3) -0.027(2) 0.000 0.000 F2 0.072(3) 0.072(3) 0.065(3) 0.000 0.025(2) 0.000 F3 0.066(3) 0.054(2) 0.059(3) 0.000 -0.027(2) 0.000 O3W 0.044(6) 0.050(6) 0.056(6) 0.000 0.023(5) 0.000 O2W 0.029(4) 0.046(5) 0.062(6) 0.000 -0.020(4) 0.000 _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 C1 O1 1.320(6) . ? C1 C2 1.427(4) . ? C1 C2 1.427(4) 6_665 ? C2 C3 1.375(5) . ? C2 C5 1.508(4) . ? C3 C4 1.379(5) . ? C3 H3 0.9400 . ? C4 C3 1.379(5) 6_665 ? C4 N1 1.496(8) . ? C5 C2 1.508(4) 7_565 ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C6 N1 1.378(10) . ? C6 H6B 0.9700 . ? C6 H6C 0.9700 . ? C6 H6A 0.9700 . ? C7 N1 1.382(6) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C7 H7C 0.9700 . ? Mn1 O1 1.887(4) 2_655 ? Mn1 O1 1.887(4) 3_665 ? Mn1 O1 1.887(4) . ? Mn1 O1 1.887(4) 4_565 ? Mn1 O1W 2.210(10) . ? Mn1 O2 2.444(10) . ? N1 C7 1.382(6) 6_665 ? O2 O3 1.249(14) . ? O1W H1X 0.9600 . ? O1W H1Y 0.9600 . ? P1 F3 1.455(4) . ? P1 F3 1.455(4) 3_655 ? P1 F1 1.544(4) 3_655 ? P1 F1 1.544(4) . ? P1 F2 1.620(5) 3_655 ? P1 F2 1.620(5) . ? O3W H3X 0.8500 . ? O3W H3Y 0.8499 . ? O2W H2X 0.8499 . ? O2W H2Y 0.8499 . ? 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 C1 C2 120.2(2) . . ? O1 C1 C2 120.2(2) . 6_665 ? C2 C1 C2 119.5(4) . 6_665 ? C3 C2 C1 118.7(3) . . ? C3 C2 C5 121.6(3) . . ? C1 C2 C5 119.7(3) . . ? C2 C3 C4 121.4(4) . . ? C2 C3 H3 119.3 . . ? C4 C3 H3 119.3 . . ? C3 C4 C3 120.3(5) . 6_665 ? C3 C4 N1 119.9(3) . . ? C3 C4 N1 119.9(3) 6_665 . ? C2 C5 C2 113.0(4) 7_565 . ? C2 C5 H5A 109.0 7_565 . ? C2 C5 H5A 109.0 . . ? C2 C5 H5B 109.0 7_565 . ? C2 C5 H5B 109.0 . . ? H5A C5 H5B 107.8 . . ? N1 C6 H6B 109.5 . . ? N1 C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? N1 C6 H6A 109.5 . . ? H6B C6 H6A 109.5 . . ? H6C C6 H6A 109.5 . . ? N1 C7 H7A 109.5 . . ? N1 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? N1 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? O1 Mn1 O1 89.963(7) 2_655 3_665 ? O1 Mn1 O1 89.963(7) 2_655 . ? O1 Mn1 O1 177.1(3) 3_665 . ? O1 Mn1 O1 177.1(3) 2_655 4_565 ? O1 Mn1 O1 89.963(7) 3_665 4_565 ? O1 Mn1 O1 89.963(7) . 4_565 ? O1 Mn1 O1W 91.45(13) 2_655 . ? O1 Mn1 O1W 91.45(13) 3_665 . ? O1 Mn1 O1W 91.45(13) . . ? O1 Mn1 O1W 91.45(13) 4_565 . ? O1 Mn1 O2 88.55(13) 2_655 . ? O1 Mn1 O2 88.55(13) 3_665 . ? O1 Mn1 O2 88.55(13) . . ? O1 Mn1 O2 88.55(13) 4_565 . ? O1W Mn1 O2 180.000(2) . . ? C6 N1 C7 107.5(4) . 6_665 ? C6 N1 C7 107.5(4) . . ? C7 N1 C7 101.1(6) 6_665 . ? C6 N1 C4 110.1(6) . . ? C7 N1 C4 114.9(4) 6_665 . ? C7 N1 C4 114.9(4) . . ? C1 O1 Mn1 124.2(3) . . ? O3 O2 Mn1 180.000(2) . . ? Mn1 O1W H1X 109.5 . . ? Mn1 O1W H1Y 109.5 . . ? H1X O1W H1Y 109.5 . . ? F3 P1 F3 112.6(5) . 3_655 ? F3 P1 F1 92.32(13) . 3_655 ? F3 P1 F1 92.32(13) 3_655 3_655 ? F3 P1 F1 92.32(13) . . ? F3 P1 F1 92.32(13) 3_655 . ? F1 P1 F1 171.6(5) 3_655 . ? F3 P1 F2 171.0(4) . 3_655 ? F3 P1 F2 76.4(3) 3_655 3_655 ? F1 P1 F2 87.16(17) 3_655 3_655 ? F1 P1 F2 87.16(17) . 3_655 ? F3 P1 F2 76.4(3) . . ? F3 P1 F2 171.0(4) 3_655 . ? F1 P1 F2 87.16(17) 3_655 . ? F1 P1 F2 87.16(17) . . ? F2 P1 F2 94.6(4) 3_655 . ? H3X O3W H3Y 109.5 . . ? H2X O2W H2Y 109.5 . . ? 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 O1 C1 C2 C3 -175.4(4) . . . . ? C2 C1 C2 C3 2.2(6) 6_665 . . . ? O1 C1 C2 C5 4.7(5) . . . . ? C2 C1 C2 C5 -177.7(3) 6_665 . . . ? C1 C2 C3 C4 -0.2(7) . . . . ? C5 C2 C3 C4 179.7(5) . . . . ? C2 C3 C4 C3 -1.8(10) . . . 6_665 ? C2 C3 C4 N1 178.0(5) . . . . ? C3 C2 C5 C2 -90.6(4) . . . 7_565 ? C1 C2 C5 C2 89.3(5) . . . 7_565 ? C3 C4 N1 C6 90.1(6) . . . . ? C3 C4 N1 C6 -90.1(6) 6_665 . . . ? C3 C4 N1 C7 -31.5(9) . . . 6_665 ? C3 C4 N1 C7 148.3(6) 6_665 . . 6_665 ? C3 C4 N1 C7 -148.3(6) . . . . ? C3 C4 N1 C7 31.5(9) 6_665 . . . ? C2 C1 O1 Mn1 -91.2(3) . . . . ? C2 C1 O1 Mn1 91.2(3) 6_665 . . . ? O1 Mn1 O1 C1 88.55(13) 2_655 . . . ? O1 Mn1 O1 C1 -0.001(9) 3_665 . . . ? O1 Mn1 O1 C1 -88.55(13) 4_565 . . . ? O1W Mn1 O1 C1 180.0 . . . . ? O2 Mn1 O1 C1 0.0 . . . . ? O1 Mn1 O2 O3 180(100) 2_655 . . . ? O1 Mn1 O2 O3 90(100) 3_665 . . . ? O1 Mn1 O2 O3 -90(100) . . . . ? O1 Mn1 O2 O3 0(100) 4_565 . . . ? O1W Mn1 O2 O3 0(100) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.392 _refine_diff_density_min -0.724 _refine_diff_density_rms 0.066 #===END