# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and # The Centre National de la Recherche Scientifique, 2001 data_MnIII_Porphyrin_like_complex _database_code_CSD 151936 _journal_coden_Cambridge 0440 _publ_requested_journal ' New J.Chem.(Nouv.J.Chim.)' loop_ _publ_author_name 'Courseille, Christian' 'Dautant, A.' 'Mathoniere, C.' 'Pierre, C.' 'Verlhac, Jean-Baptiste' 'Vincent, J.-M.' _publ_contact_author_name 'Prof Jean-Baptiste Verlhac' _publ_contact_author_address ; Prof Jean-Baptiste Verlhac Laboratoire de Chimie Organique et Organometallique - CNRS Universite Bordeaux I 351 Cours de la Liberation Talence Cedex 334405 FRANCE ; _audit_creation_method SHELXL-97 #*********************************************************************** # 1. Data block for start identification : #*********************************************************************** # 2. Person Making Publication : _publ_contact_author ' J.-M Vincent' _publ_contact_author_fax '(33) (0) 5 56 84 89 42 ' _publ_contact_author_email 'jm.vincent@lcoo.u-bordeaux.fr' _publ_requested_journal ' New Journal of Chemistry' #*********************************************************************** _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C 25 H 16 F 3 Mn 1 N 6 O 5 S' _chemical_formula_weight 624.44 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Mn' 'Mn3+' -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'C m c m' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x, -y, -z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z+1/2' 'x+1/2, -y+1/2, -z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, y, -z-1/2' '-x, y, z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, y+1/2, -z-1/2' '-x+1/2, y+1/2, z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 14.969(4) _cell_length_b 7.986(7) _cell_length_c 20.429(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2442(2) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 15 _cell_measurement_theta_max 25 _exptl_crystal_description diamond _exptl_crystal_colour 'greenish brown' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.698 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1264 _exptl_absorpt_coefficient_mu 5.877 _exptl_absorpt_correction_type 'Psi-scan (North, Phillips, Mathews, 1968)' _exptl_absorpt_correction_T_min 0.2021 _exptl_absorpt_correction_T_max 0.8670 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54180 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf-Nonius CAD-4 diffractometer' _diffrn_measurement_method \w/\q _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 180 _diffrn_standards_decay_% 0 _diffrn_reflns_number 619 _diffrn_reflns_av_R_equivalents 0.0660 _diffrn_reflns_av_sigmaI/netI 0.0376 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 4.33 _diffrn_reflns_theta_max 49.99 _reflns_number_total 619 _reflns_number_gt 505 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Enraf-Nonius