# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name 'Philipp Kurz' 'Hans-Martin Berends' 'Anne-Marie Manke' 'Felix Tuczek' _publ_contact_author_email phkurz@ac.uni-kiel.de _publ_contact_author_name 'Philipp Kurz' data_Complex_1 _database_code_depnum_ccdc_archive 'CCDC 864158' #TrackingRef '- berends_etal_MnOtpdm_Complex_1.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H32 Mn2 N6 O5, 2(Cl O4)' _chemical_formula_sum 'C36 H32 Cl2 Mn2 N6 O13' _chemical_formula_weight 937.46 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' Cl Cl 0.1484 0.1585 '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 monoclinic _symmetry_space_group_name_H-M 'C 2/c' _symmetry_space_group_name_Hall '-C 2yc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 21.3151(15) _cell_length_b 12.4458(10) _cell_length_c 20.0612(13) _cell_angle_alpha 90.00 _cell_angle_beta 121.761(6) _cell_angle_gamma 90.00 _cell_volume 4525.0(6) _cell_formula_units_Z 4 _cell_measurement_temperature 170(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 4 _cell_measurement_theta_max 25 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.376 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1912 _exptl_absorpt_coefficient_mu 0.740 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 170(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 IPDS-1 _diffrn_measurement_method 'Phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 10190 _diffrn_reflns_av_R_equivalents 0.0701 _diffrn_reflns_av_sigmaI/netI 0.0685 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.98 _diffrn_reflns_theta_max 25.03 _reflns_number_total 3875 _reflns_number_gt 2608 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'IPDS-1 program package' _computing_cell_refinement 'IPDS-1 program package' _computing_data_reduction 'IPDS-1 program package' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0906P)^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 constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0036(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3875 _refine_ls_number_parameters 269 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0815 _refine_ls_R_factor_gt 0.0533 _refine_ls_wR_factor_ref 0.1411 _refine_ls_wR_factor_gt 0.1304 _refine_ls_goodness_of_fit_ref 0.944 _refine_ls_restrained_S_all 0.944 _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 0.43696(3) 0.41813(5) 0.65989(3) 0.0253(2) Uani 1 1 d . . . N11 N 0.33284(18) 0.5199(3) 0.61060(18) 0.0308(8) Uani 1 1 d . . . N21 N 0.37098(18) 0.3389(3) 0.55373(17) 