# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'McKenzie, Christine' _publ_contact_author_email chk@ifk.sdu.dk _publ_section_title ; High Turnover Catalysis of Water Oxidation by Mn(II) complexes of Monoanionic Pentadentate Ligands ; loop_ _publ_author_name R.K.Seidler-Egdal A.Nielsen M.B.Nielsen A.D.Bond M.J.Bjerrum C.J.McKenzie # Attachment '- Mncomplexes.cif' data_[Mn(mebpena)]n(ClO4)n _database_code_depnum_ccdc_archive 'CCDC 776098' #TrackingRef '- Mncomplexes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H21 N4 O2 Mn +, Cl O4 -, H2 O' _chemical_formula_sum 'C17 H23 Cl Mn N4 O7' _chemical_formula_weight 485.78 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 triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.1700(8) _cell_length_b 12.5805(11) _cell_length_c 19.3814(17) _cell_angle_alpha 76.431(2) _cell_angle_beta 81.763(2) _cell_angle_gamma 75.643(2) _cell_volume 2097.0(3) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 1874 _cell_measurement_theta_min 2.53 _cell_measurement_theta_max 21.70 _exptl_crystal_description block _exptl_crystal_colour green _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.539 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1004 _exptl_absorpt_coefficient_mu 0.804 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.719 _exptl_absorpt_correction_T_max 0.924 _exptl_absorpt_process_details 'SADABS (Sheldrick, 2003)' _exptl_special_details ; Several crystals present - indexed and integrated only one. The diffraction patterns are well separated in parts (thus the ability to index only one of them), but overlap in other areas. This leads numerous reflections with F^2^(obs) significantly overestimated. Reflections with F^2^(obs)-F^2^(calc) greater than 5 times the esd of the difference were therefore omitted from the refinement (33 reflections omitted in total). Refinement against ALL reflections (without any omissions) gives R1 = 0.0980, wR2 = 0.3097. Crystal also relatively weakly diffracting - data truncated at 0.95 \%A. SIMU restraints placed on all C and N atoms to prevent them becoming NPD. Poorly-defined solvent modelled as 4 x 50% occupied water sites (i.e. one water molecule per Mn formula unit). H atoms omitted from O atoms of water molecules. ; _diffrn_ambient_temperature 180(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 'Bruker-Nonius X8APEX-II CCD' _diffrn_measurement_method 'thin-slice \w and \f scans' _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 10217 _diffrn_reflns_av_R_equivalents 0.0771 _diffrn_reflns_av_sigmaI/netI 0.1292 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 3.56 _diffrn_reflns_theta_max 21.97 _diffrn_measured_fraction_theta_max 0.980 _diffrn_reflns_theta_full 21.97 _diffrn_measured_fraction_theta_full 0.980 _reflns_number_total 5039 _reflns_number_gt 2990 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 v.1.0-22 (Bruker-Nonius, 2004)' _computing_cell_refinement 'SAINT v.7.06a (Bruker, 2003)' _computing_data_reduction 'SAINT v.7.06a' _computing_structure_solution 'SHELXTL v.6.12 (Sheldrick, 2001)' _computing_structure_refinement 'SHELXTL v.6.12' _computing_molecular_graphics 'SHELXTL v.6.12' _computing_publication_material 'SHELXTL v.6.12' _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^)+(0.1604P)^2^+3.0721P] 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_number_reflns 5039 _refine_ls_number_parameters 537 _refine_ls_number_restraints 284 _refine_ls_R_factor_all 0.1498 _refine_ls_R_factor_gt 0.0895 _refine_ls_wR_factor_ref 0.2723 _refine_ls_wR_factor_gt 0.2364 _refine_ls_goodness_of_fit_ref 1.033 _refine_ls_restrained_S_all 1.029 _refine_ls_shift/su_max 0.009 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 1.176 _refine_diff_density_min -0.600 _refine_diff_density_rms 0.136 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 0.38045(17) 0.66506(12) 0.27835(8) 0.0261(5) Uani 1 1 d . . . O1 O 0.1424(8) 0.7387(5) 0.2808(4) 0.0340(18) Uani 1 1 d . . . O2 O -0.0884(8) 0.7100(6) 0.3154(4) 0.0351(19) Uani 1 1 d . . . N1 N 0.5571(10) 0.5406(7) 0.3514(5) 0.036(2) Uani 1 1 d U . . N2 N 0.2611(9) 0.5189(7) 0.3288(4) 0.0299(19) Uani 1 1 d U . . N3 N 0.4080(12) 0.7499(8) 0.3639(5) 0.047(2) Uani 1 1 d U . . N4 N 0.4203(10) 0.5558(7) 0.1981(4) 0.035(2) Uani 1 1 d U . . C1 C 0.6321(14) 0.6054(10) 0.3822(6) 0.046(3) Uani 1 1 d U . . H1A H 0.7204 0.6222 0.3493 0.055 Uiso 1 1 calc R . . H1B H 0.6703 0.5590 0.4275 0.055 Uiso 1 1 calc R . . C2 C 0.5341(15) 0.7115(11) 