CAD-4 software 1976' _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SIR97 (Altomare et al, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Farrugia, 2000)' _computing_publication_material 'ORTEP-3 (Farrugia, 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^)+(0.1289P)^2^+32.5944P] 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 SHELXL _refine_ls_extinction_coef 0.0001(2) _refine_ls_extinction_expression 'Fc^*^==kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 619 _refine_ls_number_parameters 125 _refine_ls_number_restraints 55 _refine_ls_R_factor_all 0.0991 _refine_ls_R_factor_gt 0.0861 _refine_ls_wR_factor_ref 0.2514 _refine_ls_wR_factor_gt 0.2439 _refine_ls_goodness_of_fit_ref 1.162 _refine_ls_restrained_S_all 1.143 _refine_ls_shift/su_max 0.391 _refine_ls_shift/su_mean 0.101 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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn Mn3+ 0.0000 0.0000 0.5000 0.0515(15) Uani 1 4 d S . . O1W O 0.0000 -0.2332(15) 0.5631(5) 0.075(4) Uani 1 2 d S . . N1 N 0.0874(6) 0.1004(12) 0.5571(4) 0.056(3) Uani 1 1 d . . . C2 C 0.0474(8) 0.1946(15) 0.6068(6) 0.072(4) Uani 1 1 d . . . C3 C 0.1007(13) 0.2780(18) 0.6521(6) 0.093(5) Uani 1 1 d . . . H3 H 0.0753 0.3437 0.6847 0.111 Uiso 1 1 calc R . . C4 C 0.1937(14) 0.261(2) 0.6474(11) 0.115(7) Uani 1 1 d . . . H4 H 0.2305 0.3115 0.6783 0.138 Uiso 1 1 calc R . . C5 C 0.2290(11) 0.173(2) 0.5993(10) 0.107(6) Uani 1 1 d . . . H5 H 0.2909 0.1664 0.5964 0.129 Uiso 1 1 calc R . . C6 C 0.1767(9) 0.0895(16) 0.5518(7) 0.074(4) Uani 1 1 d . . . C7 C 0.2169(11) 0.0000 0.5000 0.071(5) Uani 1 2 d S . . C8 C 0.3110(13) 0.0000 0.5000 0.096(7) Uani 1 2 d S . . N9 N 0.3876(13) 0.0000 0.5000 0.145(9) Uani 1 2 d S . . O1 O 0.0845(16) -0.175(3) 0.6941(11) 0.096(8) Uani 0.25 1 d PDU . . O2 O 0.0845(16) -0.175(3) 0.8059(11) 0.096(8) Uani 0.25 1 d PDU . . O3 O 0.042(2) -0.429(2) 0.7500 0.139(15) Uani 0.50 2 d SPDU . . S S 0.0431(8) -0.2542(13) 0.7500 0.062(3) Uani 0.50 2 d SPD . . C C -0.0702(17) -0.212(5) 0.7500 0.25(8) Uani 0.50 2 d SPDU . . F1 F -0.103(3) -0.275(5) 0.6960(12) 0.231(18) Uani 0.25 1 d PDU . . F2 F -0.103(3) -0.275(5) 0.8040(12) 0.231(18) Uani 0.25 1 d PDU . . F3 F -0.074(3) -0.049(5) 0.7500 0.232(19) Uani 0.50 2 d SPDU . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn 0.047(2) 0.054(2) 0.053(2) -0.007(2) 0.000 0.000 O1W 0.108(9) 0.065(8) 0.052(7) 0.006(6) 0.000 0.000 N1 0.058(6) 0.050(6) 0.059(6) -0.003(5) -0.010(5) -0.009(5) C2 0.095(8) 0.063(8) 0.059(7) -0.006(7) -0.011(7) -0.011(7) C3 0.149(15) 0.077(10) 0.053(9) -0.015(7) -0.010(9) -0.018(10) C4 0.125(18) 0.081(13) 0.140(19) -0.004(12) -0.060(14) -0.025(11) C5 0.086(11) 0.089(14) 0.147(17) 0.022(13) -0.034(13) -0.028(10) C6 0.063(9) 0.057(8) 0.102(11) 0.009(8) -0.030(9) -0.015(7) C7 0.048(11) 0.058(11) 0.108(15) 0.006(13) 0.000 0.000 C8 0.056(14) 0.069(13) 0.16(2) 0.045(15) 0.000 