0.0269(7) Uani 1 1 d . . . N31 N 0.46129(18) 0.5293(3) 0.59599(18) 0.0294(7) Uani 1 1 d . . . C1 C 0.3325(2) 0.5140(3) 0.4889(2) 0.0277(8) Uani 1 1 d . . . H1 H 0.3011 0.5415 0.4340 0.033 Uiso 1 1 calc R . . C11 C 0.2985(2) 0.5530(3) 0.5348(2) 0.0273(8) Uani 1 1 d . . . C12 C 0.2346(3) 0.6140(3) 0.4994(3) 0.0370(10) Uani 1 1 d . . . H12 H 0.2121 0.6359 0.4463 0.044 Uiso 1 1 calc R . . C13 C 0.2042(3) 0.6423(3) 0.5434(3) 0.0447(11) Uani 1 1 d . . . H13 H 0.1608 0.6850 0.5208 0.054 Uiso 1 1 calc R . . C14 C 0.2367(3) 0.6088(4) 0.6191(3) 0.0474(12) Uani 1 1 d . . . H14 H 0.2159 0.6264 0.6495 0.057 Uiso 1 1 calc R . . C15 C 0.3008(3) 0.5485(4) 0.6510(3) 0.0390(10) Uani 1 1 d . . . H15 H 0.3235 0.5260 0.7040 0.047 Uiso 1 1 calc R . . C21 C 0.3297(2) 0.3926(3) 0.4851(2) 0.0242(8) Uani 1 1 d . . . C22 C 0.2851(2) 0.3386(3) 0.4149(2) 0.0292(9) Uani 1 1 d . . . H22 H 0.2562 0.3776 0.3675 0.035 Uiso 1 1 calc R . . C23 C 0.2831(2) 0.2272(3) 0.4148(2) 0.0358(10) Uani 1 1 d . . . H23 H 0.2526 0.1889 0.3674 0.043 Uiso 1 1 calc R . . C24 C 0.3263(2) 0.1725(3) 0.4847(2) 0.0327(9) Uani 1 1 d . . . H24 H 0.3266 0.0962 0.4856 0.039 Uiso 1 1 calc R . . C25 C 0.3686(2) 0.2295(3) 0.5527(2) 0.0318(9) Uani 1 1 d . . . H25 H 0.3971 0.1915 0.6006 0.038 Uiso 1 1 calc R . . C31 C 0.4093(2) 0.5577(3) 0.5216(2) 0.0269(8) Uani 1 1 d . . . C32 C 0.4262(2) 0.6259(3) 0.4784(2) 0.0300(9) Uani 1 1 d . . . H32 H 0.3897 0.6431 0.4257 0.036 Uiso 1 1 calc R . . C33 C 0.4966(3) 0.6689(3) 0.5126(3) 0.0402(11) Uani 1 1 d . . . H33 H 0.5091 0.7153 0.4837 0.048 Uiso 1 1 calc R . . C34 C 0.5483(3) 0.6427(4) 0.5895(3) 0.0407(11) Uani 1 1 d . . . H34 H 0.5962 0.6736 0.6152 0.049 Uiso 1 1 calc R . . C35 C 0.5292(2) 0.5711(4) 0.6286(2) 0.0383(10) Uani 1 1 d . . . H35 H 0.5657 0.5506 0.6806 0.046 Uiso 1 1 calc R . . O1 O 0.5000 0.4870(3) 0.7500 0.0295(9) Uani 1 2 d S . . O2 O 0.39679(16) 0.3167(2) 0.70480(15) 0.0363(7) Uani 1 1 d . . . O3 O 0.48209(16) 0.3120(2) 0.83273(15) 0.0346(7) Uani 1 1 d . . . C41 C 0.4230(2) 0.2810(3) 0.7745(2) 0.0309(9) Uani 1 1 d . . . C42 C 0.3794(3) 0.1970(4) 0.7854(3) 0.0490(13) Uani 1 1 d . . . H42A H 0.4048 0.1764 0.8408 0.073 Uiso 1 1 calc R . . H42B H 0.3741 0.1339 0.7536 0.073 Uiso 1 1 calc R . . H42C H 0.3304 0.2254 0.7689 0.073 Uiso 1 1 calc R . . Cl1 Cl 0.20157(8) 0.60872(10) 0.25477(6) 0.0492(3) Uani 1 1 d . . . O11 O 0.1958(3) 0.7217(3) 0.2410(3) 0.0905(15) Uani 1 1 d . . . O12 O 0.2762(3) 0.5778(5) 0.2873(3) 0.1013(17) Uani 1 1 d . . . O13 O 0.1775(3) 0.5780(4) 0.3057(2) 0.0917(16) Uani 1 1 d . . . O14 O 0.1584(3) 