0.3963(6) 0.049(3) Uani 1 1 d U . . C3 C 0.5789(18) 0.7701(12) 0.4378(7) 0.061(3) Uani 1 1 d U . . H3A H 0.6691 0.7412 0.4612 0.074 Uiso 1 1 calc R . . C4 C 0.4869(19) 0.8725(13) 0.4441(7) 0.069(3) Uani 1 1 d U . . H4A H 0.5183 0.9165 0.4704 0.083 Uiso 1 1 calc R . . C5 C 0.3540(19) 0.9136(12) 0.4145(8) 0.067(3) Uani 1 1 d U . . H5A H 0.2886 0.9819 0.4226 0.080 Uiso 1 1 calc R . . C6 C 0.3169(17) 0.8498(11) 0.3709(7) 0.063(3) Uani 1 1 d U . . H6A H 0.2278 0.8774 0.3466 0.075 Uiso 1 1 calc R . . C7 C 0.6699(14) 0.4598(10) 0.3168(7) 0.054(3) Uani 1 1 d U . . H7A H 0.7385 0.4112 0.3515 0.082 Uiso 1 1 calc R . . H7B H 0.7278 0.5002 0.2774 0.082 Uiso 1 1 calc R . . H7C H 0.6187 0.4139 0.2983 0.082 Uiso 1 1 calc R . . C8 C 0.4640(12) 0.4793(9) 0.4091(6) 0.036(2) Uani 1 1 d U . . H8A H 0.4039 0.5312 0.4392 0.044 Uiso 1 1 calc R . . H8B H 0.5313 0.4179 0.4396 0.044 Uiso 1 1 calc R . . C9 C 0.3603(12) 0.4314(9) 0.3785(6) 0.035(2) Uani 1 1 d U . . H9A H 0.4211 0.3737 0.3526 0.042 Uiso 1 1 calc R . . H9B H 0.2965 0.3944 0.4177 0.042 Uiso 1 1 calc R . . C10 C 0.2250(12) 0.4742(9) 0.2708(5) 0.032(2) Uani 1 1 d U . . H10A H 0.1304 0.5221 0.2517 0.039 Uiso 1 1 calc R . . H10B H 0.2081 0.3977 0.2901 0.039 Uiso 1 1 calc R . . C11 C 0.3503(12) 0.4706(9) 0.2116(6) 0.031(2) Uani 1 1 d U . . C12 C 0.3836(13) 0.3903(9) 0.1710(6) 0.039(3) Uani 1 1 d U . . H12A H 0.3343 0.3294 0.1825 0.047 Uiso 1 1 calc R . . C13 C 0.4910(14) 0.3995(10) 0.1126(6) 0.048(3) Uani 1 1 d U . . H13A H 0.5165 0.3443 0.0842 0.057 Uiso 1 1 calc R . . C14 C 0.5588(15) 0.4873(10) 0.0966(6) 0.050(3) Uani 1 1 d U . . H14A H 0.6303 0.4958 0.0562 0.060 Uiso 1 1 calc R . . C15 C 0.5220(13) 0.5642(10) 0.1401(6) 0.043(3) Uani 1 1 d U . . H15A H 0.5700 0.6257 0.1290 0.052 Uiso 1 1 calc R . . C16 C 0.1185(12) 0.5718(8) 0.3656(6) 0.032(2) Uani 1 1 d U . . H16A H 0.1389 0.5858 0.4111 0.038 Uiso 1 1 calc R . . H16B H 0.0473 0.5212 0.3764 0.038 Uiso 1 1 calc R . . C17 C 0.0496(13) 0.6818(8) 0.3177(5) 0.030(2) Uani 1 1 d U . . Mn2 Mn 0.83970(18) 0.84159(13) 0.22812(8) 0.0279(5) Uani 1 1 d . . . O3 O 0.6476(8) 0.7705(5) 0.2294(4) 0.0308(18) Uani 1 1 d . . . O4 O 0.4198(8) 0.7987(5) 0.1937(4) 0.0327(18) Uani 1 1 d . . . N5 N 0.9829(11) 0.9512(9) 0.1486(5) 0.046(2) Uani 1 1 d U . . N6 N 0.6554(10) 0.9877(7) 0.1750(4) 0.0320(19) Uani 1 1 d U . . N7 N 0.9604(11) 0.7396(9) 0.1475(5) 0.049(2) Uani 1 1 d U . . N8 N 0.7652(11) 0.9637(7) 0.3028(5) 0.038(2) Uani 1 1 d U . . C18 C 1.1119(14) 0.8757(12) 0.1180(7) 0.058(3) Uani 1 1 d U . . H18A H 1.1951 0.8559 0.1493 0.070 Uiso 1 1 calc R . . H18B H 1.1481 0.9165 0.0710 0.070 Uiso 1 1 calc R . . C19 C 1.0788(15) 0.7717(12) 0.1087(7) 0.059(3) Uani 1 1 d U . . C20 C 1.1737(17) 0.7072(14) 0.0628(7) 0.079(4) Uani 1 1 d U . . H20A H 1.2576 0.7310 0.0342 0.095 Uiso 1 1 calc R . . C21 C 1.1387(19) 0.6081(15) 0.0614(8) 0.085(4) Uani 1 1 d U . . H21A H 1.2034 0.5602 0.0330 0.101 Uiso 1 1 calc R . . C22 C 1.0156(17) 0.5758(13) 0.0990(7) 0.075(4) Uani 1 1 d U . . H22A H 0.9890 0.5089 0.0956 0.090 Uiso 1 1 calc R . . C23 C 0.9305(15) 0.6450(12) 0.1425(7) 0.059(3) Uani 1 1 d U . . H23A H 0.8450 0.6229 0.1706 0.070 Uiso 1 1 calc R . . C24 C 1.0343(17) 1.0285(13) 0.1791(7) 0.071(4) Uani 1 1 d U . . H24A H 1.0936 1.0722 0.1422 0.107 Uiso 1 1 calc R . . H24B H 1.0975 0.9863 0.2177 0.107 Uiso 1 1 calc R . . H24C H 0.9469 1.0794 0.1981 0.107 Uiso 1 1 calc R . . C25 C 0.8796(12) 1.0130(9) 0.0930(6) 0.039(3) Uani 1 1 d U . . H25A H 0.8662 0.9599 0.0652 0.046 Uiso 1 1 calc R . . H25B H 0.9271 1.0703 0.0599 0.046 Uiso 1 1 calc R . . C26 C 0.7284(13) 1.0691(9) 0.1219(6) 0.036(2) Uani 1 1 d U . . H26A H 0.7395 1.1290 0.1447 0.044 Uiso 1 1 calc R . . H26B H 0.6633 1.1044 0.0824 0.044 Uiso 1 1 calc R . . C27 C 0.5582(13) 1.0394(9) 0.2308(6) 0.038(2) Uani 1 1 d U . . H27A H 0.4829 0.9942 0.2531 0.046 Uiso 1 1 calc R . . H27B H 0.5030 1.1155 0.2094 0.046 Uiso 1 1 calc R . . C28 C 0.6516(14) 1.0466(9) 0.2871(6) 0.040(2) Uani 1 1 d U . . C29 C 0.6118(16) 1.1332(10) 0.3223(6) 0.050(3) Uani 1 1 d U . . H29A H 0.5275 1.1929 0.3097 0.060 Uiso 1 1 calc R . . C30 C 0.6950(17) 1.1335(11) 0.3764(7) 0.058(3) Uani 1 1 d U . . H30A H 0.6707 1.1942 0.4003 0.070 Uiso 1 1 calc R . . C31 C 0.8123(16) 1.0452(10) 0.3945(6) 0.051(3) Uani 1 1 d U . . H31A H 0.8706 1.0423 0.4320 0.061 Uiso 1 1 calc R . . C32 C 0.8451(15) 0.9588(10) 0.3569(6) 0.045(3) Uani 1 1 d U . . H32A H 0.9251 0.8956 0.3697 0.054 Uiso 1 1 calc R . . C33 C 0.5682(12) 0.9329(8) 0.1405(5) 0.028(2) Uani 1 1 d U . . H33A H 0.6253 0.9142 0.0960 0.034 Uiso 1 1 calc R . . H33B H 0.4702 0.9843 0.1285 0.034 Uiso 1 1 calc R . . C34 C 0.5413(13) 0.8264(9) 0.1922(6) 0.030(2) Uani 1 1 d U . . Cl1 Cl -0.0157(5) 0.2693(3) 0.46816(18) 0.0679(11) Uani 1 1 d D . . O5 O -0.0014(19) 0.1556(7) 0.4867(7) 0.160(7) Uani 1 1 d D . . O6 O 0.0636(11) 0.3124(10) 0.5069(6) 0.108(4) Uani 1 1 d D . . O7 O -0.1758(10) 0.3154(14) 0.4865(7) 0.161(7) Uani 1 1 d D . . O8 O 0.0074(13) 0.3111(9) 0.3954(4) 0.102(4) Uani 1 1 d D . . Cl2 Cl 0.7089(4) 0.7701(2) -0.03204(16) 0.0470(9) Uani 1 1 d D . . O9 O 0.7900(10) 0.8352(7) -0.0098(5) 0.068(3) Uani 1 1 d D . . O10 O 0.6772(10) 0.8136(7) -0.1035(4) 0.059(2) Uani 1 1 d D . . O11 O 0.7840(13) 0.6570(6) -0.0230(7) 0.114(5) Uani 1 1 d D . . O12 O 0.5659(10) 0.7770(9) 0.0093(5) 0.095(4) Uani 1 1 d D . . O100 O 0.254(4) 0.188(3) 0.3183(17) 0.143(5) Uiso 0.50 1 d P A 1 O102 O 0.085(4) 0.229(3) 0.2657(17) 0.143(5) Uiso 0.50 1 d P B 1 O101 O 0.177(4) 0.162(3) 0.2891(19) 0.143(5) Uiso 0.50 1 d P C 2 O103 O -0.100(3) 0.325(2) 0.1583(16) 0.143(5) Uiso 0.50 1 d P D 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 0.0309(10) 0.0287(9) 0.0186(10) -0.0013(7) -0.0018(7) -0.0098(7) O1 0.039(5) 0.030(4) 0.030(4) 0.002(3) 0.002(4) -0.012(4) O2 0.021(4) 0.043(5) 0.038(5) 0.000(4) -0.004(4) -0.008(4) N1 0.037(5) 0.041(5) 0.029(5) 0.001(4) -0.002(4) -0.016(4) N2 0.036(4) 0.029(4) 0.024(4) -0.004(3) -0.002(3) -0.008(3) N3 0.063(6) 0.053(5) 0.033(5) -0.010(4) 0.010(5) -0.033(5) N4 0.047(5) 0.038(4) 0.020(4) -0.007(4) 0.012(4) -0.017(4) C1 0.058(6) 0.051(6) 0.030(5) 0.008(5) -0.004(5) -0.031(5) C2 0.068(6) 0.060(5) 0.030(5) 0.000(5) -0.001(5) -0.044(5) C3 0.091(7) 0.070(6) 0.037(6) -0.001(5) -0.004(6) -0.053(6) C4 0.107(8) 0.073(7) 0.043(6) -0.015(6) 0.002(6) -0.052(6) C5 0.096(7) 0.060(6) 0.052(7) -0.013(5) 0.011(6) -0.039(6) C6 0.084(7) 0.054(6) 0.048(6) -0.003(5) 0.014(6) -0.032(6) C7 0.047(7) 0.055(8) 0.047(8) 0.008(6) 0.000(6) -0.003(6) C8 0.042(5) 0.039(5) 0.024(5) 0.004(4) -0.009(4) -0.009(4) C9 0.037(5) 0.038(5) 0.025(5) 0.005(4) -0.010(4) -0.005(4) C10 0.037(5) 0.033(5) 0.030(5) -0.004(4) -0.001(4) -0.016(4) C11 0.038(5) 0.036(5) 0.025(5) -0.008(4) 0.001(4) -0.017(4) C12 0.051(6) 0.040(5) 0.031(5) -0.012(4) 0.001(5) -0.015(5) C13 0.059(6) 0.053(6) 0.036(6) -0.022(5) 0.001(5) -0.014(5) C14 0.068(6) 0.053(6) 0.031(6) -0.012(5) 0.000(5) -0.015(5) C15 0.060(6) 0.040(5) 0.026(5) -0.002(5) 0.004(5) -0.015(5) C16 0.040(5) 0.030(5) 0.025(5) -0.008(4) 0.003(4) -0.010(4) C17 0.042(7) 0.030(5) 0.020(6) -0.003(5) -0.002(5) -0.013(5) Mn2 0.0323(10) 0.0312(10) 0.0194(10) -0.0017(7) 0.0019(7) -0.0112(8) O3 0.029(4) 0.029(4) 0.030(5) 0.006(3) -0.004(4) -0.008(3) O4 0.035(5) 0.033(4) 0.032(5) 0.006(3) -0.011(4) -0.019(4) N5 0.044(5) 0.071(5) 0.023(5) 0.011(4) -0.009(4) -0.027(4) N6 0.044(4) 0.025(4) 0.026(4) -0.005(3) 0.006(4) -0.014(3) N7 0.037(5) 0.079(6) 0.026(5) -0.018(5) -0.012(4) 0.007(5) N8 0.058(5) 0.037(5) 0.024(5) -0.008(4) 0.007(4) -0.021(4) C18 0.035(5) 0.094(7) 0.029(6) 0.014(6) -0.006(5) -0.006(5) C19 0.046(5) 0.085(6) 0.028(5) -0.007(5) -0.005(5) 0.013(5) C20 0.068(7) 0.102(8) 0.031(6) 0.001(6) -0.003(5) 0.033(7) C21 0.084(7) 0.099(8) 0.037(6) -0.013(7) -0.014(6) 0.045(7) C22 0.076(7) 0.087(7) 0.046(7) -0.019(6) -0.028(6) 0.028(7) C23 0.055(6) 0.075(7) 0.037(6) -0.019(6) -0.021(5) 0.016(6) C24 0.077(9) 0.100(10) 0.041(8) 0.024(7) -0.023(7) -0.054(8) C25 0.045(5) 0.049(5) 0.023(5) 0.009(5) -0.007(4) -0.025(5) C26 0.050(5) 0.038(5) 0.024(5) 0.005(4) -0.004(5) -0.026(4) C27 0.057(6) 0.029(5) 0.028(5) -0.006(4) 0.003(5) -0.013(5) C28 0.063(6) 0.032(5) 0.026(5) -0.008(4) 0.009(5) -0.019(4) C29 0.083(7) 0.036(5) 0.032(6) -0.015(5) 0.002(5) -0.014(5) C30 0.098(7) 0.042(6) 0.036(6) -0.015(5) 0.001(6) -0.017(5) C31 0.088(7) 0.045(6) 0.024(5) -0.009(5) -0.005(5) -0.021(5) C32 0.068(6) 0.043(5) 0.023(5) 0.000(5) 0.000(5) -0.018(5) C33 0.032(5) 0.027(5) 0.023(5) -0.002(4) 0.003(4) -0.007(4) C34 0.038(6) 0.026(5) 0.022(6) -0.002(5) 0.000(5) -0.002(5) Cl1 0.111(3) 0.062(2) 0.040(2) 0.0015(18) -0.019(2) -0.043(2) O5 0.26(2) 0.070(9) 0.150(14) 0.019(9) -0.112(14) -0.034(10) O6 0.094(9) 0.145(11) 0.118(11) -0.075(9) -0.014(7) -0.041(8) O7 0.072(9) 0.29(2) 0.110(12) -0.023(13) -0.001(8) -0.050(11) O8 0.114(9) 0.121(9) 0.046(7) 0.012(6) 0.004(6) -0.013(8) Cl2 0.067(2) 0.0428(19) 0.0321(19) 0.0000(15) -0.0109(16) -0.0182(16) O9 0.080(7) 0.085(7) 0.059(7) -0.022(5) -0.014(5) -0.046(6) O10 0.083(7) 0.060(6) 