0.000 N9 0.054(11) 0.113(15) 0.27(3) 0.017(19) 0.000 0.000 O1 0.108(15) 0.116(17) 0.064(13) 0.024(12) 0.033(11) 0.021(14) O2 0.108(15) 0.116(17) 0.064(13) -0.024(12) -0.033(11) 0.021(14) O3 0.22(4) 0.063(17) 0.13(2) 0.000 0.000 0.025(19) S 0.067(5) 0.079(7) 0.039(5) 0.000 0.000 0.024(5) C 0.24(9) 0.27(9) 0.26(9) 0.000 0.000 -0.07(5) F1 0.22(3) 0.28(3) 0.19(2) -0.06(2) -0.10(2) -0.01(3) F2 0.22(3) 0.28(3) 0.19(2) 0.06(2) 0.10(2) -0.01(3) F3 0.27(3) 0.20(3) 0.23(3) 0.000 0.000 0.15(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 Mn N1 1.928(8) . ? Mn N1 1.928(8) 9_556 ? Mn N1 1.928(8) 11 ? Mn N1 1.928(8) 3_556 ? Mn O1W 2.265(11) 9_556 ? Mn O1W 2.265(11) . ? O1W O1 3.00(3) . ? O1W N9 3.006(15) 5_445 ? O1W N9 3.006(15) 15_545 ? O1W F1 3.14(3) . ? N1 C6 1.343(15) . ? N1 C2 1.399(14) . ? C2 C3 1.392(17) . ? C2 C2 1.42(2) 11 ? C3 C4 1.40(2) . ? C4 C5 1.32(2) . ? C5 C6 1.42(2) . ? C6 C7 1.412(16) . ? C7 C6 1.412(16) 3_556 ? C7 C8 1.41(3) . ? C8 N9 1.15(2) . ? O1 S 1.445(19) . ? O2 S 1.445(19) . ? O3 S 1.396(17) . ? S C 1.73(2) . ? C F3 1.30(2) . ? C F1 1.31(2) . ? C F2 1.31(2) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Mn N1 180.0(4) . 9_556 ? N1 Mn N1 85.5(6) . 11 ? N1 Mn N1 94.5(6) 9_556 11 ? N1 Mn N1 94.5(6) . 3_556 ? N1 Mn N1 85.5(6) 9_556 3_556 ? N1 Mn N1 180.0(4) 11 3_556 ? N1 Mn O1W 90.2(3) . 9_556 ? N1 Mn O1W 89.8(3) 9_556 9_556 ? N1 Mn O1W 90.2(3) 11 9_556 ? N1 Mn O1W 89.8(3) 3_556 9_556 ? N1 Mn O1W 89.8(3) . . ? N1 Mn O1W 90.2(3) 9_556 . ? N1 Mn O1W 89.8(3) 11 . ? N1 Mn O1W 90.2(3) 3_556 . ? O1W Mn O1W 180.000(1) 9_556 . ? Mn O1W O1 112.4(6) . . ? Mn O1W N9 109.8(3) . 5_445 ? O1 O1W N9 136.9(5) . 5_445 ? Mn O1W N9 109.8(3) . 15_545 ? O1 O1W N9 104.9(6) . 15_545 ? N9 O1W N9 68.1(7) 5_445 15_545 ? Mn O1W F1 125.4(8) . . ? O1 O1W F1 56.7(6) . . ? N9 O1W F1 91.2(7) 5_445 . ? N9 O1W F1 124.8(8) 15_545 . ? C6 N1 C2 121.3(10) . . ? C6 N1 Mn 126.8(9) . . ? C2 N1 Mn 111.8(8) . . ? C3 C2 N1 119.6(12) . . ? C3 C2 C2 125.0(9) . 11 ? N1 C2 C2 115.4(6) . 11 ? C2 C3 C4 118.5(15) . . ? C5 C4 C3 120.1(17) . . ? C4 C5 C6 122.7(17) . . ? N1 C6 C7 121.2(12) . . ? N1 C6 C5 117.7(14) . . ? C7 C6 C5 121.1(14) . . ? C6 C7 C6 129.5(16) 3_556 . ? C6 C7 C8 115.2(8) 3_556 . ? C6 C7 C8 115.2(8) . . ? N9 C8 C7 180.000(5) . . ? S O1 O1W 117.1(12) . . ? O3 S O2 116.4(12) . . ? O3 S O1 116.4(12) . . ? O2 S O1 104.3(18) . . ? O3 S C 100(2) . . ? O2 S C 109.6(14) . . ? O1 S C 109.6(14) . . ? F3 C F1 111.6(19) . . ? F3 C F2 111.6(19) . . ? F1 C F2 115(3) . . ? F3 C S 104(3) . . ? F1 C S 107(2) . . ? F2 C S 107(2) . . ? C F1 O1W 120.3(19) . . ? 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 S C F1 61(2) . . . . ? O2 S C F2 -61(2) . . . . ? O3 S C F3 180.0 . . . . ? _diffrn_measured_fraction_theta_max 0.908 _diffrn_reflns_theta_full 49.99 _diffrn_measured_fraction_theta_full 0.908 _refine_diff_density_max 1.068 _refine_diff_density_min -0.383 _refine_diff_density_rms 0.099