# 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 #TrackingRef '- mor121pub.cif' # 1. SUBMISSION DETAILS _publ_contact_author ; Dr. Grace Morgan School of Chemistry and Chemical Biology University College Dublin Belfield Dublin 4 Ireland ; _publ_contact_author_phone '00353 1 716-2295' _publ_contact_author_fax '00353 1 716-2501' _publ_contact_author_email grace.morgan@ucd.ie _publ_requested_coeditor_name ? # 2. TITLE AND AUTHOR LIST _publ_section_title ; ; loop_ _publ_author_name _publ_author_address 'Grace Morgan' ; School of Chemistry and Chemical Biology University College Dublin Belfield Dublin 4 Ireland ; 'Brendan Gildea' ; School of Chemistry and Chemical Biology University College Dublin Belfield Dublin 4 Ireland ; _publ_contact_author_name 'Dr. Grace Morgan' #===END_data_global #TrackingRef '- mor121pub.cif' data_mor121 _database_code_depnum_ccdc_archive 'CCDC 718584' #TrackingRef '- mor121pub.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C30 H30 Mn N4 O4, C32 H38 Mn N4 O6, 2 (Cl O4)' _chemical_formula_sum 'C62 H68 Cl2 Mn2 N8 O18' _chemical_formula_weight 1394.02 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 10.0933(7) _cell_length_b 10.5813(8) _cell_length_c 15.0387(11) _cell_angle_alpha 87.740(1) _cell_angle_beta 84.350(1) _cell_angle_gamma 84.701(1) _cell_volume 1590.8(2) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 7153 _cell_measurement_theta_min 2.33 _cell_measurement_theta_max 28.03 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 1.00 _exptl_crystal_size_mid 1.00 _exptl_crystal_size_min 0.80 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.455 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 724 _exptl_absorpt_coefficient_mu 0.559 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5489 _exptl_absorpt_correction_T_max 0.6633 _exptl_absorpt_process_details ; SADABS v.2.10 (Bruker,2003) was used for absorption correction. R(int) for selected reflections was 0.059 before and 0.021 after correction. The Ratio of minimum to maximum transmission is 0.827489. The \l/2 correction factor is 0.0015 ; _exptl_special_details ; The dataset was collected at room temperature without temperature control ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 27111 _diffrn_reflns_av_R_equivalents 0.0220 _diffrn_reflns_av_sigmaI/netI 0.0187 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.36 _diffrn_reflns_theta_max 28.37 _reflns_number_total 7394 _reflns_number_gt 6536 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0626P)^2^+0.4533P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 7394 _refine_ls_number_parameters 521 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0430 _refine_ls_R_factor_gt 0.0383 _refine_ls_wR_factor_ref 0.1083 _refine_ls_wR_factor_gt 0.1049 _refine_ls_goodness_of_fit_ref 1.066 _refine_ls_restrained_S_all 1.066 _refine_ls_shift/su_max 0.002 _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 0.5000 0.5000 0.02991(9) Uani 1 2 d S . . O1 O -0.04108(12) 0.59447(10) 0.39590(7) 0.0349(2) Uani 1 1 d . . . C1 C -0.09915(15) 0.55120(14) 0.32996(10) 0.0317(3) Uani 1 1 d . . . C2 C -0.17504(16) 0.63836(15) 0.27786(11) 0.0345(3) Uani 1 1 d . . . H2 H -0.1801(19) 0.7243(19) 0.2904(13) 0.037(5) Uiso 1 1 d . . . C3 C -0.23796(17) 0.59627(16) 0.20843(11) 0.0382(3) Uani 1 1 d . . . C4 C -0.2234(2) 0.46797(18) 0.18660(13) 0.0483(4) Uani 1 1 d . . . H4 H -0.266(2) 0.442(2) 0.1373(16) 0.058(6) Uiso 1 1 d . . . C5 C -0.1463(2) 0.38353(17) 0.23483(13) 0.0461(4) Uani 1 1 d . . . H5 H -0.129(2) 0.293(2) 0.2162(15) 0.055(6) Uiso 1 1 d . . . C6 C -0.08351(17) 0.42145(15) 0.30780(11) 0.0354(3) Uani 1 1 d . . . O4 O -0.31837(14) 0.67089(12) 0.15739(9) 0.0495(3) Uani 1 1 d . . . C29 C -0.3420(2) 0.80259(19) 0.17512(16) 0.0573(5) Uani 1 1 d . . . H29A H -0.3765 0.8129 0.2365 0.086 Uiso 1 1 calc R . . H29B H -0.4059 0.8417 0.1369 0.086 Uiso 1 1 calc R . . H29C H -0.2598 0.8419 0.1640 0.086 Uiso 1 1 calc R . . C7 C 0.00593(17) 0.33091(15) 0.35106(11) 0.0362(3) Uani 1 1 d . . . H8 H 0.0349(19) 0.2559(19) 0.3200(13) 0.038(5) Uiso 1 1 d . . . N1 N 0.05456(13) 0.34642(12) 0.42545(9) 0.0336(3) Uani 1 1 d . . . C8 C 0.1578(2) 0.24951(17) 0.45394(14) 0.0433(4) Uani 1 1 d . . . H8A H 0.180(2) 0.194(2) 0.4090(15) 0.048(6) Uiso 1 1 d . . . H8B H 0.121(2) 0.201(2) 0.4997(17) 0.061(7) Uiso 1 1 d . . . C9 C 0.2826(2) 0.30452(19) 0.48095(14) 0.0470(4) Uani 1 1 d . . . H9A H 0.357(3) 0.248(2) 0.4654(16) 0.057(6) Uiso 1 1 d . . . H9B H 0.276(2) 0.308(2) 0.5473(16) 0.055(6) Uiso 1 1 d . . . C10 C 0.31455(17) 0.43341(18) 0.44384(12) 0.0416(4) Uani 1 1 d . . . C11 C 0.4356(2) 0.4524(2) 0.39560(15) 0.0558(5) Uani 1 1 d . . . H11 H 0.489(3) 0.387(3) 0.3835(17) 0.066(7) Uiso 1 1 d . . . C12 C 0.4660(2) 0.5730(3) 0.36989(16) 0.0658(6) Uani 1 1 d . . . H12 H 0.553(3) 0.586(2) 0.3402(18) 0.071(7) Uiso 1 1 d . . . C13 C 0.3747(2) 0.6738(3) 0.39097(17) 0.0630(6) Uani 1 1 d . . . H13 H 0.393(3) 0.754(2) 0.3722(17) 0.066(7) Uiso 1 1 d . . . C14 C 0.2544(2) 0.6496(2) 0.43690(15) 0.0532(5) Uani 1 1 d . . . H14 H 0.182(3) 0.720(2) 0.4544(17) 0.066(7) Uiso 1 1 d . . . N2 N 0.22419(14) 0.53238(14) 0.46352(10) 0.0414(3) Uani 1 1 d . . . Mn2 Mn 0.0000 1.0000 0.0000 0.03081(9) Uani 1 2 d S . . O2 O -0.08573(12) 1.03229(12) 0.11442(7) 0.0413(3) Uani 1 1 d . . . C15 C -0.04783(16) 1.00719(14) 0.19498(10) 0.0315(3) Uani 1 1 d . . . C16 C -0.14237(17) 1.03112(15) 0.26905(10) 0.0340(3) Uani 1 1 d . . . H16 H -0.232(2) 1.0643(19) 0.2596(14) 0.043(5) Uiso 1 1 d . . . C17 C -0.10434(18) 1.00957(16) 0.35486(10) 0.0366(3) Uani 1 1 d . . . C18 C 0.02661(19) 0.96436(18) 0.36950(11) 0.0431(4) Uani 1 1 d . . . H18 H 0.055(2) 0.949(2) 0.4282(15) 0.048(5) Uiso 1 1 d . . . C19 C 0.11761(18) 0.94081(18) 0.29774(11) 0.0419(4) Uani 1 1 d . . . H19 H 0.212(2) 0.9105(19) 0.3056(14) 0.045(5) Uiso 1 1 d . . . C20 C 0.08357(16) 0.96040(15) 0.20934(10) 0.0342(3) Uani 1 1 d . . . O5 O -0.18681(14) 1.03175(14) 0.43072(8) 0.0516(3) Uani 1 1 d . . . C30 C -0.3245(2) 1.0658(3) 0.42267(16) 0.0769(8) Uani 1 1 d . . . H30A H -0.3354 1.1483 0.3941 0.115 Uiso 1 1 calc R . . H30B H -0.3725 1.0675 0.4810 0.115 Uiso 1 1 calc R . . H30C H -0.3587 1.0047 0.3875 0.115 Uiso 1 1 calc R . . C21 C 0.18633(16) 0.93540(16) 0.13817(11) 0.0345(3) Uani 1 1 d . . . H21 H 0.269(2) 0.9090(18) 0.1577(12) 0.037(5) Uiso 1 1 d . . . N3 N 0.17542(13) 0.94576(12) 0.05332(8) 0.0311(3) Uani 1 1 d . . . C22 C 0.29811(16) 0.90872(16) -0.00489(11) 0.0358(3) Uani 1 1 d . . . H22A H 0.371(2) 0.9190(17) 0.0278(13) 0.037(5) Uiso 1 1 d . . . H22B H 0.3021(19) 0.9702(19) -0.0542(14) 0.039(5) Uiso 1 1 d . . . C23 C 0.29914(19) 0.77284(17) -0.03668(11) 0.0393(4) Uani 1 1 d . . . H23A H 0.379(2) 0.7553(19) -0.0719(14) 0.046(5) Uiso 1 1 d . . . H23B H 0.225(2) 0.7720(19) -0.0751(14) 0.045(5) Uiso 1 1 d . . . C24 C 0.28917(17) 0.67528(15) 0.03839(11) 0.0367(3) Uani 1 1 d . . . C25 C 0.4014(2) 0.6136(2) 0.07264(14) 0.0492(4) Uani 1 1 d . . . H25 H 0.485(2) 0.630(2) 0.0470(15) 0.051(6) Uiso 1 1 d . . . C26 C 0.3855(2) 0.5266(2) 0.14285(17) 0.0620(6) Uani 1 1 d . . . H26 H 0.460(3) 0.482(3) 0.1620(18) 0.074(8) Uiso 1 1 d . . . C27 C 0.2591(3) 0.5038(2) 0.17793(16) 0.0614(6) Uani 1 1 d . . . H27 H 0.240(3) 0.448(3) 0.225(2) 0.083(9) Uiso 1 1 d . . . C28 C 0.1524(2) 0.5686(2) 0.14127(15) 0.0533(5) Uani 1 1 d . . . H28 H 0.056(3) 0.561(2) 0.1650(16) 0.062(7) Uiso 1 1 d . . . N4 N 0.16543(15) 0.65294(14) 0.07265(10) 0.0429(3) Uani 1 1 d . . . O3 O -0.05135(14) 0.79802(13) 0.01959(10) 0.0475(3) Uani 1 1 d . . . H1O5 H 0.006(3) 0.752(3) 0.0361(19) 0.070(8) Uiso 1 1 d . . . C31 C -0.1186(3) 