0.037(6) -0.003(5) -0.017(5) -0.020(5) O11 0.147(11) 0.045(6) 0.158(13) -0.014(7) -0.098(10) 0.006(7) O12 0.090(8) 0.139(10) 0.066(8) -0.022(7) 0.026(6) -0.060(8) _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 O4 2.118(7) . ? Mn1 O1 2.148(7) . ? Mn1 N4 2.244(8) . ? Mn1 N3 2.244(10) . ? Mn1 N2 2.320(8) . ? Mn1 N1 2.332(9) . ? O1 C17 1.280(12) . ? O2 C17 1.231(12) . ? O2 Mn2 2.121(7) 1_455 ? N1 C1 1.455(14) . ? N1 C7 1.467(14) . ? N1 C8 1.491(13) . ? N2 C10 1.477(12) . ? N2 C16 1.478(13) . ? N2 C9 1.491(13) . ? N3 C2 1.324(16) . ? N3 C6 1.350(15) . ? N4 C11 1.339(13) . ? N4 C15 1.355(13) . ? C1 C2 1.473(16) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 C3 1.373(17) . ? C3 C4 1.375(19) . ? C3 H3A 0.9500 . ? C4 C5 1.35(2) . ? C4 H4A 0.9500 . ? C5 C6 1.418(18) . ? C5 H5A 0.9500 . ? C6 H6A 0.9500 . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 C9 1.495(15) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 C11 1.504(14) . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 C12 1.372(14) . ? C12 C13 1.393(15) . ? C12 H12A 0.9500 . ? C13 C14 1.351(16) . ? C13 H13A 0.9500 . ? C14 C15 1.379(15) . ? C14 H14A 0.9500 . ? C15 H15A 0.9500 . ? C16 C17 1.519(15) . ? C16 H16A 0.9900 . ? C16 H16B 0.9900 . ? Mn2 O2 2.121(7) 1_655 ? Mn2 O3 2.159(7) . ? Mn2 N7 2.248(9) . ? Mn2 N8 2.271(9) . ? Mn2 N5 2.307(9) . ? Mn2 N6 2.316(9) . ? O3 C34 1.259(13) . ? O4 C34 1.242(12) . ? N5 C24 1.448(16) . ? N5 C18 1.470(15) . ? N5 C25 1.482(14) . ? N6 C27 1.468(12) . ? N6 C26 1.484(12) . ? N6 C33 1.485(13) . ? N7 C23 1.314(16) . ? N7 C19 1.322(16) . ? N8 C28 1.292(15) . ? N8 C32 1.344(15) . ? C18 C19 1.470(19) . ? C18 H18A 0.9900 . ? C18 H18B 0.9900 . ? C19 C20 1.405(18) . ? C20 C21 1.37(2) . ? C20 H20A 0.9500 . ? C21 C22 1.35(2) . ? C21 H21A 0.9500 . ? C22 C23 1.378(17) . ? C22 H22A 0.9500 . ? C23 H23A 0.9500 . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C25 C26 1.487(15) . ? C25 H25A 0.9900 . ? C25 H25B 0.9900 . ? C26 H26A 0.9900 . ? C26 H26B 0.9900 . ? C27 C28 1.512(16) . ? C27 H27A 0.9900 . ? C27 H27B 0.9900 . ? C28 C29 1.366(14) . ? C29 C30 1.383(18) . ? C29 H29A 0.9500 . ? C30 C31 1.359(18) . ? C30 H30A 0.9500 . ? C31 C32 1.397(15) . ? C31 H31A 0.9500 . ? C32 H32A 0.9500 . ? C33 C34 1.524(14) . ? C33 H33A 0.9900 . ? C33 H33B 0.9900 . ? Cl1 O5 1.368(8) . ? Cl1 O6 1.389(7) . ? Cl1 O8 1.391(7) . ? Cl1 O7 1.464(8) . ? Cl2 O11 1.400(7) . ? Cl2 O9 1.404(7) . ? Cl2 O10 1.408(7) . ? Cl2 O12 1.429(7) . ? 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 O4 Mn1 O1 89.5(3) . . ? O4 Mn1 N4 88.2(3) . . ? O1 Mn1 N4 104.2(3) . . ? O4 Mn1 N3 94.4(3) . . ? O1 Mn1 N3 91.8(3) . . ? N4 Mn1 N3 163.9(4) . . ? O4 Mn1 N2 151.3(3) . . ? O1 Mn1 N2 74.2(3) . . ? N4 Mn1 N2 73.7(3) . . ? N3 Mn1 N2 109.3(3) . . ? O4 Mn1 N1 127.1(3) . . ? O1 Mn1 N1 140.1(3) . . ? N4 Mn1 N1 93.6(3) . . ? N3 Mn1 N1 72.2(4) . . ? N2 Mn1 N1 77.1(3) . . ? C17 O1 Mn1 119.1(7) . . ? C17 O2 Mn2 114.3(7) . 1_455 ? C1 N1 C7 110.0(9) . . ? C1 N1 C8 109.1(9) . . ? C7 N1 C8 109.5(8) . . ? C1 N1 Mn1 108.4(7) . . ? C7 N1 Mn1 115.4(7) . . ? C8 N1 Mn1 104.1(6) . . ? C10 N2 C16 108.9(8) . . ? C10 N2 C9 112.1(8) . . ? C16 N2 C9 112.6(8) . . ? C10 N2 Mn1 108.5(6) . . ? C16 N2 Mn1 104.7(6) . . ? C9 N2 Mn1 109.6(6) . . ? C2 N3 C6 120.6(11) . . ? C2 N3 Mn1 117.2(8) . . ? C6 N3 Mn1 120.6(9) . . ? C11 N4 C15 117.7(9) . . ? C11 N4 Mn1 118.2(6) . . ? C15 N4 Mn1 123.8(7) . . ? N1 C1 C2 113.9(10) . . ? N1 C1 H1A 108.8 . . ? C2 C1 H1A 108.8 . . ? N1 C1 H1B 108.8 . . ? C2 C1 H1B 108.8 . . ? H1A C1 H1B 107.7 . . ? N3 C2 C3 122.4(13) . . ? N3 C2 C1 117.2(11) . . ? C3 C2 C1 120.2(13) . . ? C2 C3 C4 116.8(15) . . ? C2 C3 H3A 121.6 . . ? C4 C3 H3A 121.6 . . ? C5 C4 C3 123.1(14) . . ? C5 C4 H4A 118.4 . . ? C3 C4 H4A 118.4 . . ? C4 C5 C6 116.7(15) . . ? C4 C5 H5A 121.6 . . ? C6 C5 H5A 121.6 . . ? N3 C6 C5 120.1(15) . . ? N3 C6 H6A 120.0 . . ? C5 C6 H6A 120.0 . . ? 