0.5575(4) 0.1806(2) 0.0886(15) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.0163(3) 0.0446(4) 0.0144(3) 0.0008(2) 0.0077(2) -0.0015(3) N11 0.0213(18) 0.049(2) 0.0247(17) -0.0024(14) 0.0140(15) -0.0024(15) N21 0.0185(18) 0.0432(19) 0.0181(16) -0.0005(13) 0.0091(14) -0.0027(13) N31 0.0175(18) 0.052(2) 0.0193(16) -0.0020(14) 0.0100(14) -0.0061(15) C1 0.023(2) 0.041(2) 0.0167(18) 0.0023(15) 0.0088(16) 0.0015(16) C11 0.022(2) 0.034(2) 0.029(2) -0.0018(15) 0.0158(18) -0.0050(16) C12 0.033(3) 0.037(2) 0.047(3) 0.0023(18) 0.025(2) -0.0009(18) C13 0.041(3) 0.033(2) 0.071(3) -0.003(2) 0.038(3) 0.0074(19) C14 0.047(3) 0.052(3) 0.066(3) -0.024(2) 0.046(3) -0.010(2) C15 0.034(3) 0.061(3) 0.034(2) -0.0134(19) 0.026(2) -0.011(2) C21 0.020(2) 0.039(2) 0.0164(18) -0.0017(14) 0.0117(16) -0.0025(15) C22 0.025(2) 0.041(2) 0.0205(19) 0.0005(16) 0.0108(17) -0.0043(16) C23 0.026(2) 0.053(3) 0.029(2) -0.0086(18) 0.0144(19) -0.0088(19) C24 0.027(2) 0.035(2) 0.037(2) -0.0035(17) 0.018(2) -0.0022(17) C25 0.025(2) 0.043(2) 0.028(2) 0.0081(17) 0.0147(18) 0.0011(17) C31 0.024(2) 0.041(2) 0.0200(19) -0.0013(15) 0.0138(17) -0.0003(16) C32 0.027(2) 0.040(2) 0.027(2) 0.0002(16) 0.0172(18) -0.0032(17) C33 0.047(3) 0.047(2) 0.043(3) -0.0062(19) 0.035(2) -0.011(2) C34 0.026(2) 0.063(3) 0.039(2) -0.010(2) 0.021(2) -0.013(2) C35 0.026(2) 0.065(3) 0.027(2) -0.005(2) 0.0164(19) -0.012(2) O1 0.020(2) 0.052(2) 0.0146(18) 0.000 0.0076(16) 0.000 O2 0.0260(16) 0.0620(18) 0.0183(14) 0.0060(12) 0.0098(12) -0.0083(13) O3 0.0207(16) 0.0570(17) 0.0177(14) 0.0042(12) 0.0044(12) -0.0067(12) C41 0.020(2) 0.050(2) 0.025(2) 0.0024(17) 0.0139(19) 0.0022(18) C42 0.032(3) 0.075(3) 0.031(2) 0.006(2) 0.011(2) -0.021(2) Cl1 0.0521(8) 0.0617(7) 0.0329(6) 0.0026(5) 0.0218(6) 0.0006(6) O11 0.115(5) 0.058(2) 0.090(3) -0.002(2) 0.048(3) 0.001(2) O12 0.073(4) 0.171(5) 0.058(3) 0.016(3) 0.033(3) 0.025(3) O13 0.074(3) 0.163(5) 0.053(2) 0.033(3) 0.044(2) 0.017(3) O14 0.108(4) 0.098(3) 0.058(3) -0.029(2) 0.043(3) -0.034(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 O1 1.8032(19) . ? Mn1 O2 1.988(3) . ? Mn1 N21 2.082(3) . ? Mn1 O3 2.116(3) 2_656 ? Mn1 N31 2.128(3) . ? Mn1 N11 2.280(3) . ? Mn1 Mn1 3.1724(11) 2_656 ? N11 C15 1.353(5) . ? N11 C11 1.358(5) . ? N21 C21 1.356(5) . ? N21 C25 1.362(5) . ? N31 C35 1.341(5) . ? N31 C31 1.356(5) . ? C1 C31 1.507(5) . ? C1 C21 1.513(5) . ? C1 C11 1.523(5) . ? C11 C12 1.384(6) . ? C12 C13 1.388(6) . ? C13 C14 1.360(7) . ? C14 C15 1.386(7) . ? C21 C22 1.389(5) . ? C22 C23 1.388(6) . ? C23 C24 1.385(6) . ? C24 C25 1.372(6) . ? C31 C32 1.389(5) . ? C32 C33 1.389(6) . ? C33 C34 1.382(6) . ? C34 C35 1.382(6) . ? O1 Mn1 1.8032(19) 2_656 ? O2 C41 1.281(4) . ? O3 C41 1.245(5) . ? O3 Mn1 2.116(3) 2_656 ? C41 C42 1.490(6) . ? Cl1 O13 1.415(4) . ? Cl1 O12 1.419(5) . ? Cl1 O14 1.423(4) . ? Cl1 O11 1.425(4) . ? 