0.7304(2) -0.03919(17) 0.0630(6) Uani 1 1 d . . . H31A H -0.1975 0.7810 -0.0546 0.094 Uiso 1 1 calc R . . H31B H -0.1433 0.6524 -0.0103 0.094 Uiso 1 1 calc R . . H31C H -0.0606 0.7122 -0.0925 0.094 Uiso 1 1 calc R . . Cl3 Cl 0.42649(5) 0.13149(5) 0.23867(4) 0.05415(13) Uani 1 1 d . . . O6 O 0.5302(2) 0.2113(2) 0.24768(13) 0.0839(5) Uani 1 1 d . . . O7 O 0.3002(2) 0.1998(2) 0.24607(18) 0.1024(7) Uani 1 1 d . . . O8 O 0.4240(2) 0.0342(3) 0.3064(2) 0.1321(12) Uani 1 1 d . . . O9 O 0.4477(3) 0.0755(3) 0.1551(2) 0.1449(13) 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 0.03308(17) 0.02741(16) 0.02869(17) -0.00125(12) -0.00069(12) -0.00193(12) O1 0.0440(6) 0.0291(5) 0.0322(5) -0.0005(4) -0.0049(5) -0.0052(4) C1 0.0333(7) 0.0321(7) 0.0295(7) -0.0008(6) 0.0026(6) -0.0069(6) C2 0.0372(8) 0.0311(7) 0.0352(8) -0.0015(6) -0.0005(6) -0.0053(6) C3 0.0355(8) 0.0409(8) 0.0384(8) 0.0015(7) -0.0043(6) -0.0049(6) C4 0.0559(11) 0.0446(10) 0.0477(10) -0.0100(8) -0.0184(9) -0.0047(8) C5 0.0573(11) 0.0355(8) 0.0477(10) -0.0092(7) -0.0113(8) -0.0054(8) C6 0.0406(8) 0.0310(7) 0.0346(8) -0.0027(6) -0.0013(6) -0.0057(6) O4 0.0505(7) 0.0456(7) 0.0549(8) 0.0003(6) -0.0213(6) -0.0017(6) C29 0.0608(12) 0.0425(10) 0.0700(14) 0.0060(9) -0.0214(11) 0.0014(9) C7 0.0425(9) 0.0284(7) 0.0367(8) -0.0030(6) 0.0021(7) -0.0040(6) N1 0.0366(7) 0.0279(6) 0.0351(7) -0.0002(5) 0.0009(5) -0.0013(5) C8 0.0488(10) 0.0318(8) 0.0477(10) -0.0004(8) -0.0054(8) 0.0050(7) C9 0.0421(9) 0.0462(10) 0.0507(11) -0.0006(8) -0.0054(8) 0.0082(8) C10 0.0347(8) 0.0524(10) 0.0375(8) -0.0042(7) -0.0038(7) -0.0012(7) C11 0.0383(10) 0.0748(14) 0.0524(11) -0.0124(10) 0.0041(8) -0.0002(10) C12 0.0458(11) 0.0941(18) 0.0583(13) -0.0006(12) 0.0083(10) -0.0249(12) C13 0.0544(12) 0.0667(14) 0.0697(14) 0.0098(11) -0.0007(10) -0.0255(11) C14 0.0458(10) 0.0484(10) 0.0657(13) 0.0044(9) -0.0011(9) -0.0122(9) N2 0.0356(7) 0.0414(7) 0.0461(8) 0.0005(6) 0.0016(6) -0.0038(6) Mn2 0.03245(17) 0.03904(18) 0.02089(15) -0.00036(12) -0.00561(12) 0.00016(13) O2 0.0394(6) 0.0605(7) 0.0224(5) -0.0008(5) -0.0068(4) 0.0081(5) C15 0.0388(8) 0.0326(7) 0.0240(7) -0.0006(5) -0.0062(6) -0.0040(6) C16 0.0392(8) 0.0353(8) 0.0276(7) -0.0015(6) -0.0044(6) -0.0017(6) C17 0.0472(9) 0.0366(8) 0.0258(7) -0.0007(6) -0.0017(6) -0.0052(7) C18 0.0515(10) 0.0545(10) 0.0242(7) 0.0033(7) -0.0093(7) -0.0045(8) C19 0.0406(9) 0.0547(10) 0.0307(8) 0.0041(7) -0.0104(7) -0.0009(7) C20 0.0382(8) 0.0387(8) 0.0261(7) 0.0012(6) -0.0066(6) -0.0031(6) O5 0.0549(8) 0.0717(9) 0.0256(6) -0.0032(6) 0.0009(5) 0.0031(7) C30 0.0546(13) 0.127(2) 0.0436(11) -0.0126(13) 0.0054(10) 0.0156(14) C21 0.0340(8) 0.0394(8) 0.0307(7) 0.0012(6) -0.0083(6) -0.0023(6) N3 0.0316(6) 0.0344(6) 0.0275(6) -0.0011(5) -0.0039(5) -0.0028(5) C22 0.0324(8) 0.0429(9) 0.0318(8) 0.0015(7) -0.0016(6) -0.0044(6) C23 0.0415(9) 0.0452(9) 0.0298(8) -0.0036(7) 0.0017(7) 0.0002(7) C24 0.0403(8) 0.0369(8) 0.0324(8) -0.0063(6) -0.0025(6) 0.0008(6) C25 0.0399(9) 0.0536(11) 0.0525(11) -0.0010(9) -0.0041(8) 0.0033(8) C26 0.0594(13) 0.0603(13) 0.0646(14) 0.0101(10) -0.0185(11) 0.0119(10) C27 0.0712(14) 0.0537(12) 0.0571(13) 0.0190(10) -0.0070(11) -0.0020(10) C28 0.0529(11) 0.0496(11) 0.0553(11) 0.0084(9) 0.0028(9) -0.0064(9) N4 0.0389(7) 0.0425(8) 0.0458(8) 0.0036(6) -0.0011(6) -0.0006(6) O3 0.0433(7) 0.0437(7) 0.0569(8) 0.0001(6) -0.0140(6) -0.0028(6) C31 0.0674(14) 0.0609(13) 0.0647(14) -0.0108(11) -0.0133(11) -0.0161(11) Cl3 0.0440(2) 0.0539(3) 0.0630(3) -0.0097(2) 0.0037(2) -0.0021(2) O6 0.0906(13) 0.0930(13) 0.0745(12) -0.0103(10) -0.0072(10) -0.0403(11) O7 0.0707(12) 0.0927(15) 0.1318(19) 0.0161(13) 0.0141(12) 0.0230(11) O8 0.0851(15) 0.1201(19) 0.196(3) 0.086(2) -0.0521(17) -0.0334(14) O9 0.125(2) 0.175(3) 0.141(2) -0.108(2) 0.0562(18) -0.074(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn1 O1 1.8840(11) 2_566 ? Mn1 O1 1.8841(11) . ? Mn1 N1 2.0144(13) . ? Mn1 N1 2.0145(13) 2_566 ? Mn1 N2 2.3287(14) . ? Mn1 N2 2.3287(14) 2_566 ? O1 C1 1.3177(19) . ? C1 C2 1.408(2) . ? C1 C6 1.417(2) . ? C2 C3 1.383(2) . ? C2 H2 0.93(2) . ? C3 O4 1.352(2) . ? C3 C4 1.400(3) . ? C4 C5 1.364(3) . ? C4 H4 0.95(2) . ? C5 C6 1.409(2) . ? C5 H5 1.00(2) . ? C6 C7 1.436(2) . ? O4 C29 1.423(2) . ? C29 H29A 0.9600 . ? C29 H29B 0.9600 . ? C29 H29C 0.9600 . ? C7 N1 1.287(2) . ? C7 H8 0.94(2) . ? N1 C8 1.475(2) . ? C8 C9 1.532(3) . ? C8 H8A 0.91(2) . ? C8 H8B 0.91(3) . ? C9 C10 1.504(3) . ? C9 H9A 0.93(3) . ? C9 H9B 1.00(2) . ? C10 N2 1.346(2) . ? C10 C11 1.386(3) . ? C11 C12 1.371(4) . ? C11 H11 0.85(3) . ? C12 C13 1.369(4) . ? C12 H12 0.96(3) . ? C13 C14 1.377(3) . ? C13 H13 0.91(3) . ? C14 N2 1.341(2) . ? C14 H14 1.02(3) . ? Mn2 O2 1.8775(11) 2_575 ? Mn2 O2 1.8775(11) . ? Mn2 N3 2.0403(13) . ? Mn2 N3 2.0403(13) 2_575 ? Mn2 O3 2.2468(13) . ? Mn2 O3 2.2468(14) 2_575 ? O2 C15 1.3159(18) . ? C15 C20 1.406(2) . ? C15 C16 1.409(2) . ? C16 C17 1.387(2) . ? C16 H16 0.96(2) . ? C17 O5 1.359(2) . ? C17 C18 1.399(3) . ? C18 C19 1.362(3) . ? C18 H18 0.96(2) . ? C19 C20 1.408(2) . ? C19 H19 0.99(2) . ? C20 C21 1.430(2) . ? O5 C30 1.419(3) . ? C30 H30A 0.9600 . ? C30 H30B 0.9600 . ? C30 H30C 0.9600 . ? C21 N3 1.291(2) . ? C21 H21 0.93(2) . ? N3 C22 1.476(2) . ? C22 C23 1.532(2) . ? C22 H22A 0.94(2) . ? C22 H22B 0.97(2) . ? C23 C24 1.502(2) . ? C23 H23A 0.93(2) . ? C23 H23B 0.99(2) . ? C24 N4 1.341(2) . ? C24 C25 1.388(2) . ? C25 C26 1.381(3) . ? C25 H25 0.93(2) . ? C26 C27 1.370(4) . ? C26 H26 0.91(3) . ? C27 C28 1.373(3) . ? C27 H27 0.92(3) . ? C28 N4 1.342(2) . ? C28 H28 1.01(3) . ? O3 C31 1.418(3) . ? O3 H1O5 0.78(3) . ? C31 H31A 0.9600 . ? C31 H31B 0.9600 . ? C31 H31C 0.9600 . ? Cl3 O9 1.400(2) . ? Cl3 O7 1.403(2) . ? Cl3 O8 1.419(2) . ? Cl3 O6 1.4243(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 180.0 2_566 . ? O1 Mn1 N1 90.49(5) 2_566 . ? O1 Mn1 N1 89.51(5) . . ? O1 Mn1 N1 89.51(5) 2_566 2_566 ? O1 Mn1 N1 90.49(5) . 2_566 ? N1 Mn1 N1 180.0 . 2_566 ? O1 Mn1 N2 91.17(5) 2_566 . ? O1 Mn1 N2 88.83(5) . . ? N1 Mn1 N2 81.14(5) . . ? N1 Mn1 N2 98.86(5) 2_566 . ? O1 Mn1 N2 88.83(5) 2_566 2_566 ? O1 Mn1 N2 91.17(5) . 2_566 ? N1 Mn1 N2 98.86(5) . 2_566 ? N1 Mn1 N2 81.14(5) 2_566 2_566 ? N2 Mn1 N2 180.0 . 2_566 ? C1 O1 Mn1 124.92(9) . . ? O1 C1 C2 118.46(14) . . ? O1 C1 C6 122.31(14) . . ? C2 C1 C6 119.18(14) . . ? C3 C2 C1 120.05(15) . . ? C3 C2 H2 121.2(12) . . ? C1 C2 H2 118.7(12) . . ? O4 C3 C2 124.72(16) . . ? O4 C3 C4 114.36(15) . . ? C2 C3 C4 120.91(16) . . ? C5 C4 C3 119.40(17) . . ? C5 C4 H4 121.5(14) . . ? C3 C4 H4 119.1(14) . . ? C4 C5 C6 121.66(16) . . ? C4 C5 H5 119.8(13) . . ? C6 C5 H5 118.4(13) . . ? C5 C6 C1 118.73(15) . . ? C5 C6 C7 119.16(15) . . ? C1 C6 C7 121.74(15) . . ? C3 O4 C29 118.92(15) . . ? O4 C29 H29A 109.5 . . ? O4 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? O4 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? N1 C7 C6 125.62(15) . . ? N1 C7 H8 117.9(12) . . ? C6 C7 H8 116.3(12) . . ? C7 N1 C8 117.77(14) . . ? C7 N1 Mn1 122.38(11) . . ? C8 N1 Mn1 119.81(11) . . ? N1 C8 C9 113.88(15) . . ? N1 C8 H8A 108.6(14) . . ? C9 C8 H8A 110.4(14) . . ? N1 C8 H8B 108.9(15) . . ? C9 C8 H8B 110.5(15) . . ? H8A C8 H8B 104(2) . . ? C10 C9 C8 118.57(16) . . ? C10 C9 H9A 106.9(14) . . ? C8 C9 H9A 109.1(15) . . ? C10 C9 H9B 107.3(13) . . ? C8 C9 H9B 108.8(13) . . ? H9A C9 H9B 105.4(19) . . ? N2 C10 C11 120.42(19) . . ? N2 C10 C9 117.62(15) . . ? C11 C10 C9 121.85(18) . . ? C12 C11 C10 120.1(2) . . ? C12 C11 H11 122.4(18) . . ? C10 C11 H11 117.5(18) . . ? C13 C12 C11 119.4(2) . . ? C13 C12 H12 120.7(16) . . ? C11 C12 H12 119.8(16) . . ? C12 C13 C14 118.3(2) . . ? C12 C13 H13 120.1(16) . . ? C14 C13 H13 121.6(17) . . ? N2 C14 C13 122.9(2) . . ? N2 C14 H14 114.5(14) . . ? C13 C14 H14 122.6(14) . . ? C14 N2 C10 118.82(16) . . ? C14 N2 Mn1 118.00(13) . . ? C10 N2 Mn1 120.29(12) . . ? O2 Mn2 O2 180.0 2_575 . ? O2 Mn2 N3 89.35(5) 2_575 . ? O2 Mn2 N3 90.65(5) . . ? O2 Mn2 N3 90.65(5) 2_575 2_575 ? O2 Mn2 N3 89.35(5) . 