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 C9 110.8(9) . . ? N1 C8 H8A 109.5 . . ? C9 C8 H8A 109.5 . . ? N1 C8 H8B 109.5 . . ? C9 C8 H8B 109.5 . . ? H8A C8 H8B 108.1 . . ? N2 C9 C8 112.2(8) . . ? N2 C9 H9A 109.2 . . ? C8 C9 H9A 109.2 . . ? N2 C9 H9B 109.2 . . ? C8 C9 H9B 109.2 . . ? H9A C9 H9B 107.9 . . ? N2 C10 C11 111.4(8) . . ? N2 C10 H10A 109.3 . . ? C11 C10 H10A 109.3 . . ? N2 C10 H10B 109.3 . . ? C11 C10 H10B 109.3 . . ? H10A C10 H10B 108.0 . . ? N4 C11 C12 122.3(9) . . ? N4 C11 C10 115.0(8) . . ? C12 C11 C10 122.6(9) . . ? C11 C12 C13 118.8(11) . . ? C11 C12 H12A 120.6 . . ? C13 C12 H12A 120.6 . . ? C14 C13 C12 119.7(11) . . ? C14 C13 H13A 120.1 . . ? C12 C13 H13A 120.1 . . ? C13 C14 C15 118.6(11) . . ? C13 C14 H14A 120.7 . . ? C15 C14 H14A 120.7 . . ? N4 C15 C14 122.8(11) . . ? N4 C15 H15A 118.6 . . ? C14 C15 H15A 118.6 . . ? N2 C16 C17 108.9(8) . . ? N2 C16 H16A 109.9 . . ? C17 C16 H16A 109.9 . . ? N2 C16 H16B 109.9 . . ? C17 C16 H16B 109.9 . . ? H16A C16 H16B 108.3 . . ? O2 C17 O1 124.1(10) . . ? O2 C17 C16 119.6(9) . . ? O1 C17 C16 116.3(10) . . ? O2 Mn2 O3 88.2(3) 1_655 . ? O2 Mn2 N7 92.8(3) 1_655 . ? O3 Mn2 N7 87.7(3) . . ? O2 Mn2 N8 89.9(3) 1_655 . ? O3 Mn2 N8 105.6(3) . . ? N7 Mn2 N8 166.5(4) . . ? O2 Mn2 N5 128.1(3) 1_655 . ? O3 Mn2 N5 138.9(3) . . ? N7 Mn2 N5 73.5(4) . . ? N8 Mn2 N5 94.5(3) . . ? O2 Mn2 N6 150.6(3) 1_655 . ? O3 Mn2 N6 74.2(3) . . ? N7 Mn2 N6 109.4(3) . . ? N8 Mn2 N6 73.0(3) . . ? N5 Mn2 N6 78.0(3) . . ? C34 O3 Mn2 118.9(7) . . ? C34 O4 Mn1 115.3(7) . . ? C24 N5 C18 110.6(11) . . ? C24 N5 C25 110.7(10) . . ? C18 N5 C25 109.9(9) . . ? C24 N5 Mn2 114.3(8) . . ? C18 N5 Mn2 107.7(7) . . ? C25 N5 Mn2 103.4(6) . . ? C27 N6 C26 112.2(8) . . ? C27 N6 C33 110.1(8) . . ? C26 N6 C33 111.6(8) . . ? C27 N6 Mn2 108.6(6) . . ? C26 N6 Mn2 109.5(6) . . ? C33 N6 Mn2 104.4(6) . . ? C23 N7 C19 118.9(11) . . ? C23 N7 Mn2 123.9(9) . . ? C19 N7 Mn2 116.8(9) . . ? C28 N8 C32 120.0(10) . . ? C28 N8 Mn2 117.6(8) . . ? C32 N8 Mn2 122.0(8) . . ? N5 C18 C19 114.5(11) . . ? N5 C18 H18A 108.6 . . ? C19 C18 H18A 108.6 . . ? N5 C18 H18B 108.6 . . ? C19 C18 H18B 108.6 . . ? H18A C18 H18B 107.6 . . ? N7 C19 C20 121.9(15) . . ? N7 C19 C18 117.1(11) . . ? C20 C19 C18 120.9(14) . . ? C21 C20 C19 116.4(16) . . ? C21 C20 H20A 121.8 . . ? C19 C20 H20A 121.8 . . ? C22 C21 C20 122.4(15) . . ? C22 C21 H21A 118.8 . . ? C20 C21 H21A 118.8 . . ? C21 C22 C23 116.4(16) . . ? C21 C22 H22A 121.8 . . ? C23 C22 H22A 121.8 . . ? N7 C23 C22 123.9(15) . . ? N7 C23 H23A 118.0 . . ? C22 C23 H23A 118.0 . . ? N5 C24 H24A 109.5 . . ? N5 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? N5 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? N5 C25 C26 113.7(9) . . ? N5 C25 H25A 108.8 . . ? C26 C25 H25A 108.8 . . ? N5 C25 H25B 108.8 . . ? C26 C25 H25B 108.8 . . ? H25A C25 H25B 107.7 . . ? N6 C26 C25 111.1(9) . . ? N6 C26 H26A 109.4 . . ? C25 C26 H26A 109.4 . . ? N6 C26 H26B 109.4 . . ? C25 C26 H26B 109.4 . . ? H26A C26 H26B 108.0 . . ? N6 C27 C28 110.5(9) . . ? N6 C27 H27A 109.6 . . ? C28 C27 H27A 109.6 . . ? N6 C27 H27B 109.6 . . ? C28 C27 H27B 109.6 . . ? H27A C27 H27B 108.1 . . ? N8 C28 C29 122.1(12) . . ? N8 C28 C27 116.5(9) . . ? C29 C28 C27 121.3(11) . . ? C28 C29 C30 119.6(13) . . ? C28 C29 H29A 120.2 . . ? C30 C29 H29A 120.2 . . ? C31 C30 C29 118.7(12) . . ? C31 C30 H30A 120.6 . . ? C29 C30 H30A 120.6 . . ? C30 C31 C32 118.4(13) . . ? C30 C31 H31A 120.8 . . ? C32 C31 H31A 120.8 . . ? N8 C32 C31 121.0(12) . . ? N8 C32 H32A 119.5 . . ? C31 C32 H32A 119.5 . . ? N6 C33 C34 108.4(9) . . ? N6 C33 H33A 110.0 . . ? C34 C33 H33A 110.0 . . ? N6 C33 H33B 110.0 . . ? C34 C33 H33B 110.0 . . ? H33A C33 H33B 108.4 . . ? O4 C34 O3 124.5(9) . . ? O4 C34 C33 118.7(10) . . ? O3 C34 C33 116.8(10) . . ? O5 Cl1 O6 115.1(8) . . ? O5 Cl1 O8 114.5(8) . . ? O6 Cl1 O8 111.5(7) . . ? O5 Cl1 O7 104.3(9) . . ? O6 Cl1 O7 105.7(7) . . ? O8 Cl1 O7 104.5(7) . . ? O11 Cl2 O9 112.4(6) . . ? O11 Cl2 O10 110.4(6) . . ? O9 Cl2 O10 110.7(5) . . ? O11 Cl2 O12 108.3(7) . . ? O9 Cl2 O12 108.6(6) . . ? O10 Cl2 O12 106.3(6) . . ? #============================================================================= data_[Mn(bzbpena)]n(ClO4)n _database_code_depnum_ccdc_archive 'CCDC 776099' #TrackingRef '- Mncomplexes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C23 H25 Mn N4 O2 +, Cl O4 -, C H4 O' _chemical_formula_sum 'C24 H29 Cl Mn N4 O7' _chemical_formula_weight 575.90 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 'P 21/n' _symmetry_space_group_name_Hall '-P 2yn' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 13.4609(13) _cell_length_b 9.6079(9) _cell_length_c 20.2349(19) _cell_angle_alpha 90.00 _cell_angle_beta 91.263(4) _cell_angle_gamma 90.00 _cell_volume 2616.4(4) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 3410 _cell_measurement_theta_min 2.35 _cell_measurement_theta_max 22.58 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.462 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1196 _exptl_absorpt_coefficient_mu 0.657 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.756 _exptl_absorpt_correction_T_max 0.974 _exptl_absorpt_process_details 