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 O2 96.84(11) . . ? O1 Mn1 N21 175.28(9) . . ? O2 Mn1 N21 86.71(12) . . ? O1 Mn1 O3 94.41(10) . 2_656 ? O2 Mn1 O3 95.84(12) . 2_656 ? N21 Mn1 O3 82.10(12) . 2_656 ? O1 Mn1 N31 90.30(12) . . ? O2 Mn1 N31 170.38(12) . . ? N21 Mn1 N31 86.53(12) . . ? O3 Mn1 N31 90.00(12) 2_656 . ? O1 Mn1 N11 102.24(12) . . ? O2 Mn1 N11 89.78(12) . . ? N21 Mn1 N11 80.82(12) . . ? O3 Mn1 N11 161.67(11) 2_656 . ? N31 Mn1 N11 82.38(12) . . ? O1 Mn1 Mn1 28.40(11) . 2_656 ? O2 Mn1 Mn1 78.00(8) . 2_656 ? N21 Mn1 Mn1 151.26(9) . 2_656 ? O3 Mn1 Mn1 75.51(7) 2_656 2_656 ? N31 Mn1 Mn1 110.96(9) . 2_656 ? N11 Mn1 Mn1 122.79(8) . 2_656 ? C15 N11 C11 116.5(4) . . ? C15 N11 Mn1 124.7(3) . . ? C11 N11 Mn1 118.8(2) . . ? C21 N21 C25 118.5(3) . . ? C21 N21 Mn1 122.2(2) . . ? C25 N21 Mn1 119.3(2) . . ? C35 N31 C31 118.9(3) . . ? C35 N31 Mn1 120.1(3) . . ? C31 N31 Mn1 121.0(3) . . ? C31 C1 C21 112.8(3) . . ? C31 C1 C11 112.0(3) . . ? C21 C1 C11 109.2(3) . . ? N11 C11 C12 123.1(4) . . ? N11 C11 C1 115.6(3) . . ? C12 C11 C1 121.2(3) . . ? C11 C12 C13 118.3(4) . . ? C14 C13 C12 119.9(4) . . ? C13 C14 C15 118.7(4) . . ? N11 C15 C14 123.5(4) . . ? N21 C21 C22 121.5(3) . . ? N21 C21 C1 117.0(3) . . ? C22 C21 C1 121.4(3) . . ? C23 C22 C21 119.2(4) . . ? C24 C23 C22 119.1(4) . . ? C25 C24 C23 119.4(4) . . ? N21 C25 C24 122.2(4) . . ? N31 C31 C32 121.0(4) . . ? N31 C31 C1 117.2(3) . . ? C32 C31 C1 121.8(3) . . ? C33 C32 C31 119.7(4) . . ? C34 C33 C32 118.6(4) . . ? C35 C34 C33 119.1(4) . . ? N31 C35 C34 122.5(4) . . ? Mn1 O1 Mn1 123.2(2) . 2_656 ? C41 O2 Mn1 132.1(3) . . ? C41 O3 Mn1 130.1(2) . 2_656 ? O3 C41 O2 124.1(4) . . ? O3 C41 C42 118.7(3) . . ? O2 C41 C42 117.1(4) . . ? O13 Cl1 O12 109.8(3) . . ? O13 Cl1 O14 110.7(3) . . ? O12 Cl1 O14 108.1(3) . . ? O13 Cl1 O11 112.3(3) . . ? O12 Cl1 O11 108.6(3) . . ? O14 Cl1 O11 107.3(3) . . ? _diffrn_measured_fraction_theta_max 0.970 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.970 _refine_diff_density_max 0.431 _refine_diff_density_min -0.536 _refine_diff_density_rms 0.094 # SQUEEZE RESULTS (APPEND TO CIF) loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons 1 0.500 0.000 0.035 474.9 171.1 2 1.000 0.500 0.221 474.9 171.1 _platon_squeeze_details ; ;