2_575 ? N3 Mn2 N3 180.0 . 2_575 ? O2 Mn2 O3 91.71(6) 2_575 . ? O2 Mn2 O3 88.29(6) . . ? N3 Mn2 O3 88.01(5) . . ? N3 Mn2 O3 91.99(5) 2_575 . ? O2 Mn2 O3 88.29(6) 2_575 2_575 ? O2 Mn2 O3 91.70(6) . 2_575 ? N3 Mn2 O3 91.99(5) . 2_575 ? N3 Mn2 O3 88.01(5) 2_575 2_575 ? O3 Mn2 O3 180.0 . 2_575 ? C15 O2 Mn2 132.09(10) . . ? O2 C15 C20 122.38(14) . . ? O2 C15 C16 118.29(14) . . ? C20 C15 C16 119.32(14) . . ? C17 C16 C15 119.66(15) . . ? C17 C16 H16 120.7(12) . . ? C15 C16 H16 119.6(12) . . ? O5 C17 C16 124.38(16) . . ? O5 C17 C18 114.38(14) . . ? C16 C17 C18 121.23(15) . . ? C19 C18 C17 118.96(15) . . ? C19 C18 H18 118.2(13) . . ? C17 C18 H18 122.8(13) . . ? C18 C19 C20 121.91(16) . . ? C18 C19 H19 121.1(12) . . ? C20 C19 H19 117.0(12) . . ? C15 C20 C19 118.92(15) . . ? C15 C20 C21 123.04(14) . . ? C19 C20 C21 118.01(15) . . ? C17 O5 C30 118.30(15) . . ? O5 C30 H30A 109.5 . . ? O5 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? O5 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? N3 C21 C20 127.58(15) . . ? N3 C21 H21 118.9(12) . . ? C20 C21 H21 113.5(12) . . ? C21 N3 C22 115.63(13) . . ? C21 N3 Mn2 123.55(11) . . ? C22 N3 Mn2 120.73(10) . . ? N3 C22 C23 111.49(13) . . ? N3 C22 H22A 107.2(12) . . ? C23 C22 H22A 112.2(12) . . ? N3 C22 H22B 106.8(12) . . ? C23 C22 H22B 112.1(12) . . ? H22A C22 H22B 106.7(16) . . ? C24 C23 C22 113.49(14) . . ? C24 C23 H23A 109.0(13) . . ? C22 C23 H23A 106.9(13) . . ? C24 C23 H23B 111.7(12) . . ? C22 C23 H23B 107.2(12) . . ? H23A C23 H23B 108.3(18) . . ? N4 C24 C25 121.35(16) . . ? N4 C24 C23 116.45(15) . . ? C25 C24 C23 122.18(16) . . ? C26 C25 C24 119.35(19) . . ? C26 C25 H25 121.4(14) . . ? C24 C25 H25 119.2(14) . . ? C27 C26 C25 119.3(2) . . ? C27 C26 H26 122.1(17) . . ? C25 C26 H26 118.4(17) . . ? C26 C27 C28 118.4(2) . . ? C26 C27 H27 124.6(19) . . ? C28 C27 H27 117.1(19) . . ? N4 C28 C27 123.4(2) . . ? N4 C28 H28 113.1(14) . . ? C27 C28 H28 123.4(14) . . ? C24 N4 C28 118.22(16) . . ? C31 O3 Mn2 126.15(13) . . ? C31 O3 H1O5 107(2) . . ? Mn2 O3 H1O5 114(2) . . ? O3 C31 H31A 109.5 . . ? O3 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? O3 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? O9 Cl3 O7 108.85(19) . . ? O9 Cl3 O8 108.9(2) . . ? O7 Cl3 O8 106.99(16) . . ? O9 Cl3 O6 109.31(13) . . ? O7 Cl3 O6 111.65(15) . . ? O8 Cl3 O6 111.07(14) . . ? 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 N1 Mn1 O1 C1 39.50(12) . . . . ? N1 Mn1 O1 C1 -140.50(12) 2_566 . . . ? N2 Mn1 O1 C1 120.64(12) . . . . ? N2 Mn1 O1 C1 -59.36(12) 2_566 . . . ? Mn1 O1 C1 C2 152.68(11) . . . . ? Mn1 O1 C1 C6 -29.8(2) . . . . ? O1 C1 C2 C3 -179.66(14) . . . . ? C6 C1 C2 C3 2.8(2) . . . . ? C1 C2 C3 O4 176.52(16) . . . . ? C1 C2 C3 C4 -2.4(3) . . . . ? O4 C3 C4 C5 -178.84(18) . . . . ? C2 C3 C4 C5 0.2(3) . . . . ? C3 C4 C5 C6 1.7(3) . . . . ? C4 C5 C6 C1 -1.3(3) . . . . ? C4 C5 C6 C7 -174.48(18) . . . . ? O1 C1 C6 C5 -178.40(15) . . . . ? C2 C1 C6 C5 -0.9(2) . . . . ? O1 C1 C6 C7 -5.4(2) . . . . ? C2 C1 C6 C7 172.08(15) . . . . ? C2 C3 O4 C29 -0.2(3) . . . . ? C4 C3 O4 C29 178.81(18) . . . . ? C5 C6 C7 N1 -169.34(17) . . . . ? C1 C6 C7 N1 17.7(3) . . . . ? C6 C7 N1 C8 -172.62(16) . . . . ? C6 C7 N1 Mn1 4.9(2) . . . . ? O1 Mn1 N1 C7 153.19(13) 2_566 . . . ? O1 Mn1 N1 C7 -26.81(13) . . . . ? N2 Mn1 N1 C7 -115.70(13) . . . . ? N2 Mn1 N1 C7 64.30(13) 2_566 . . . ? O1 Mn1 N1 C8 -29.34(13) 2_566 . . . ? O1 Mn1 N1 C8 150.66(13) . . . . ? N2 Mn1 N1 C8 61.76(13) . . . . ? N2 Mn1 N1 C8 -118.24(13) 2_566 . . . ? C7 N1 C8 C9 130.15(17) . . . . ? Mn1 N1 C8 C9 -47.4(2) . . . . ? N1 C8 C9 C10 -23.9(3) . . . . ? C8 C9 C10 N2 60.9(2) . . . . ? C8 C9 C10 C11 -123.0(2) . . . . ? N2 C10 C11 C12 2.0(3) . . . . ? C9 C10 C11 C12 -174.0(2) . . . . ? C10 C11 C12 C13 -1.1(4) . . . . ? C11 C12 C13 C14 -0.6(4) . . . . ? C12 C13 C14 N2 1.6(4) . . . . ? C13 C14 N2 C10 -0.7(3) . . . . ? C13 C14 N2 Mn1 -161.55(19) . . . . ? C11 C10 N2 C14 -1.1(3) . . . . ? C9 C10 N2 C14 175.10(18) . . . . ? C11 C10 N2 Mn1 159.30(15) . . . . ? C9 C10 N2 Mn1 -24.5(2) . . . . ? O1 Mn1 N2 C14 -134.86(15) 2_566 . . . ? O1 Mn1 N2 C14 45.14(15) . . . . ? N1 Mn1 N2 C14 134.82(16) . . . . ? N1 Mn1 N2 C14 -45.18(16) 2_566 . . . ? O1 Mn1 N2 C10 64.60(14) 2_566 . . . ? O1 Mn1 N2 C10 -115.40(14) . . . . ? N1 Mn1 N2 C10 -25.71(13) . . . . ? N1 Mn1 N2 C10 154.29(13) 2_566 . . . ? N3 Mn2 O2 C15 -9.79(15) . . . . ? N3 Mn2 O2 C15 170.21(15) 2_575 . . . ? O3 Mn2 O2 C15 78.20(15) . . . . ? O3 Mn2 O2 C15 -101.80(15) 2_575 . . . ? Mn2 O2 C15 C20 8.7(2) . . . . ? Mn2 O2 C15 C16 -172.78(12) . . . . ? O2 C15 C16 C17 -177.90(15) . . . . ? C20 C15 C16 C17 0.7(2) . . . . ? C15 C16 C17 O5 178.71(15) . . . . ? C15 C16 C17 C18 0.0(2) . . . . ? O5 C17 C18 C19 -179.11(17) . . . . ? C16 C17 C18 C19 -0.3(3) . . . . ? C17 C18 C19 C20 -0.1(3) . . . . ? O2 C15 C20 C19 177.44(16) . . . . ? C16 C15 C20 C19 -1.1(2) . . . . ? O2 C15 C20 C21 -0.5(2) . . . . ? C16 C15 C20 C21 -178.98(15) . . . . ? C18 C19 C20 C15 0.8(3) . . . . ? C18 C19 C20 C21 178.83(17) . . . . ? C16 C17 O5 C30 7.3(3) . . . . ? C18 C17 O5 C30 -173.9(2) . . . . ? C15 C20 C21 N3 -3.0(3) . . . . ? C19 C20 C21 N3 179.06(17) . . . . ? C20 C21 N3 C22 -177.79(15) . . . . ? C20 C21 N3 Mn2 -1.1(2) . . . . ? O2 Mn2 N3 C21 -174.35(13) 2_575 . . . ? O2 Mn2 N3 C21 5.65(13) . . . . ? O3 Mn2 N3 C21 -82.62(13) . . . . ? O3 Mn2 N3 C21 97.38(13) 2_575 . . . ? O2 Mn2 N3 C22 2.23(12) 2_575 . . . ? O2 Mn2 N3 C22 -177.77(12) . . . . ? O3 Mn2 N3 C22 93.96(12) . . . . ? O3 Mn2 N3 C22 -86.04(12) 2_575 . . . ? C21 N3 C22 C23 97.86(17) . . . . ? Mn2 N3 C22 C23 -78.98(15) . . . . ? N3 C22 C23 C24 -58.72(19) . . . . ? C22 C23 C24 N4 87.15(19) . . . . ? C22 C23 C24 C25 -91.1(2) . . . . ? N4 C24 C25 C26 0.6(3) . . . . ? C23 C24 C25 C26 178.79(19) . . . . ? C24 C25 C26 C27 -0.7(3) . . . . ? C25 C26 C27 C28 0.3(4) . . . . ? C26 C27 C28 N4 0.1(4) . . . . ? C25 C24 N4 C28 -0.2(3) . . . . ? C23 C24 N4 C28 -178.44(17) . . . . ? C27 C28 N4 C24 -0.2(3) . . . . ? O2 Mn2 O3 C31 -53.15(17) 2_575 . . . ? O2 Mn2 O3 C31 126.85(17) . . . . ? N3 Mn2 O3 C31 -142.44(17) . . . . ? N3 Mn2 O3 C31 37.56(17) 2_575 . . . ? 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 O3 H1O5 N4 0.78(3) 1.95(3) 2.722(2) 173(3) . _diffrn_measured_fraction_theta_max 0.928 _diffrn_reflns_theta_full 27.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.404 _refine_diff_density_min -0.445 _refine_diff_density_rms 0.078 #===END data_mor125 _database_code_depnum_ccdc_archive 'CCDC 718585' #TrackingRef '- mor121pub.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C28 H22 Cl4 Mn N4 O2, C32 H34 Cl4 Mn N4 O4, 2 (Cl O4)' _chemical_formula_sum 'C60 H56 Cl10 Mn2 N8 O14' _chemical_formula_weight 1577.51 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 10.3459(11) _cell_length_b 10.6187(11) _cell_length_c 17.4583(19) _cell_angle_alpha 100.014(2) _cell_angle_beta 96.329(2) _cell_angle_gamma 115.590(2) _cell_volume 1666.0(3) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5691 _cell_measurement_theta_min 2.30 _cell_measurement_theta_max 26.66 _exptl_crystal_description chunk _exptl_crystal_colour red _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.572 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 804 _exptl_absorpt_coefficient_mu 0.850 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6763 _exptl_absorpt_correction_T_max 0.9198 _exptl_absorpt_process_details ; SADABS v.2.10 (Bruker,2003) was used for absorption correction. R(int) for selected reflections was 0.043 before and 0.019 after correction. The Ratio of minimum to maximum transmission is 0.735259. The \l/2 correction factor is 0.0015 ; _exptl_special_details ; The dataset was collected at room temperature without temperature control. ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12358 _diffrn_reflns_av_R_equivalents 0.0195 _diffrn_reflns_av_sigmaI/netI 0.0269 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.19 _diffrn_reflns_theta_max 26.69 _reflns_number_total 6193 _reflns_number_gt 5210 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0627P)^2^+0.6333P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6193 _refine_ls_number_parameters 442 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0494 _refine_ls_R_factor_gt 0.0414 _refine_ls_wR_factor_ref 0.1137 _refine_ls_wR_factor_gt 0.1076 _refine_ls_goodness_of_fit_ref 1.033 _refine_ls_restrained_S_all 1.033 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 1.0000 0.5000 0.0000 0.04292(14) Uani 1 2 d S . . O1 O 0.89483(17) 0.60752(17) 0.01149(10) 0.0478(4) Uani 1 1 d . . . C1 C 0.7636(3) 0.5693(3) -0.02936(13) 0.0428(5) Uani 1 1 d . . . C2 C 0.7201(3) 0.6737(3) -0.04209(14) 0.0460(5) Uani 1 1 d . . . Cl1 Cl 0.84246(9) 0.85369(7) -0.00194(5) 0.0706(2) Uani 1 1 d . . . C3 C 0.5834(3) 0.6379(3) -0.08456(15) 0.0513(6) Uani 1 1 d . . . H3 H 0.5590 0.7096 -0.0933 0.062 Uiso 1 1 calc R . . C4 C 0.4837(3) 0.4951(3) -0.11380(14) 0.0499(6) Uani 1 1 d . . . Cl2 Cl 0.31069(8) 0.45229(9) -0.16644(5) 0.0730(2) Uani 1 1 d . . . C5 C 0.5162(3) 0.3880(3) -0.10084(14) 0.0492(6) Uani 1 1 d . . . H5 H 0.4460 0.2920 -0.1192 0.059 Uiso 1 1 calc R . . C6 C 0.6562(3) 0.4237(3) -0.05967(14) 0.0450(5) Uani 1 1 d . . . C7 C 0.6832(3) 0.3091(3) -0.04041(15) 0.0489(6) Uani 1 1 d . . . H7 H 0.6023 0.2201 -0.0469 0.059 Uiso 1 1 calc R . . N1 N 0.8095(2) 0.3202(2) -0.01512(12) 0.0479(5) Uani 1 1 d . A . C8 C 0.8150(3) 0.2001(3) 0.01405(19) 0.0611(7) Uani 1 1 d . . . H8A H 0.9035 0.1940 0.0059 0.073 Uiso 0.729(12) 1 calc PR A 1 H8B H 0.7312 0.1097 -0.0145 0.073 Uiso 0.729(12) 1 calc PR A 1 H8C H 0.8459 0.1496 -0.0258 0.073 Uiso 0.271(12) 1 d PR A 2 H8D H 0.7152 0.1340 0.0150 0.073 Uiso 0.271(12) 1 d PR A 2 C9A C 0.8132(6) 0.2283(5) 0.1008(3) 0.0693(18) Uani 0.729(12) 1 d P A 1 H9A H 0.8157 0.1486 0.1198 0.083 Uiso 0.729(12) 1 calc PR A 1 H9B H 0.7198 0.2258 0.1061 0.083 Uiso 0.729(12) 1 calc PR A 1 C9B C 0.910(2) 0.2262(12) 0.0949(7) 0.065(5) Uani 0.271(12) 1 d P A 2 H9C H 1.0044 0.2350 0.0872 0.078 Uiso 0.271(12) 1 calc PR A 2 H9D H 0.8633 0.1435 0.1168 0.078 Uiso 0.271(12) 1 calc PR A 2 C10 C 0.9332(3) 0.3673(3) 0.15674(18) 0.0617(7) Uani 1 1 d . . . C11 C 0.9382(4) 0.3725(4) 0.2364(2) 0.0738(9) Uani 1 1 d . A . H11 H 0.8817 0.2902 0.2525 0.089 Uiso 1 1 calc R . . C12 C 1.0254(5) 0.4975(5) 0.2908(2) 0.0973(12) Uani 1 1 d . . . H12 H 1.0294 0.5023 0.3448 0.117 Uiso 1 1 calc R A . C13 C 1.1083(5) 0.6175(5) 0.2658(2) 0.0989(13) Uani 1 1 d . A . H13 H 1.1722 0.7039 0.3023 0.119 Uiso 1 1 calc R . . C14 C 1.0945(4) 0.6067(4) 0.18604(18) 0.0711(8) Uani 1 1 d . . . H14 H 1.1466 0.6893 0.1690 0.085 Uiso 1 1 calc R A . N2 N 1.0109(2) 0.4852(2) 0.13171(13) 0.0544(5) Uani 1 1 d . A . Mn2 Mn 0.5000 0.5000 0.5000 0.03846(14) Uani 1 2 d S . . O2 O 0.50293(18) 0.62613(17) 0.43733(9) 0.0460(4) Uani 1 1 d . . . C15 C 0.5633(2) 0.7671(2) 0.45552(14) 0.0423(5) Uani 1 1 d . . . C16 C 0.5803(3) 0.8390(3) 0.39361(15) 0.0484(6) Uani 1 1 d . . . Cl3 Cl 0.52165(10) 0.73651(8) 0.29674(4) 0.0718(2) Uani 1 1 d . . . C17 C 0.6417(3) 0.9869(3) 0.40844(17) 0.0536(6) Uani 1 1 d . . . H17 H 0.6515 1.0316 0.3666 0.064 Uiso 1 1 calc R . . C18 C 0.6888(3) 1.0681(3) 0.48660(18) 0.0525(6) Uani 1 1 d . . . Cl4 Cl 0.76226(8) 1.25478(7) 0.50445(5) 0.0727(2) Uani 1 1 d . . . C19 C 0.6731(3) 1.0040(3) 0.54875(16) 0.0502(6) Uani 1 1 d . . . H19 H 0.7034 1.0599 0.6008 0.060 Uiso 1 1 calc R . . C20 C 0.6109(2) 0.8528(3) 0.53373(15) 0.0440(5) Uani 1 1 d . . . C21 C 0.5938(3) 0.7910(3) 0.60142(15) 0.0451(5) Uani 1 1 d . . . H21 H 0.6159 0.8541 0.6507 0.054 Uiso 1 1 calc R . . N3 N 0.5512(2) 0.6579(2) 0.60091(11) 0.0416(4) Uani 1 1 d . . . C22 C 0.5578(3) 0.6267(3) 0.68033(14) 0.0491(6) Uani 1 1 d . . . H22A H 0.4798 0.5316 0.6772 0.059 Uiso 1 1 calc R . . H22B H 0.5437 0.6964 0.7176 0.059 Uiso 1 1 calc R . . C23 C 0.7055(3) 0.6332(3) 0.70990(16) 0.0581(7) Uani 1 1 d . . . H23A H 0.7071 0.6122 0.7618 0.070 Uiso 1 1 calc R . . H23B H 0.7161 0.5594 0.6739 0.070 Uiso 1 1 calc R . . C24 C 0.8332(3) 0.7770(3) 0.71607(17) 0.0609(7) Uani 1 1 d . . . C25 C 0.8792(4) 0.8910(4) 0.78169(19) 0.0825(10) Uani 1 1 d . . . H25 H 0.8321 0.8799 0.8243 0.099 Uiso 1 1 calc R . . C26 C 0.9961(5) 1.0220(4) 0.7838(2) 0.1062(15) Uani 1 1 d . . . H26 H 1.0293 1.0996 0.8278 0.127 Uiso 1 1 calc R . . C27 C 1.0614(4) 1.0350(5) 0.7202(3) 0.1036(14) Uani 1 1 d . . . H27 H 1.1397 1.1218 0.7198 0.124 Uiso 1 1 calc R . . C28 C 1.0102(4) 0.9188(4) 0.6569(2) 0.0910(12) Uani 1 1 d . . . H28 H 1.0566 0.9288 0.6140 0.109 Uiso 1 1 calc R . . N4 N 0.8965(3) 0.7907(3) 0.65279(15) 0.0666(6) Uani 1 1 d . . . O3 O 0.7427(2) 0.5838(2) 0.51172(14) 0.0594(5) Uani 1 1 d . . . H1O3 H 0.783(3) 0.635(3) 0.5508(16) 0.043(8) Uiso 1 1 d . . . C29 C 0.8268(3) 0.5835(4) 0.4525(2) 0.0673(8) Uani 1 1 d . . . H15A H 0.7697 0.4980 0.4094 0.081 Uiso 1 1 calc R . . H15B H 0.9138 0.5785 0.4753 0.081 Uiso 1 1 calc R . . C30 C 0.8719(4) 0.7132(4) 0.4198(3) 0.0924(12) Uani 1 1 d . . . H16A H 0.7862 0.7172 0.3956 0.139 Uiso 1 1 calc R . . H16B H 0.9288 0.7078 0.3806 0.139 Uiso 1 1 calc R . . H16C H 0.9297 0.7982 0.4621 0.139 Uiso 1 1 calc R . . Cl5 Cl 0.50025(9) 0.04164(8) 0.19860(5) 0.0696(2) Uani 1 1 d . . . O4 O 0.5960(3) 0.1537(3) 0.26533(16) 0.0955(8) Uani 1 1 d . . . O5 O 0.4598(4) 0.1001(4) 0.1411(2) 0.1419(13) Uani 1 1 d . . . O6 O 0.5753(3) -0.0344(3) 0.16867(18) 0.1046(9) Uani 1 1 d . . . O7 O 0.3752(3) -0.0509(3) 0.2242(2) 0.1271(11) 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 0.0369(3) 0.0362(3) 0.0513(3) 0.0143(2) 0.0046(2) 0.0128(2) O1 0.0413(9) 0.0394(9) 0.0585(10) 0.0128(7) 0.0048(7) 0.0158(7) C1 0.0448(13) 0.0462(13) 0.0419(12) 0.0166(10) 0.0127(10) 0.0221(11) C2 0.0470(13) 0.0430(13) 0.0479(13) 0.0146(10) 0.0111(10) 0.0191(11) Cl1 0.0697(5) 0.0417(4) 0.0913(5) 0.0170(3) -0.0009(4) 0.0216(3) C3 0.0565(15) 0.0570(16) 0.0522(14) 0.0204(12) 0.0155(12) 0.0331(13) C4 0.0434(13) 0.0620(16) 0.0470(13) 0.0138(11) 0.0089(10) 0.0267(12) Cl2 0.0519(4) 0.0861(5) 0.0806(5) 0.0146(4) -0.0010(3) 0.0372(4) C5 0.0430(13) 0.0475(14) 0.0504(13) 0.0083(11) 0.0087(11) 0.0164(11) C6 0.0431(13) 0.0426(13) 0.0496(13) 0.0125(10) 0.0108(10) 0.0192(11) C7 0.0389(13) 0.0373(12) 0.0613(15) 0.0098(11) 0.0079(11) 0.0109(10) N1 0.0427(11) 0.0360(10) 0.0598(12) 0.0142(9) 0.0056(9) 0.0138(9) C8 0.0491(15) 0.0380(13) 0.091(2) 0.0245(13) 0.0048(14) 0.0148(12) C9A 0.057(3) 0.060(3) 0.089(3) 0.046(2) 0.010(2) 0.016(2) C9B 0.089(12) 0.059(7) 0.068(7) 0.035(5) 0.025(6) 0.042(7) C10 0.0602(17) 0.0647(18) 0.0685(18) 0.0300(14) 0.0110(14) 0.0319(15) C11 0.070(2) 0.092(2) 0.074(2) 0.0412(19) 0.0233(16) 0.0405(19) C12 0.126(3) 0.113(3) 0.065(2) 0.031(2) 0.036(2) 0.060(3) C13 0.131(4) 0.084(3) 0.064(2) 0.0036(18) 0.021(2) 0.039(3) C14 0.073(2) 0.0635(19) 0.0631(18) 0.0106(15) 0.0152(15) 0.0213(16) N2 0.0515(12) 0.0566(13) 0.0587(13) 0.0187(11) 0.0118(10) 0.0266(11) Mn2 0.0420(3) 0.0352(3) 0.0444(3) 0.0165(2) 0.0164(2) 0.0191(2) O2 