'SADABS (Sheldrick, 2003)' _exptl_special_details ? _diffrn_ambient_temperature 180(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 'Bruker-Nonius X8APEX-II CCD' _diffrn_measurement_method 'thin-slice \w and \f scans' _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 23627 _diffrn_reflns_av_R_equivalents 0.0783 _diffrn_reflns_av_sigmaI/netI 0.0733 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 3.60 _diffrn_reflns_theta_max 25.12 _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.12 _diffrn_measured_fraction_theta_full 0.993 _reflns_number_total 4635 _reflns_number_gt 2853 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 v.1.0-22 (Bruker-Nonius, 2004)' _computing_cell_refinement 'SAINT v.7.06a (Bruker, 2003)' _computing_data_reduction 'SAINT v.7.06a' _computing_structure_solution 'SHELXTL v.6.12 (Sheldrick, 2001)' _computing_structure_refinement 'SHELXTL v.6.12' _computing_molecular_graphics 'SHELXTL v.6.12' _computing_publication_material 'SHELXTL v.6.12' _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^)+(0.0527P)^2^+1.7292P] 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_number_reflns 4635 _refine_ls_number_parameters 362 _refine_ls_number_restraints 19 _refine_ls_R_factor_all 0.1014 _refine_ls_R_factor_gt 0.0461 _refine_ls_wR_factor_ref 0.1252 _refine_ls_wR_factor_gt 0.1028 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 1.034 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.330 _refine_diff_density_min -0.348 _refine_diff_density_rms 0.068 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 0.68921(4) 0.27505(6) 0.77029(2) 0.02841(18) Uani 1 1 d . . . O1 O 0.73706(18) 0.4944(3) 0.76722(11) 0.0324(6) Uani 1 1 d . . . O2 O 0.70153(17) 0.7106(3) 0.79782(12) 0.0335(6) Uani 1 1 d . . . N1 N 0.6120(2) 0.1210(3) 0.84486(13) 0.0306(7) Uani 1 1 d . . . N2 N 0.5569(2) 0.4039(3) 0.80783(14) 0.0296(7) Uani 1 1 d . . . N3 N 0.8001(2) 0.2295(3) 0.85201(14) 0.0330(7) Uani 1 1 d . . . N4 N 0.5744(2) 0.2662(3) 0.68756(14) 0.0328(7) Uani 1 1 d . . . C1 C 0.5364(3) 0.0269(4) 0.81364(18) 0.0362(9) Uani 1 1 d . . . H1A H 0.5715 -0.0452 0.7882 0.043 Uiso 1 1 calc R . . H1B H 0.4956 0.0820 0.7818 0.043 Uiso 1 1 calc R . . C2 C 0.4674(3) -0.0451(4) 0.86062(18) 0.0367(9) Uani 1 1 d . . . C3 C 0.4988(3) -0.1620(4) 0.89615(19) 0.0404(10) Uani 1 1 d . . . H3A H 0.5650 -0.1947 0.8920 0.048 Uiso 1 1 calc R . . C4 C 0.4344(3) -0.2310(5) 0.93748(19) 0.0461(11) Uani 1 1 d . . . H4A H 0.4558 -0.3128 0.9600 0.055 Uiso 1 1 calc R . . C5 C 0.3401(3) -0.1818(5) 0.94598(19) 0.0474(11) Uani 1 1 d . . . H5A H 0.2962 -0.2292 0.9744 0.057 Uiso 1 1 calc R . . C6 C 0.3090(3) -0.0629(5) 0.9131(2) 0.0495(11) Uani 1 1 d . . . H6A H 0.2442 -0.0273 0.9200 0.059 Uiso 1 1 calc R . . C7 C 0.3718(3) 0.0047(4) 0.8702(2) 0.0433(10) Uani 1 1 d . . . H7A H 0.3494 0.0855 0.8473 0.052 Uiso 1 1 calc R . . C8 C 0.5659(3) 0.2202(4) 0.89140(17) 0.0343(9) Uani 1 1 d . . . H8A H 0.6188 0.2709 0.9161 0.041 Uiso 1 1 calc R . . H8B H 0.5265 0.1676 0.9237 0.041 Uiso 1 1 calc R . . C9 C 0.4994(3) 0.3235(4) 0.85594(18) 0.0350(9) Uani 1 1 d . . . H9A H 0.4446 0.2737 0.8327 0.042 Uiso 1 1 calc R . . H9B H 0.4699 0.3876 0.8884 0.042 Uiso 1 1 calc R . . C10 C 0.6012(3) 0.5287(4) 0.83870(19) 0.0364(9) Uani 1 1 d . . . H10A H 0.6256 0.5060 0.8839 0.044 Uiso 1 1 calc R . . H10B H 0.5501 0.6024 0.8420 0.044 Uiso 1 1 calc R . . C11 C 0.6857(3) 0.5807(4) 0.79843(17) 0.0304(9) Uani 1 1 d . . . C12 C 0.4937(3) 0.4446(4) 0.75024(19) 0.0373(9) Uani 1 1 d . . . H12A H 0.5208 0.5303 0.7303 0.045 Uiso 1 1 calc R . . H12B H 0.4258 0.4655 0.7653 0.045 Uiso 1 1 calc R . . C13 C 0.4885(3) 0.3322(4) 0.69897(17) 0.0340(9) Uani 1 1 d . . . C14 C 0.4032(3) 0.3023(5) 0.6637(2) 0.0508(12) Uani 1 1 d . . . H14A H 0.3425 0.3469 0.6740 0.061 Uiso 1 1 calc R . . C15 C 0.4068(3) 0.2062(5) 0.6131(2) 0.0628(14) Uani 1 1 d . . . H15A H 0.3482 0.1834 0.5884 0.075 Uiso 1 1 calc R . . C16 C 0.4952(3) 0.1442(5) 0.5989(2) 0.0538(12) Uani 1 1 d . . . H16A H 0.4997 0.0805 0.5632 0.065 Uiso 1 1 calc R . . C17 C 0.5765(3) 0.1758(4) 0.63701(18) 0.0401(10) Uani 1 1 d . . . H17A H 0.6377 0.1318 0.6274 0.048 Uiso 1 1 calc R . . C18 C 0.6894(3) 0.0390(4) 0.88021(18) 0.0354(9) Uani 1 1 d . . . H18A H 0.7018 -0.0476 0.8552 0.043 Uiso 1 1 calc R . . H18B H 0.6647 0.0123 0.9242 0.043 Uiso 1 1 calc R . . C19 C 0.7855(3) 0.1167(4) 0.88919(17) 0.0334(9) Uani 1 1 d . . . C20 C 0.8588(3) 0.0682(5) 0.9327(2) 0.0493(11) Uani 1 1 d . . . H20A H 0.8479 -0.0132 0.9582 0.059 Uiso 1 1 calc R . . C21 C 0.9475(3) 0.1392(5) 0.9385(2) 0.0561(13) Uani 1 1 d . . . H21A H 0.9978 0.1085 0.9688 0.067 Uiso 1 1 calc R . . C22 C 0.9625(3) 0.2549(4) 0.9002(2) 0.0486(11) Uani 1 1 d . . . H22A H 1.0236 0.3043 0.9027 0.058 Uiso 1 1 calc R . . C23 C 0.8875(3) 0.2973(4) 0.85836(19) 0.0400(10) Uani 1 1 d . . . H23A H 0.8974 0.3784 0.8325 0.048 Uiso 1 1 calc R . . Cl1 Cl 0.74998(9) 0.11036(13) 0.48673(5) 0.0550(3) Uani 1 1 d D . . O11 O 0.7127(3) 0.0030(4) 0.52682(18) 0.0951(13) Uani 1 1 d D A . O12 O 0.7359(10) 0.2361(7) 0.5211(6) 0.149(6) Uani 0.50 1 d PD A 1 O13 O 0.7040(9) 0.1115(15) 0.4263(4) 0.157(8) Uani 0.50 1 d PD A 1 O14 O 0.8512(5) 0.0885(13) 0.4816(6) 0.118(5) Uani 0.50 1 d PD A 1 O22 O 0.6826(7) 0.2197(9) 0.4841(6) 0.112(4) Uani 0.50 1 d PD A 2 O23 O 0.7565(10) 0.0555(11) 0.4212(3) 0.120(5) Uani 0.50 1 d PD A 2 O24 O 0.8425(6) 0.1512(13) 0.5052(6) 0.123(6) Uani 0.50 1 d PD A 2 O1S O 0.7606(3) 0.1679(5) 0.2950(2) 0.1081(15) Uani 1 1 d . . . H1S H 0.7590 0.1343 0.3381 0.162 Uiso 1 1 d R . . C1S C 0.6774(4) 0.2441(8) 0.2741(3) 0.107(2) Uani 1 1 d . . . H1S1 H 0.6651 0.3195 0.3054 0.161 Uiso 1 1 d R . . H1S2 H 0.6193 0.1827 0.2714 0.161 Uiso 1 1 d R . . H1S3 H 0.6896 0.2835 0.2303 0.161 Uiso 1 1 d R . . 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 0.0329(3) 0.0247(3) 0.0275(3) 0.0003(3) -0.0015(2) -0.0005(3) O1 0.0374(14) 0.0251(15) 0.0348(15) 0.0003(12) 0.0025(12) 0.0030(12) O2 0.0398(15) 0.0237(15) 0.0370(14) -0.0021(12) 0.0021(11) -0.0056(12) N1 0.0366(17) 0.0259(18) 0.0293(16) -0.0020(14) -0.0014(14) -0.0048(14) N2 0.0327(17) 0.0253(19) 0.0308(16) -0.0045(14) 0.0016(14) -0.0042(14) N3 0.0378(18) 0.0301(19) 0.0310(16) 0.0030(15) -0.0041(13) -0.0019(15) N4 0.0371(18) 0.0312(19) 0.0300(16) 0.0016(15) -0.0008(13) 0.0026(15) C1 0.046(2) 0.029(2) 0.034(2) -0.0055(18) -0.0006(18) -0.0065(18) C2 0.047(2) 0.030(2) 0.032(2) -0.0058(19) -0.0007(18) -0.0085(19) C3 0.047(2) 0.032(2) 0.042(2) -0.008(2) 0.0105(19) -0.006(2) C4 0.060(3) 0.037(3) 0.041(2) -0.002(2) 0.003(2) -0.008(2) C5 0.050(3) 0.057(3) 0.036(2) -0.003(2) 0.002(2) -0.018(2) C6 0.039(2) 0.057(3) 0.052(3) -0.007(2) -0.002(2) -0.007(2) C7 0.042(2) 0.038(3) 0.050(3) -0.001(2) -0.007(2) -0.008(2) C8 0.042(2) 0.033(2) 0.0280(19) -0.0026(18) 0.0041(16) -0.0083(19) C9 0.037(2) 0.031(2) 0.037(2) -0.0024(18) 0.0055(17) -0.0054(17) C10 0.042(2) 0.026(2) 0.041(2) -0.0079(18) 0.0047(18) -0.0068(18) C11 0.035(2) 0.027(2) 0.0281(19) 0.0020(18) -0.0065(16) -0.0041(18) C12 0.039(2) 0.029(2) 0.045(2) 0.0028(19) 0.0024(18) 0.0036(18) C13 0.039(2) 0.033(2) 0.030(2) 0.0016(17) -0.0056(17) 0.0045(18) C14 0.045(3) 0.056(3) 0.051(3) -0.003(2) -0.012(2) 0.011(2) C15 0.056(3) 0.068(4) 0.064(3) -0.018(3) -0.026(2) 0.006(3) C16 0.066(3) 0.056(3) 0.039(2) -0.014(2) -0.016(2) 0.013(2) C17 0.046(2) 0.040(3) 0.034(2) -0.0016(19) -0.0029(19) 0.0102(19) C18 0.050(2) 0.024(2) 0.032(2) 0.0030(17) -0.0027(18) -0.0012(18) C19 0.041(2) 0.029(2) 0.029(2) -0.0015(18) -0.0009(17) 0.0044(18) C20 0.055(3) 0.043(3) 0.049(3) 0.013(2) -0.009(2) 0.003(2) C21 0.050(3) 0.062(3) 0.056(3) 0.017(3) -0.018(2) 0.003(2) C22 0.042(2) 0.050(3) 0.053(3) -0.002(2) -0.008(2) -0.005(2) C23 0.041(2) 0.034(3) 0.045(2) 0.0001(19) -0.0066(19) -0.0084(19) Cl1 0.0532(7) 0.0651(9) 0.0467(7) -0.0041(6) 0.0003(6) -0.0054(6) O11 0.125(3) 0.074(3) 0.088(3) -0.001(2) 0.043(3) -0.017(2) O12 0.226(15) 0.066(7) 0.162(11) -0.069(7) 0.133(10) -0.071(9) O13 0.149(11) 0.206(19) 0.113(11) 0.039(11) -0.101(9) -0.017(11) O14 0.066(7) 0.189(13) 0.101(10) -0.012(8) 0.038(7) 0.004(7) O22 0.089(7) 0.091(8) 0.154(11) -0.015(7) -0.023(7) 0.044(6) O23 0.243(16) 0.083(7) 0.036(5) 0.001(4) 0.027(7) -0.032(9) O24 0.079(8) 0.191(14) 0.096(9) 0.021(9) -0.055(7) -0.048(8) O1S 0.089(3) 0.150(4) 0.086(3) 0.021(3) 0.010(2) 0.036(3) C1S 0.074(4) 0.156(7) 0.091(5) -0.002(4) -0.015(3) 0.040(4) _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 2.130(2) 2_646 ? Mn1 O1 2.205(3) . ? Mn1 N3 2.246(3) . ? Mn1 N4 2.254(3) . ? Mn1 N2 2.312(3) . ? Mn1 N1 2.370(3) . ? O1 C11 1.259(4) . ? O2 C11 1.266(4) . ? O2 Mn1 2.130(2) 2_656 ? N1 C18 1.478(5) . ? N1 C8 1.486(4) . ? N1 C1 1.492(4) . ? N2 C10 1.473(4) . ? N2 C9 1.475(4) . ? N2 C12 1.480(5) . ? N4 C17 1.342(5) . ? N4 C13 1.344(4) . ? N3 C19 1.337(5) . ? N3 C23 1.348(5) . ? C1 C2 1.511(5) . ? C1 H1A 0.990 . ? C1 H1B 0.990 . ? C2 C7 1.391(5) . ? C2 C3 1.394(5) . ? C3 C4 1.387(5) . ? C3 H3A 0.950 . ? C4 C5 1.368(6) . ? C4 H4A 0.950 . ? C5 C6 1.382(6) . ? C5 H5A 