0.0578(10) 0.0373(9) 0.0473(9) 0.0178(7) 0.0150(7) 0.0221(8) C15 0.0386(12) 0.0408(13) 0.0559(14) 0.0205(10) 0.0159(10) 0.0214(10) C16 0.0472(13) 0.0493(14) 0.0572(14) 0.0229(11) 0.0152(11) 0.0252(12) Cl3 0.1031(6) 0.0618(4) 0.0542(4) 0.0280(3) 0.0199(4) 0.0356(4) C17 0.0437(13) 0.0514(15) 0.0759(18) 0.0352(14) 0.0178(12) 0.0226(12) C18 0.0361(12) 0.0372(13) 0.0845(19) 0.0245(13) 0.0094(12) 0.0144(10) Cl4 0.0542(4) 0.0391(4) 0.1146(6) 0.0290(4) 0.0023(4) 0.0122(3) C19 0.0414(13) 0.0404(13) 0.0663(16) 0.0135(11) 0.0063(11) 0.0177(11) C20 0.0381(12) 0.0416(12) 0.0572(14) 0.0176(11) 0.0130(10) 0.0201(10) C21 0.0429(12) 0.0435(13) 0.0517(13) 0.0132(10) 0.0139(10) 0.0211(11) N3 0.0416(10) 0.0420(11) 0.0456(10) 0.0148(8) 0.0153(8) 0.0204(9) C22 0.0590(15) 0.0454(13) 0.0461(13) 0.0173(10) 0.0205(11) 0.0225(12) C23 0.0652(17) 0.0592(16) 0.0512(14) 0.0256(12) 0.0110(12) 0.0258(14) C24 0.0573(16) 0.0630(17) 0.0566(16) 0.0243(13) -0.0008(13) 0.0219(14) C25 0.088(2) 0.079(2) 0.0559(17) 0.0208(16) 0.0031(16) 0.0177(19) C26 0.107(3) 0.077(2) 0.077(2) 0.0105(19) -0.021(2) 0.003(2) C27 0.080(2) 0.083(3) 0.089(3) 0.029(2) -0.010(2) -0.011(2) C28 0.0578(19) 0.100(3) 0.090(3) 0.040(2) 0.0116(18) 0.0081(19) N4 0.0506(13) 0.0724(16) 0.0688(15) 0.0250(12) 0.0118(11) 0.0186(12) O3 0.0433(10) 0.0683(13) 0.0626(13) 0.0179(11) 0.0202(10) 0.0195(10) C29 0.0547(16) 0.082(2) 0.084(2) 0.0366(17) 0.0370(15) 0.0368(16) C30 0.083(2) 0.117(3) 0.122(3) 0.074(3) 0.059(2) 0.061(2) Cl5 0.0862(5) 0.0510(4) 0.0726(5) 0.0144(3) 0.0061(4) 0.0351(4) O4 0.0902(17) 0.0804(16) 0.0920(17) -0.0029(13) 0.0122(14) 0.0285(14) O5 0.187(3) 0.136(3) 0.126(3) 0.059(2) -0.005(2) 0.094(3) O6 0.137(2) 0.0790(17) 0.119(2) 0.0213(15) 0.0397(18) 0.0672(18) O7 0.0820(18) 0.089(2) 0.194(3) 0.050(2) 0.041(2) 0.0157(16) _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 1.8892(17) 2_765 ? Mn1 O1 1.8892(17) . ? Mn1 N1 2.0150(19) . ? Mn1 N1 2.0150(19) 2_765 ? Mn1 N2 2.326(2) 2_765 ? Mn1 N2 2.326(2) . ? O1 C1 1.314(3) . ? C1 C2 1.405(3) . ? C1 C6 1.416(3) . ? C2 C3 1.379(3) . ? C2 Cl1 1.731(2) . ? C3 C4 1.373(4) . ? C3 H3 0.9300 . ? C4 C5 1.365(4) . ? C4 Cl2 1.744(2) . ? C5 C6 1.399(3) . ? C5 H5 0.9300 . ? C6 C7 1.445(3) . ? C7 N1 1.280(3) . ? C7 H7 0.9300 . ? N1 C8 1.473(3) . ? C8 C9A 1.496(6) . ? C8 C9B 1.534(14) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C8 H8C 0.9700 . ? C8 H8D 0.9700 . ? C9A C10 1.524(5) . ? C9A H9A 0.9700 . ? C9A H9B 0.9700 . ? C9B C10 1.593(12) . ? C9B H9C 0.9700 . ? C9B H9D 0.9700 . ? C10 N2 1.342(4) . ? C10 C11 1.376(4) . ? C11 C12 1.348(5) . ? C11 H11 0.9300 . ? C12 C13 1.372(6) . ? C12 H12 0.9300 . ? C13 C14 1.364(5) . ? C13 H13 0.9300 . ? C14 N2 1.320(4) . ? C14 H14 0.9300 . ? Mn2 O2 1.8637(15) 2_666 ? Mn2 O2 1.8638(15) . ? Mn2 N3 2.0481(19) 2_666 ? Mn2 N3 2.0482(19) . ? Mn2 O3 2.2429(19) 2_666 ? Mn2 O3 2.2430(19) . ? O2 C15 1.310(3) . ? C15 C20 1.403(3) . ? C15 C16 1.412(3) . ? C16 C17 1.377(4) . ? C16 Cl3 1.725(3) . ? C17 C18 1.387(4) . ? C17 H17 0.9300 . ? C18 C19 1.367(4) . ? C18 Cl4 1.742(2) . ? C19 C20 1.408(3) . ? C19 H19 0.9300 . ? C20 C21 1.440(3) . ? C21 N3 1.284(3) . ? C21 H21 0.9300 . ? N3 C22 1.482(3) . ? C22 C23 1.525(4) . ? C22 H22A 0.9700 . ? C22 H22B 0.9700 . ? C23 C24 1.502(4) . ? C23 H23A 0.9700 . ? C23 H23B 0.9700 . ? C24 N4 1.343(4) . ? C24 C25 1.380(5) . ? C25 C26 1.385(5) . ? C25 H25 0.9300 . ? C26 C27 1.359(6) . ? C26 H26 0.9300 . ? C27 C28 1.362(6) . ? C27 H27 0.9300 . ? C28 N4 1.344(4) . ? C28 H28 0.9300 . ? O3 C29 1.424(3) . ? O3 H1O3 0.74(3) . ? C29 C30 1.490(4) . ? C29 H15A 0.9700 . ? C29 H15B 0.9700 . ? C30 H16A 0.9600 . ? C30 H16B 0.9600 . ? C30 H16C 0.9600 . ? Cl5 O5 1.384(3) . ? Cl5 O4 1.414(3) . ? Cl5 O6 1.419(3) . ? Cl5 O7 1.422(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Mn1 O1 180.0 2_765 . ? O1 Mn1 N1 91.77(8) 2_765 . ? O1 Mn1 N1 88.23(8) . . ? O1 Mn1 N1 88.23(8) 2_765 2_765 ? O1 Mn1 N1 91.77(8) . 2_765 ? N1 Mn1 N1 180.0 . 2_765 ? O1 Mn1 N2 91.95(7) 2_765 2_765 ? O1 Mn1 N2 88.05(7) . 2_765 ? N1 Mn1 N2 98.46(8) . 2_765 ? N1 Mn1 N2 81.54(8) 2_765 2_765 ? O1 Mn1 N2 88.05(7) 2_765 . ? O1 Mn1 N2 91.95(7) . . ? N1 Mn1 N2 81.54(8) . . ? N1 Mn1 N2 98.46(8) 2_765 . ? N2 Mn1 N2 180.0 2_765 . ? C1 O1 Mn1 125.72(15) . . ? O1 C1 C2 120.7(2) . . ? O1 C1 C6 123.1(2) . . ? C2 C1 C6 116.1(2) . . ? C3 C2 C1 122.4(2) . . ? C3 C2 Cl1 118.95(19) . . ? C1 C2 Cl1 118.60(18) . . ? C4 C3 C2 119.3(2) . . ? C4 C3 H3 120.4 . . ? C2 C3 H3 120.4 . . ? C5 C4 C3 121.5(2) . . ? C5 C4 Cl2 120.0(2) . . ? C3 C4 Cl2 118.5(2) . . ? C4 C5 C6 119.5(2) . . ? C4 C5 H5 120.3 . . ? C6 C5 H5 120.3 . . ? C5 C6 C1 121.2(2) . . ? C5 C6 C7 118.2(2) . . ? C1 C6 C7 120.2(2) . . ? N1 C7 C6 125.3(2) . . ? N1 C7 H7 117.4 . . ? C6 C7 H7 117.4 . . ? C7 N1 C8 117.7(2) . . ? C7 N1 Mn1 124.28(17) . . ? C8 N1 Mn1 117.53(16) . . ? N1 C8 C9A 107.7(3) . . ? N1 C8 C9B 121.4(5) . . ? N1 C8 H8A 110.2 . . ? C9A C8 H8A 110.2 . . ? N1 C8 H8B 110.2 . . ? C9A C8 H8B 110.2 . . ? H8A C8 H8B 108.5 . . ? N1 C8 H8C 107.0 . . ? C9B C8 H8C 107.1 . . ? N1 C8 H8D 107.0 . . ? C9B C8 H8D 106.8 . . ? H8C C8 H8D 106.7 . . ? C8 C9A C10 118.9(3) . . ? C8 C9A H9A 107.6 . . ? C10 C9A H9A 107.6 . . ? C8 C9A H9B 107.6 . . ? C10 C9A H9B 107.6 . . ? H9A C9A H9B 107.0 . . ? C8 C9B C10 112.6(8) . . ? C8 C9B H9C 109.1 . . ? C10 C9B H9C 109.1 . . ? C8 C9B H9D 109.1 . . ? C10 C9B H9D 109.1 . . ? H9C C9B H9D 107.8 . . ? N2 C10 C11 121.5(3) . . ? N2 C10 C9A 122.8(3) . . ? C11 C10 C9A 114.7(3) . . ? N2 C10 C9B 110.3(5) . . ? C11 C10 C9B 121.3(4) . . ? C12 C11 C10 119.6(3) . . ? C12 C11 H11 120.2 . . ? C10 C11 H11 120.2 . . ? C11 C12 C13 119.3(3) . . ? C11 C12 H12 120.3 . . ? C13 C12 H12 120.3 . . ? C14 C13 C12 118.2(4) . . ? C14 C13 H13 120.9 . . ? C12 C13 H13 120.9 . . ? N2 C14 C13 123.4(3) . . ? N2 C14 H14 118.3 . . ? C13 C14 H14 118.3 . . ? C14 N2 C10 117.9(3) . . ? C14 N2 Mn1 116.10(19) . . ? C10 N2 Mn1 125.84(19) . . ? O2 Mn2 O2 180.0 2_666 . ? O2 Mn2 N3 90.41(7) 2_666 2_666 ? O2 Mn2 N3 89.59(7) . 2_666 ? O2 Mn2 N3 89.59(7) 2_666 . ? O2 Mn2 N3 90.41(7) . . ? N3 Mn2 N3 180.000(1) 2_666 . ? O2 Mn2 O3 89.95(8) 2_666 2_666 ? O2 Mn2 O3 90.05(8) . 2_666 ? N3 Mn2 O3 85.89(8) 2_666 2_666 ? N3 Mn2 O3 94.11(8) . 2_666 ? O2 Mn2 O3 90.05(7) 2_666 . ? O2 Mn2 O3 89.95(8) . . ? N3 Mn2 O3 94.11(8) 2_666 . ? N3 Mn2 O3 85.89(8) . . ? O3 Mn2 O3 180.00(4) 2_666 . ? C15 O2 Mn2 130.37(15) . . ? O2 C15 C20 123.8(2) . . ? O2 C15 C16 119.0(2) . . ? C20 C15 C16 117.2(2) . . ? C17 C16 C15 122.1(2) . . ? C17 C16 Cl3 119.6(2) . . ? C15 C16 Cl3 118.27(19) . . ? C16 C17 C18 119.1(2) . . ? C16 C17 H17 120.4 . . ? C18 C17 H17 120.4 . . ? C19 C18 C17 121.2(2) . . ? C19 C18 Cl4 120.1(2) . . ? C17 C18 Cl4 118.6(2) . . ? C18 C19 C20 119.8(2) . . ? C18 C19 H19 120.1 . . ? C20 C19 H19 120.1 . . ? C15 C20 C19 120.7(2) . . ? C15 C20 C21 122.0(2) . . ? C19 C20 C21 117.3(2) . . ? N3 C21 C20 126.8(2) . . ? N3 C21 H21 116.6 . . ? C20 C21 H21 116.6 . . ? C21 N3 C22 115.3(2) . . ? C21 N3 Mn2 123.59(16) . . ? C22 N3 Mn2 120.76(15) . . ? N3 C22 C23 110.44(19) . . ? N3 C22 H22A 109.6 . . ? C23 C22 H22A 109.6 . . ? N3 C22 H22B 109.6 . . ? C23 C22 H22B 109.6 . . ? H22A C22 H22B 108.1 . . ? C24 C23 C22 113.2(2) . . ? C24 C23 H23A 108.9 . . ? C22 C23 H23A 108.9 . . ? C24 C23 H23B 108.9 . . ? C22 C23 H23B 108.9 . . ? H23A C23 H23B 107.8 . . ? N4 C24 C25 121.6(3) . . ? N4 C24 C23 116.4(3) . . ? C25 C24 C23 121.9(3) . . ? C24 C25 C26 119.6(4) . . ? C24 C25 H25 120.2 . . ? C26 C25 H25 120.2 . . ? C27 C26 C25 118.7(4) . . ? C27 C26 H26 120.7 . . ? C25 C26 H26 120.7 . . ? C26 C27 C28 119.0(4) . . ? C26 C27 H27 120.5 . . ? C28 C27 H27 120.5 . . ? N4 C28 C27 123.8(4) . . ? N4 C28 H28 118.1 . . ? C27 C28 H28 118.1 . . ? C24 N4 C28 117.3(3) . . ? C29 O3 Mn2 130.3(2) . . ? C29 O3 H1O3 116(2) . . ? Mn2 O3 H1O3 111(2) . . ? O3 C29 C30 113.0(3) . . ? O3 C29 H15A 109.0 . . ? C30 C29 H15A 109.0 . . ? O3 C29 H15B 109.0 . . ? C30 C29 H15B 109.0 . . ? H15A C29 H15B 107.8 . . ? C29 C30 H16A 109.5 . . ? C29 C30 H16B 109.5 . . ? H16A C30 H16B 109.5 . . ? C29 C30 H16C 109.5 . . ? H16A C30 H16C 109.5 . . ? H16B C30 H16C 109.5 . . ? O5 Cl5 O4 109.4(2) . . ? O5 Cl5 O6 110.3(2) . . ? O4 Cl5 O6 108.15(18) . . ? O5 Cl5 O7 110.5(2) . . ? O4 Cl5 O7 108.0(2) . . ? O6 Cl5 O7 110.47(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 N1 Mn1 O1 C1 -38.67(18) . . . . ? N1 Mn1 O1 C1 141.33(18) 2_765 . . . ? N2 Mn1 O1 C1 59.86(18) 2_765 . . . ? N2 Mn1 O1 C1 -120.14(18) . . . . ? Mn1 O1 C1 C2 -152.93(17) . . . . ? Mn1 O1 C1 C6 30.1(3) . . . . ? O1 C1 C2 C3 -180.0(2) . . . . ? C6 C1 C2 C3 -2.8(3) . . . . ? O1 C1 C2 Cl1 -0.7(3) . . . . ? C6 C1 C2 Cl1 176.50(17) . . . . ? C1 C2 C3 C4 1.9(4) . . . . ? Cl1 C2 C3 C4 -177.35(19) . . . . ? C2 C3 C4 C5 0.9(4) . . . . ? C2 C3 C4 Cl2 179.32(19) . . . . ? C3 C4 C5 C6 -2.6(4) . . . . ? Cl2 C4 C5 C6 178.96(19) . . . . ? C4 C5 C6 C1 1.7(4) . . . . ? C4 C5 C6 C7 174.4(2) . . . . ? O1 C1 C6 C5 178.1(2) . . . . ? C2 C1 C6 C5 1.0(3) . . . . ? O1 C1 C6 C7 5.5(4) . . . . ? C2 C1 C6 C7 -171.6(2) . . . . ? C5 C6 C7 N1 167.9(2) . . . . ? C1 C6 C7 N1 -19.4(4) . . . . ? C6 C7 N1 C8 170.1(3) . . . . ? C6 C7 N1 Mn1 -2.1(4) . . . . ? O1 Mn1 N1 C7 -155.3(2) 2_765 . . . ? O1 Mn1 N1 C7 24.7(2) . . . . ? N2 Mn1 N1 C7 -63.0(2) 2_765 . . . ? N2 Mn1 N1 C7 117.0(2) . . . . ? O1 Mn1 N1 C8 32.5(2) 2_765 . . . ? O1 Mn1 N1 C8 -147.5(2) . . . . ? N2 Mn1 N1 C8 124.8(2) 2_765 . . . ? N2 Mn1 N1 C8 -55.2(2) . . . . ? C7 N1 C8 C9A -88.9(3) . . . . ? Mn1 N1 C8 C9A 83.8(3) . . . . ? C7 N1 C8 C9B -130.0(8) . . . . ? Mn1 N1 C8 C9B 42.7(9) . . . . ? N1 C8 C9A C10 -58.1(5) . . . . ? N1 C8 C9B C10 27.8(14) . . . . ? C8 C9A C10 N2 22.4(7) . . . . ? C8 C9A C10 C11 -168.9(4) . . . . ? C8 C9B C10 N2 -65.2(12) . . . . ? C8 C9B C10 C11 143.5(6) . . . . ? N2 C10 C11 C12 -1.6(5) . . . . ? C9A C10 C11 C12 -170.4(4) . . . . ? C9B C10 C11 C12 146.6(9) . . . . ? C10 C11 C12 C13 -0.3(6) . . . . ? C11 C12 C13 C14 2.6(7) . . . . ? C12 C13 C14 N2 -3.4(6) . . . . ? C13 C14 N2 C10 1.7(5) . . . . ? C13 C14 N2 Mn1 177.4(3) . . . . ? C11 C10 N2 C14 0.9(4) . . . . ? C9A C10 N2 C14 168.8(4) . . . . ? C9B C10 N2 C14 -150.4(7) . . . . ? C11 C10 N2 Mn1 -174.4(2) . . . . ? C9A C10 N2 Mn1 -6.5(5) . . . . ? C9B C10 N2 Mn1 34.3(7) . . . . ? O1 Mn1 N2 C14 111.0(2) 2_765 . . . ? O1 Mn1 N2 C14 -69.0(2) . . . . ? N1 Mn1 N2 C14 -156.9(2) . . . . ? N1 Mn1 N2 C14 23.1(2) 2_765 . . . ? O1 Mn1 N2 C10 -73.6(2) 2_765 . . . ? O1 Mn1 N2 C10 106.4(2) . . . . ? N1 Mn1 N2 C10 18.5(2) . . . . ? N1 Mn1 N2 C10 -161.5(2) 2_765 . . . ? N3 Mn2 O2 C15 -160.6(2) 2_666 . . . ? N3 Mn2 O2 C15 19.4(2) . . . . ? O3 Mn2 O2 C15 113.6(2) 2_666 . . . ? O3 Mn2 O2 C15 -66.4(2) . . . . ? Mn2 O2 C15 C20 -16.1(3) . . . . ? Mn2 O2 C15 C16 164.87(17) . . . . ? O2 C15 C16 C17 179.5(2) . . . . ? C20 C15 C16 C17 0.4(4) . . . . ? O2 C15 C16 Cl3 -0.5(3) . . . . ? C20 C15 C16 Cl3 -179.57(17) . . . . ? C15 C16 C17 C18 0.2(4) . . . . ? Cl3 C16 C17 C18 -179.85(19) . . . . ? C16 C17 C18 C19 -1.1(4) . . . . ? C16 C17 C18 Cl4 -178.49(19) . . . . ? C17 C18 C19 C20 1.3(4) . . . . ? Cl4 C18 C19 C20 178.72(18) . . . . ? O2 C15 C20 C19 -179.2(2) . . . . ? C16 C15 C20 C19 -0.1(3) . . . . ? O2 C15 C20 C21 -1.5(4) . . . . ? C16 C15 C20 C21 177.6(2) . . . . ? C18 C19 C20 C15 -0.7(4) . . . . ? C18 C19 C20 C21 -178.5(2) . . . . ? C15 C20 C21 N3 8.4(4) . . . . ? C19 C20 C21 N3 -173.8(2) . . . . ? C20 C21 N3 C22 174.1(2) . . . . ? C20 C21 N3 Mn2 1.1(3) . . . . ? O2 Mn2 N3 C21 168.40(19) 2_666 . . . ? O2 Mn2 N3 C21 -11.60(19) . . . . ? O3 Mn2 N3 C21 -101.68(19) 2_666 . . . ? O3 Mn2 N3 C21 78.32(19) . . . . ? O2 Mn2 N3 C22 -4.28(17) 2_666 . . . ? O2 Mn2 N3 C22 175.72(17) . . . . ? O3 Mn2 N3 C22 85.64(17) 2_666 . . . ? O3 Mn2 N3 C22 -94.36(17) . . . . ? C21 N3 C22 C23 -91.1(3) . . . . ? Mn2 N3 C22 C23 82.2(2) . . . . ? N3 C22 C23 C24 58.8(3) . . . . ? C22 C23 C24 N4 -93.9(3) . . . . ? C22 C23 C24 C25 83.3(3) . . . . ? N4 C24 C25 C26 -1.8(5) . . . . ? C23 C24 C25 C26 -178.9(3) . . . . ? C24 C25 C26 C27 0.8(6) . . . . ? C25 C26 C27 C28 -0.3(7) . . . . ? C26 C27 C28 N4 0.8(7) . . . . ? C25 C24 N4 C28 2.2(5) . . . . ? C23 C24 N4 C28 179.5(3) . . . . ? C27 C28 N4 C24 -1.8(5) . . . . ? O2 Mn2 O3 C29 119.5(2) 2_666 . . . ? O2 Mn2 O3 C29 -60.5(2) . . . . ? N3 Mn2 O3 C29 29.1(2) 2_666 . . . ? N3 Mn2 O3 C29 -150.9(2) . . . . ? Mn2 O3 C29 C30 88.7(3) . . . . ? 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 O3 H1O3 N4 0.74(3) 2.03(3) 2.767(3) 175(3) . _diffrn_measured_fraction_theta_max 0.879 _diffrn_reflns_theta_full 24.50 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.455 _refine_diff_density_min -0.343 _refine_diff_density_rms 0.062 #===END data_mor184 _database_code_depnum_ccdc_archive 'CCDC 718586' #TrackingRef '- mor121pub.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C30 H34 Mn N4 O4, C30 H30 Mn N4 O2, 2 (Cl O4)' _chemical_formula_sum 'C60 H64 Cl2 Mn2 N8 O14' _chemical_formula_weight 1301.97 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 11.041(2) _cell_length_b 22.468(4) _cell_length_c 11.656(2) _cell_angle_alpha 90.00 _cell_angle_beta 95.026(3) _cell_angle_gamma 90.00 _cell_volume 2880.4(9) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 5535 _cell_measurement_theta_min 2.44 _cell_measurement_theta_max 29.40 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.50 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.501 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1352 _exptl_absorpt_coefficient_mu 0.607 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5892 _exptl_absorpt_correction_T_max 0.7934 _exptl_absorpt_process_details ; SADABS v.2.10 (Bruker,2003) was used for absorption correction. R(int) for selected reflections was 0.094 before and 0.040 after correction. The Ratio of minimum to maximum transmission is 0.742631. The \l/2 correction factor is 0.0015 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 23011 _diffrn_reflns_av_R_equivalents 0.0485 _diffrn_reflns_av_sigmaI/netI 0.0434 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -27 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.81 _diffrn_reflns_theta_max 26.00 _reflns_number_total 5654 _reflns_number_gt 4497 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0561P)^2^+1.2746P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5654 _refine_ls_number_parameters 401 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0599 _refine_ls_R_factor_gt 0.0442 _refine_ls_wR_factor_ref 0.1130 _refine_ls_wR_factor_gt 0.1042 _refine_ls_goodness_of_fit_ref 1.075 _refine_ls_restrained_S_all 1.075 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.5000 0.0000 0.5000 0.01463(14) Uani 1 2 d S . . O1 O 0.35325(15) 0.02749(7) 0.54930(14) 0.0172(4) Uani 1 1 d . . . C1 C 0.3004(2) 0.07899(11) 0.5214(2) 0.0159(5) Uani 1 1 d . . . C2 C 0.2271(2) 0.10559(12) 0.6011(2) 0.0196(6) Uani 1 1 d . . . C29 C 0.2164(2) 0.07561(13) 0.7141(2) 0.0246(6) Uani 1 1 d . . . H29A H 0.2919 0.0812 0.7637 0.037 Uiso 1 1 calc R . . H29B H 0.2018 0.0330 0.7015 0.037 Uiso 1 1 calc R . . H29C H 0.1484 0.0930 0.7512 0.037 Uiso 1 1 calc R . . C3 C 0.1705(2) 0.15893(12) 0.5716(2) 0.0232(6) Uani 1 1 d . . . H3 H 0.1212 0.1768 0.6249 0.028 Uiso 1 1 calc R . . C4 C 0.1822(2) 0.18752(12) 0.4684(2) 0.0238(6) Uani 1 1 d . . . H4 H 0.1429 0.2246 