0.950 . ? C6 C7 1.386(6) . ? C6 H6A 0.950 . ? C7 H7A 0.950 . ? C8 C9 1.508(5) . ? C8 H8A 0.990 . ? C8 H8B 0.990 . ? C9 H9A 0.990 . ? C9 H9B 0.990 . ? C10 C11 1.500(5) . ? C10 H10A 0.990 . ? C10 H10B 0.990 . ? C12 C13 1.498(5) . ? C12 H12A 0.990 . ? C12 H12B 0.990 . ? C13 C14 1.369(5) . ? C14 C15 1.380(6) . ? C14 H14A 0.950 . ? C15 C16 1.368(6) . ? C15 H15A 0.950 . ? C16 C17 1.359(5) . ? C16 H16A 0.950 . ? C17 H17A 0.950 . ? C18 C19 1.501(5) . ? C18 H18A 0.990 . ? C18 H18B 0.990 . ? C19 C20 1.388(5) . ? C20 C21 1.379(6) . ? C20 H20A 0.950 . ? C21 C22 1.373(6) . ? C21 H21A 0.950 . ? C22 C23 1.364(5) . ? C22 H22A 0.950 . ? C23 H23A 0.950 . ? Cl1 O11 1.411(3) . ? Cl1 O12 1.409(6) . ? Cl1 O13 1.357(6) . ? Cl1 O14 1.385(7) . ? Cl1 O22 1.388(6) . ? Cl1 O23 1.431(6) . ? Cl1 O24 1.351(6) . ? O1S C1S 1.396(6) . ? O1S H1S 0.9307 . ? C1S H1S1 0.980 . ? C1S H1S2 0.980 . ? C1S H1S3 0.980 . ? 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 93.06(10) 2_646 . ? O2 Mn1 N3 87.85(10) 2_646 . ? O1 Mn1 N3 90.97(10) . . ? O2 Mn1 N4 88.86(10) 2_646 . ? O1 Mn1 N4 102.19(10) . . ? N3 Mn1 N4 166.59(12) . . ? O2 Mn1 N2 156.45(10) 2_646 . ? O1 Mn1 N2 74.05(10) . . ? N3 Mn1 N2 111.52(10) . . ? N4 Mn1 N2 75.15(10) . . ? O2 Mn1 N1 123.31(10) 2_646 . ? O1 Mn1 N1 138.35(9) . . ? N3 Mn1 N1 72.74(10) . . ? N4 Mn1 N1 98.42(10) . . ? N2 Mn1 N1 76.90(10) . . ? C11 O1 Mn1 116.9(2) . . ? C11 O2 Mn1 114.3(2) . 2_656 ? C18 N1 C8 109.6(3) . . ? C18 N1 C1 110.4(3) . . ? C8 N1 C1 111.5(3) . . ? C18 N1 Mn1 109.1(2) . . ? C8 N1 Mn1 101.4(2) . . ? C1 N1 Mn1 114.4(2) . . ? C10 N2 C9 111.1(3) . . ? C10 N2 C12 109.8(3) . . ? C9 N2 C12 111.0(3) . . ? C10 N2 Mn1 105.5(2) . . ? C9 N2 Mn1 110.9(2) . . ? C12 N2 Mn1 108.4(2) . . ? C17 N4 C13 118.0(3) . . ? C17 N4 Mn1 124.4(2) . . ? C13 N4 Mn1 115.7(2) . . ? C19 N3 C23 118.5(3) . . ? C19 N3 Mn1 117.9(2) . . ? C23 N3 Mn1 122.7(2) . . ? N1 C1 C2 115.7(3) . . ? N1 C1 H1A 108.4 . . ? C2 C1 H1A 108.4 . . ? N1 C1 H1B 108.4 . . ? C2 C1 H1B 108.4 . . ? H1A C1 H1B 107.4 . . ? C7 C2 C3 118.4(4) . . ? C7 C2 C1 120.9(4) . . ? C3 C2 C1 120.7(4) . . ? C4 C3 C2 120.6(4) . . ? C4 C3 H3A 119.7 . . ? C2 C3 H3A 119.7 . . ? C5 C4 C3 120.3(4) . . ? C5 C4 H4A 119.8 . . ? C3 C4 H4A 119.8 . . ? C4 C5 C6 119.8(4) . . ? C4 C5 H5A 120.1 . . ? C6 C5 H5A 120.1 . . ? C5 C6 C7 120.4(4) . . ? C5 C6 H6A 119.8 . . ? C7 C6 H6A 119.8 . . ? C6 C7 C2 120.4(4) . . ? C6 C7 H7A 119.8 . . ? C2 C7 H7A 119.8 . . ? N1 C8 C9 111.9(3) . . ? N1 C8 H8A 109.2 . . ? C9 C8 H8A 109.2 . . ? N1 C8 H8B 109.2 . . ? C9 C8 H8B 109.2 . . ? H8A C8 H8B 107.9 . . ? N2 C9 C8 110.1(3) . . ? N2 C9 H9A 109.6 . . ? C8 C9 H9A 109.6 . . ? N2 C9 H9B 109.6 . . ? C8 C9 H9B 109.6 . . ? H9A C9 H9B 108.1 . . ? N2 C10 C11 110.3(3) . . ? N2 C10 H10A 109.6 . . ? C11 C10 H10A 109.6 . . ? N2 C10 H10B 109.6 . . ? C11 C10 H10B 109.6 . . ? H10A C10 H10B 108.1 . . ? O1 C11 O2 123.4(3) . . ? O1 C11 C10 119.0(3) . . ? O2 C11 C10 117.6(3) . . ? N2 C12 C13 111.8(3) . . ? N2 C12 H12A 109.3 . . ? C13 C12 H12A 109.3 . . ? N2 C12 H12B 109.3 . . ? C13 C12 H12B 109.3 . . ? H12A C12 H12B 107.9 . . ? N4 C13 C14 121.8(4) . . ? N4 C13 C12 115.6(3) . . ? C14 C13 C12 122.5(4) . . ? C13 C14 C15 119.0(4) . . ? C13 C14 H14A 120.5 . . ? C15 C14 H14A 120.5 . . ? C16 C15 C14 119.5(4) . . ? C16 C15 H15A 120.3 . . ? C14 C15 H15A 120.3 . . ? C17 C16 C15 118.5(4) . . ? C17 C16 H16A 120.7 . . ? C15 C16 H16A 120.7 . . ? N4 C17 C16 123.1(4) . . ? N4 C17 H17A 118.4 . . ? C16 C17 H17A 118.4 . . ? N1 C18 C19 112.9(3) . . ? N1 C18 H18A 109.0 . . ? C19 C18 H18A 109.0 . . ? N1 C18 H18B 109.0 . . ? C19 C18 H18B 109.0 . . ? H18A C18 H18B 107.8 . . ? N3 C19 C20 121.2(4) . . ? N3 C19 C18 118.2(3) . . ? C20 C19 C18 120.5(4) . . ? C21 C20 C19 119.4(4) . . ? C21 C20 H20A 120.3 . . ? C19 C20 H20A 120.3 . . ? C22 C21 C20 119.3(4) . . ? C22 C21 H21A 120.3 . . ? C20 C21 H21A 120.3 . . ? C23 C22 C21 118.4(4) . . ? C23 C22 H22A 120.8 . . ? C21 C22 H22A 120.8 . . ? N3 C23 C22 123.2(4) . . ? N3 C23 H23A 118.4 . . ? C22 C23 H23A 118.4 . . ? O13 Cl1 O11 111.3(5) . . ? O14 Cl1 O11 107.2(5) . . ? O13 Cl1 O12 111.9(6) . . ? O13 Cl1 O14 111.4(6) . . ? O14 Cl1 O12 108.1(5) . . ? O12 Cl1 O11 106.8(4) . . ? O24 Cl1 O22 112.9(6) . . ? O24 Cl1 O11 113.0(5) . . ? O22 Cl1 O11 109.6(4) . . ? O24 Cl1 O23 106.8(5) . . ? O22 Cl1 O23 107.2(5) . . ? O11 Cl1 O23 107.0(4) . . ? C1S O1S H1S 115.5 . . ? O1S C1S H1S1 109.7 . . ? O1S C1S H1S2 109.6 . . ? H1S1 C1S H1S2 109.5 . . ? O1S C1S H1S3 109.1 . . ? H1S1 C1S H1S3 109.5 . . ? H1S2 C1S H1S3 109.5 . . ?