0.4520 0.029 Uiso 1 1 calc R . . C5 C 0.2516(2) 0.16164(11) 0.3896(2) 0.0203(6) Uani 1 1 d . . . H5 H 0.2590 0.1806 0.3177 0.024 Uiso 1 1 calc R . . C6 C 0.3115(2) 0.10746(11) 0.4146(2) 0.0172(5) Uani 1 1 d . . . C7 C 0.3756(2) 0.07941(11) 0.3277(2) 0.0175(5) Uani 1 1 d . . . H7 H 0.3618 0.0944 0.2515 0.021 Uiso 1 1 calc R . . N1 N 0.45013(19) 0.03576(9) 0.34376(17) 0.0163(4) Uani 1 1 d . . . C8 C 0.4926(2) 0.00695(11) 0.2420(2) 0.0188(5) Uani 1 1 d . . . H8A H 0.5806 -0.0017 0.2559 0.023 Uiso 1 1 calc R . . H8B H 0.4809 0.0343 0.1753 0.023 Uiso 1 1 calc R . . C9 C 0.4233(2) -0.05111(12) 0.2138(2) 0.0204(6) Uani 1 1 d . . . H9A H 0.3362 -0.0409 0.1980 0.025 Uiso 1 1 calc R . . H9B H 0.4512 -0.0669 0.1413 0.025 Uiso 1 1 calc R . . C10 C 0.4322(2) -0.10087(11) 0.3008(2) 0.0189(5) Uani 1 1 d . . . C11 C 0.4436(3) -0.15883(12) 0.2628(2) 0.0261(6) Uani 1 1 d . . . H11 H 0.4568 -0.1664 0.1847 0.031 Uiso 1 1 calc R . . C12 C 0.4356(3) -0.20547(12) 0.3384(3) 0.0294(7) Uani 1 1 d . . . H12 H 0.4433 -0.2454 0.3131 0.035 Uiso 1 1 calc R . . C13 C 0.4163(2) -0.19350(12) 0.4511(3) 0.0255(6) Uani 1 1 d . . . H13 H 0.4070 -0.2248 0.5044 0.031 Uiso 1 1 calc R . . C14 C 0.4110(2) -0.13496(12) 0.4846(2) 0.0205(6) Uani 1 1 d . . . H14 H 0.3999 -0.1267 0.5629 0.025 Uiso 1 1 calc R . . N2 N 0.42051(18) -0.08886(9) 0.41268(18) 0.0176(5) Uani 1 1 d . . . Mn2 Mn 1.0000 0.0000 1.0000 0.01348(14) Uani 1 2 d S . . O2 O 0.95604(16) 0.03016(7) 0.85206(14) 0.0179(4) Uani 1 1 d . . . C15 C 0.9267(2) 0.08426(11) 0.8149(2) 0.0153(5) Uani 1 1 d . . . C16 C 0.8930(2) 0.09240(11) 0.6957(2) 0.0175(5) Uani 1 1 d . . . C30 C 0.8871(3) 0.04095(12) 0.6144(2) 0.0238(6) Uani 1 1 d . . . H30A H 0.8476 0.0535 0.5397 0.036 Uiso 1 1 calc R . . H30B H 0.8401 0.0087 0.6455 0.036 Uiso 1 1 calc R . . H30C H 0.9696 0.0269 0.6045 0.036 Uiso 1 1 calc R . . C17 C 0.8685(2) 0.14931(12) 0.6557(2) 0.0202(6) Uani 1 1 d . . . H17 H 0.8480 0.1550 0.5756 0.024 Uiso 1 1 calc R . . C18 C 0.8726(2) 0.19906(12) 0.7282(2) 0.0235(6) Uani 1 1 d . . . H18 H 0.8542 0.2376 0.6980 0.028 Uiso 1 1 calc R . . C19 C 0.9036(2) 0.19107(11) 0.8433(2) 0.0215(6) Uani 1 1 d . . . H19 H 0.9066 0.2244 0.8935 0.026 Uiso 1 1 calc R . . C20 C 0.9312(2) 0.13421(11) 0.8883(2) 0.0176(5) Uani 1 1 d . . . C21 C 0.9737(2) 0.13045(11) 1.0074(2) 0.0160(5) Uani 1 1 d . . . H21 H 0.9774 0.1670 1.0486 0.019 Uiso 1 1 calc R . . N3 N 1.00750(18) 0.08378(9) 1.06628(17) 0.0147(4) Uani 1 1 d . . . C22 C 1.0484(2) 0.09412(11) 1.1883(2) 0.0167(5) Uani 1 1 d . . . H22A H 1.0756 0.1359 1.1984 0.020 Uiso 1 1 calc R . . H22B H 1.1189 0.0681 1.2107 0.020 Uiso 1 1 calc R . . C23 C 0.9477(2) 0.08176(11) 1.2676(2) 0.0191(5) Uani 1 1 d . . . H23A H 0.9236 0.0394 1.2602 0.023 Uiso 1 1 calc R . . H23B H 0.9800 0.0887 1.3484 0.023 Uiso 1 1 calc R . . C24 C 0.8380(2) 0.11976(11) 1.2411(2) 0.0173(5) Uani 1 1 d . . . C25 C 0.8270(2) 0.17561(11) 1.2910(2) 0.0212(6) Uani 1 1 d . . . H25 H 0.8890 0.1900 1.3457 0.025 Uiso 1 1 calc R . . C26 C 0.7250(3) 0.20994(12) 1.2604(2) 0.0257(6) Uani 1 1 d . . . H26 H 0.7160 0.2481 1.2937 0.031 Uiso 1 1 calc R . . C27 C 0.6367(2) 0.18769(12) 1.1805(2) 0.0253(6) Uani 1 1 d . . . H27 H 0.5656 0.2101 1.1578 0.030 Uiso 1 1 calc R . . C28 C 0.6543(2) 0.13214(12) 1.1346(2) 0.0223(6) Uani 1 1 d . . . H28 H 0.5936 0.1170 1.0795 0.027 Uiso 1 1 calc R . . N4 N 0.7521(2) 0.09833(9) 1.16345(19) 0.0199(5) Uani 1 1 d . . . O3 O 0.80067(17) 0.00001(9) 1.02730(17) 0.0201(4) Uani 1 1 d . . . H1O3 H 0.778(3) 0.0282(13) 1.068(2) 0.019(8) Uiso 1 1 d . . . H2O3 H 0.767(3) -0.0292(14) 1.035(2) 0.020(8) Uiso 1 1 d . . . Cl Cl 0.31760(6) 0.16196(3) 0.99784(5) 0.01770(15) Uani 1 1 d . . . O4 O 0.36479(17) 0.10269(8) 0.98295(17) 0.0272(4) Uani 1 1 d . . . O5 O 0.40725(17) 0.20474(8) 0.97286(17) 0.0287(5) Uani 1 1 d . . . O6 O 0.20962(17) 0.16997(9) 0.92309(17) 0.0287(5) Uani 1 1 d . . . O7 O 0.2892(2) 0.16824(9) 1.11446(17) 0.0359(5) 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 0.0153(3) 0.0167(3) 0.0122(3) 0.0014(2) 0.0032(2) -0.0003(2) O1 0.0166(9) 0.0186(9) 0.0170(9) 0.0021(7) 0.0040(7) -0.0005(7) C1 0.0124(12) 0.0174(12) 0.0176(13) -0.0020(10) 0.0001(10) -0.0045(10) C2 0.0136(13) 0.0235(14) 0.0219(14) -0.0028(11) 0.0031(10) -0.0067(11) C29 0.0187(13) 0.0346(16) 0.0219(14) -0.0023(12) 0.0097(11) 0.0001(12) C3 0.0152(13) 0.0267(15) 0.0279(15) -0.0099(12) 0.0035(11) -0.0021(11) C4 0.0219(14) 0.0171(13) 0.0318(16) -0.0030(11) -0.0014(12) 0.0022(11) C5 0.0191(13) 0.0206(13) 0.0210(14) 0.0004(11) 0.0000(11) -0.0027(11) C6 0.0131(12) 0.0193(13) 0.0189(13) -0.0032(10) -0.0008(10) -0.0040(10) C7 0.0183(13) 0.0186(13) 0.0155(13) 0.0042(10) 0.0000(10) -0.0047(10) N1 0.0171(11) 0.0182(11) 0.0140(11) 0.0016(8) 0.0037(8) -0.0034(9) C8 0.0224(14) 0.0200(13) 0.0147(13) 0.0024(10) 0.0054(10) -0.0009(11) C9 0.0221(14) 0.0268(14) 0.0126(13) -0.0031(11) 0.0026(10) -0.0018(11) C10 0.0118(12) 0.0216(13) 0.0235(14) -0.0023(11) 0.0019(10) -0.0014(10) C11 0.0265(15) 0.0255(15) 0.0271(15) -0.0050(12) 0.0063(12) 0.0006(12) C12 0.0299(16) 0.0196(14) 0.0386(18) -0.0052(12) 0.0031(13) 0.0041(12) C13 0.0203(14) 0.0219(14) 0.0338(16) 0.0073(12) -0.0007(12) -0.0010(11) C14 0.0126(12) 0.0262(14) 0.0225(14) 0.0027(11) 0.0003(10) -0.0026(11) N2 0.0136(11) 0.0206(11) 0.0186(11) 0.0015(9) 0.0021(9) -0.0017(8) Mn2 0.0154(3) 0.0122(3) 0.0129(3) 0.0007(2) 0.0012(2) -0.0003(2) O2 0.0227(10) 0.0158(9) 0.0154(9) 0.0017(7) 0.0015(7) 0.0025(7) C15 0.0086(11) 0.0179(12) 0.0199(13) 0.0029(10) 0.0041(10) -0.0015(9) C16 0.0109(12) 0.0229(13) 0.0189(13) 0.0003(10) 0.0031(10) 0.0002(10) C30 0.0250(15) 0.0283(15) 0.0179(14) 0.0028(11) 0.0007(11) 0.0021(12) C17 0.0116(12) 0.0283(14) 0.0202(14) 0.0063(11) -0.0006(10) 0.0012(11) C18 0.0183(14) 0.0177(13) 0.0340(16) 0.0085(11) -0.0007(12) 0.0021(11) C19 0.0180(13) 0.0159(13) 0.0304(15) 0.0023(11) 0.0013(11) 0.0001(10) C20 0.0104(12) 0.0190(13) 0.0236(14) 0.0030(11) 0.0020(10) -0.0016(10) C21 0.0109(12) 0.0156(12) 0.0221(14) -0.0022(10) 0.0045(10) -0.0031(10) N3 0.0129(10) 0.0154(10) 0.0162(11) 0.0002(8) 0.0029(8) -0.0006(8) C22 0.0157(12) 0.0164(12) 0.0174(13) -0.0024(10) -0.0015(10) -0.0030(10) C23 0.0247(14) 0.0172(13) 0.0154(13) -0.0010(10) 0.0022(11) -0.0010(11) C24 0.0203(13) 0.0184(13) 0.0139(13) 0.0006(10) 0.0059(10) -0.0010(10) C25 0.0260(14) 0.0213(14) 0.0167(13) -0.0035(10) 0.0035(11) -0.0042(11) C26 0.0337(16) 0.0200(14) 0.0247(15) -0.0029(11) 0.0097(12) 0.0038(12) C27 0.0193(14) 0.0264(15) 0.0309(16) 0.0003(12) 0.0053(12) 0.0054(11) C28 0.0187(13) 0.0235(14) 0.0248(15) -0.0005(11) 0.0021(11) -0.0030(11) N4 0.0196(11) 0.0179(11) 0.0226(12) -0.0017(9) 0.0036(9) -0.0019(9) O3 0.0196(10) 0.0149(10) 0.0268(11) -0.0047(8) 0.0069(8) -0.0028(8) Cl 0.0202(3) 0.0164(3) 0.0167(3) 0.0002(2) 0.0032(2) -0.0019(2) O4 0.0239(10) 0.0209(10) 0.0362(12) -0.0052(8) 0.0001(9) 0.0026(8) O5 0.0251(10) 0.0274(10) 0.0338(11) 0.0055(9) 0.0033(9) -0.0096(8) O6 0.0206(10) 0.0285(10) 0.0358(12) 0.0061(9) -0.0042(9) 0.0009(8) O7 0.0602(15) 0.0279(11) 0.0212(11) -0.0034(8) 0.0131(10) -0.0075(10) _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 1.8708(17) 3_656 ? Mn1 O1 1.8709(17) . ? Mn1 N1 2.022(2) 3_656 ? Mn1 N1 2.022(2) . ? Mn1 N2 2.374(2) . ? Mn1 N2 2.374(2) 3_656 ? O1 C1 1.323(3) . ? C1 C6 1.415(4) . ? C1 C2 1.417(4) . ? C2 C3 1.381(4) . ? C2 C29 1.493(4) . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C3 C4 1.380(4) . ? C3 H3 0.9500 . ? C4 C5 1.375(4) . ? C4 H4 0.9500 . ? C5 C6 1.404(4) . ? C5 H5 0.9500 . ? C6 C7 1.432(4) . ? C7 N1 1.283(3) . ? C7 H7 0.9500 . ? N1 C8 1.464(3) . ? C8 C9 1.533(3) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 C10 1.507(4) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 N2 1.349(3) . ? C10 C11 1.385(4) . ? C11 C12 1.378(4) . ? C11 H11 0.9500 . ? C12 C13 1.375(4) . ? C12 H12 0.9500 . ? C13 C14 1.375(4) . ? C13 H13 0.9500 . ? C14 N2 1.342(3) . ? C14 H14 0.9500 . ? Mn2 O2 1.8765(17) 3_757 ? Mn2 O2 1.8765(17) . ? Mn2 N3 2.034(2) 3_757 ? Mn2 N3 2.034(2) . ? Mn2 O3 2.251(2) 3_757 ? Mn2 O3 2.251(2) . ? O2 C15 1.321(3) . ? C15 C20 1.409(4) . ? C15 C16 1.418(4) . ? C16 C17 1.380(4) . ? C16 C30 1.493(4) . ? C30 H30A 0.9800 . ? C30 H30B 0.9800 . ? C30 H30C 0.9800 . ? C17 C18 1.399(4) . ? C17 H17 0.9500 . ? C18 C19 1.367(4) . ? C18 H18 0.9500 . ? C19 C20 1.404(3) . ? C19 H19 0.9500 . ? C20 C21 1.429(4) . ? C21 N3 1.290(3) . ? C21 H21 0.9500 . ? N3 C22 1.472(3) . ? C22 C23 1.533(3) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 C24 1.492(4) . ? C23 H23A 0.9900 . ? C23 H23B 0.9900 . ? C24 N4 1.342(3) . ? C24 C25 1.393(3) . ? C25 C26 1.386(4) . ? C25 H25 0.9500 . ? C26 C27 1.382(4) . ? C26 H26 0.9500 . ? C27 C28 1.378(4) . ? C27 H27 0.9500 . ? C28 N4 1.339(3) . ? C28 H28 0.9500 . ? O3 H1O3 0.85(3) . ? O3 H2O3 0.76(3) . ? Cl O6 1.4252(19) . ? Cl O5 1.4279(19) . ? Cl O7 1.429(2) . ? Cl O4 1.4459(19) . ? 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 180.0 3_656 . ? O1 Mn1 N1 88.31(8) 3_656 3_656 ? O1 Mn1 N1 91.69(8) . 3_656 ? O1 Mn1 N1 91.69(8) 3_656 . ? O1 Mn1 N1 88.31(8) . . ? N1 Mn1 N1 180.0 3_656 . ? O1 Mn1 N2 83.59(7) 3_656 . ? O1 Mn1 N2 96.41(7) . . ? N1 Mn1 N2 96.50(8) 3_656 . ? N1 Mn1 N2 83.50(8) . . ? O1 Mn1 N2 96.42(7) 3_656 3_656 ? O1 Mn1 N2 83.59(7) . 3_656 ? N1 Mn1 N2 83.50(8) 3_656 3_656 ? N1 Mn1 N2 96.50(8) . 3_656 ? N2 Mn1 N2 180.0 . 3_656 ? C1 O1 Mn1 126.02(15) . . ? O1 C1 C6 122.8(2) . . ? O1 C1 C2 118.2(2) . . ? C6 C1 C2 119.0(2) . . ? C3 C2 C1 118.4(2) . . ? C3 C2 C29 122.8(2) . . ? C1 C2 C29 118.8(2) . . ? C2 C29 H29A 109.5 . . ? C2 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C2 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C4 C3 C2 123.1(2) . . ? C4 C3 H3 118.5 . . ? C2 C3 H3 118.5 . . ? C5 C4 C3 119.0(2) . . ? C5 C4 H4 120.5 . . ? C3 C4 H4 120.5 . . ? C4 C5 C6 120.6(2) . . ? C4 C5 H5 119.7 . . ? C6 C5 H5 119.7 . . ? C5 C6 C1 119.9(2) . . ? C5 C6 C7 119.2(2) . . ? C1 C6 C7 120.7(2) . . ? N1 C7 C6 125.7(2) . . ? N1 C7 H7 117.1 . . ? C6 C7 H7 117.1 . . ? C7 N1 C8 117.8(2) . . ? C7 N1 Mn1 123.75(17) . . ? C8 N1 Mn1 118.22(16) . . ? N1 C8 C9 111.1(2) . . ? N1 C8 H8A 109.4 . . ? C9 C8 H8A 109.4 . . ? N1 C8 H8B 109.4 . . ? C9 C8 H8B 109.4 . . ? H8A C8 H8B 108.0 . . ? C10 C9 C8 119.0(2) . . ? C10 C9 H9A 107.6 . . ? C8 C9 H9A 107.6 . . ? C10 C9 H9B 107.6 . . ? C8 C9 H9B 107.6 . . ? H9A C9 H9B 107.0 . . ? N2 C10 C11 121.1(2) . . ? N2 C10 C9 119.7(2) . . ? C11 C10 C9 119.0(2) . . ? C12 C11 C10 119.8(3) . . ? C12 C11 H11 120.1 . . ? C10 C11 H11 120.1 . . ? C13 C12 C11 119.1(3) . . ? C13 C12 H12 120.4 . . ? C11 C12 H12 120.4 . . ? C14 C13 C12 118.2(3) . . ? C14 C13 H13 120.9 . . ? C12 C13 H13 120.9 . . ? N2 C14 C13 123.6(3) . . ? N2 C14 H14 118.2 . . ? C13 C14 H14 118.2 . . ? C14 N2 C10 117.9(2) . . ? C14 N2 Mn1 115.31(17) . . ? C10 N2 Mn1 121.30(16) . . ? O2 Mn2 O2 180.0 3_757 . ? O2 Mn2 N3 90.77(8) 3_757 3_757 ? O2 Mn2 N3 89.23(8) . 3_757 ? O2 Mn2 N3 89.23(8) 3_757 . ? O2 Mn2 N3 90.77(8) . . ? N3 Mn2 N3 180.0 3_757 . ? O2 Mn2 O3 87.27(7) 3_757 3_757 ? O2 Mn2 O3 92.73(7) . 3_757 ? N3 Mn2 O3 87.36(8) 3_757 3_757 ? N3 Mn2 O3 92.64(8) . 3_757 ? O2 Mn2 O3 92.72(7) 3_757 . ? O2 Mn2 O3 87.27(7) . . ? N3 Mn2 O3 92.64(8) 3_757 . ? N3 Mn2 O3 87.36(8) . . ? O3 Mn2 O3 180.0 3_757 . ? C15 O2 Mn2 132.05(16) . . ? O2 C15 C20 122.6(2) . . ? O2 C15 C16 118.4(2) . . ? C20 C15 C16 119.0(2) . . ? C17 C16 C15 118.5(2) . . ? C17 C16 C30 120.4(2) . . ? C15 C16 C30 121.0(2) . . ? C16 C30 H30A 109.5 . . ? C16 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? C16 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? C16 C17 C18 122.8(2) . . ? C16 C17 H17 118.6 . . ? C18 C17 H17 118.6 . . ? C19 C18 C17 118.7(2) . . ? C19 C18 H18 120.7 . . ? C17 C18 H18 120.7 . . ? C18 C19 C20 120.9(2) . . ? C18 C19 H19 119.5 . . ? C20 C19 H19 119.5 . . ? C19 C20 C15 120.2(2) . . ? C19 C20 C21 117.3(2) . . ? C15 C20 C21 122.3(2) . . ? N3 C21 C20 128.3(2) . . ? N3 C21 H21 115.8 . . ? C20 C21 H21 115.8 . . ? C21 N3 C22 115.8(2) . . ? C21 N3 Mn2 123.36(17) . . ? C22 N3 Mn2 120.78(15) . . ? N3 C22 C23 112.1(2) . . ? N3 C22 H22A 109.2 . . ? C23 C22 H22A 109.2 . . ? N3 C22 H22B 109.2 . . ? C23 C22 H22B 109.2 . . ? H22A C22 H22B 107.9 . . ? C24 C23 C22 113.0(2) . . ? C24 C23 H23A 109.0 . . ? C22 C23 H23A 109.0 . . ? C24 C23 H23B 109.0 . . ? C22 C23 H23B 109.0 . . ? H23A C23 H23B 107.8 . . ? N4 C24 C25 121.5(2) . . ? N4 C24 C23 116.6(2) . . ? C25 C24 C23 121.9(2) . . ? C26 C25 C24 119.5(2) . . ? C26 C25 H25 120.3 . . ? C24 C25 H25 120.3 . . ? C27 C26 C25 118.8(3) . . ? C27 C26 H26 120.6 . . ? C25 C26 H26 120.6 . . ? C28 C27 C26 118.3(3) . . ? C28 C27 H27 120.9 . . ? C26 C27 H27 120.9 . . ? N4 C28 C27 123.7(3) . . ? N4 C28 H28 118.2 . . ? C27 C28 H28 118.2 . . ? C28 N4 C24 118.2(2) . . ? Mn2 O3 H1O3 115.0(19) . . ? Mn2 O3 H2O3 121(2) . . ? H1O3 O3 H2O3 114(3) . . ? O6 Cl O5 110.37(12) . . ? O6 Cl O7 109.12(13) . . ? O5 Cl O7 109.97(12) . . ? O6 Cl O4 109.50(12) . . ? O5 Cl O4 109.39(12) . . ? O7 Cl O4 108.47(12) . . ? 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 N1 Mn1 O1 C1 141.27(19) 3_656 . . . ? N1 Mn1 O1 C1 -38.73(19) . . . . ? N2 Mn1 O1 C1 -122.00(18) . . . . ? N2 Mn1 O1 C1 58.00(18) 3_656 . . . ? Mn1 O1 C1 C6 30.9(3) . . . . ? Mn1 O1 C1 C2 -150.88(18) . . . . ? O1 C1 C2 C3 -179.1(2) . . . . ? C6 C1 C2 C3 -0.8(3) . . . . ? O1 C1 C2 C29 2.2(3) . . . . ? C6 C1 C2 C29 -179.5(2) . . . . ? C1 C2 C3 C4 -0.1(4) . . . . ? C29 C2 C3 C4 178.5(3) . . . . ? C2 C3 C4 C5 1.1(4) . . . . ? C3 C4 C5 C6 -1.2(4) . . . . ? C4 C5 C6 C1 0.2(4) . . . . ? C4 C5 C6 C7 175.4(2) . . . . ? O1 C1 C6 C5 179.0(2) . . . . ? C2 C1 C6 C5 0.8(3) . . . . ? O1 C1 C6 C7 3.9(4) . . . . ? C2 C1 C6 C7 -174.3(2) . . . . ? C5 C6 C7 N1 167.8(2) . . . . ? C1 C6 C7 N1 -17.1(4) . . . . ? C6 C7 N1 C8 170.7(2) . . . . ? C6 C7 N1 Mn1 -3.5(4) . . . . ? O1 Mn1 N1 C7 -154.9(2) 3_656 . . . ? O1 Mn1 N1 C7 25.1(2) . . . . ? N2 Mn1 N1 C7 121.8(2) . . . . ? N2 Mn1 N1 C7 -58.2(2) 3_656 . . . ? O1 Mn1 N1 C8 30.86(17) 3_656 . . . ? O1 Mn1 N1 C8 -149.13(17) . . . . ? N2 Mn1 N1 C8 -52.48(17) . . . . ? N2 Mn1 N1 C8 127.52(17) 3_656 . . . ? C7 N1 C8 C9 -100.5(3) . . . . ? Mn1 N1 C8 C9 74.1(2) . . . . ? N1 C8 C9 C10 -61.8(3) . . . . ? C8 C9 C10 N2 45.8(3) . . . . ? C8 C9 C10 C11 -138.9(3) . . . . ? N2 C10 C11 C12 3.9(4) . . . . ? C9 C10 C11 C12 -171.4(2) . . . . ? C10 C11 C12 C13 0.0(4) . . . . ? C11 C12 C13 C14 -2.7(4) . . . . ? C12 C13 C14 N2 1.7(4) . . . . ? C13 C14 N2 C10 2.1(4) . . . . ? C13 C14 N2 Mn1 -152.2(2) . . . . ? C11 C10 N2 C14 -4.9(4) . . . . ? C9 C10 N2 C14 170.3(2) . . . . ? C11 C10 N2 Mn1 147.8(2) . . . . ? C9 C10 N2 Mn1 -36.9(3) . . . . ? O1 Mn1 N2 C14 96.53(18) 3_656 . . . ? O1 Mn1 N2 C14 -83.47(18) . . . . ? N1 Mn1 N2 C14 8.97(18) 3_656 . . . ? N1 Mn1 N2 C14 -171.03(18) . . . . ? O1 Mn1 N2 C10 -56.87(19) 3_656 . . . ? O1 Mn1 N2 C10 123.13(19) . . . . ? N1 Mn1 N2 C10 -144.43(19) 3_656 . . . ? N1 Mn1 N2 C10 35.58(19) . . . . ? N3 Mn2 O2 C15 172.1(2) 3_757 . . . ? N3 Mn2 O2 C15 -7.9(2) . . . . ? O3 Mn2 O2 C15 -100.6(2) 3_757 . . . ? O3 Mn2 O2 C15 79.4(2) . . . . ? Mn2 O2 C15 C20 4.3(3) . . . . ? Mn2 O2 C15 C16 -177.71(16) . . . . ? O2 C15 C16 C17 -176.7(2) . . . . ? C20 C15 C16 C17 1.4(3) . . . . ? O2 C15 C16 C30 1.8(3) . . . . ? C20 C15 C16 C30 179.9(2) . . . . ? C15 C16 C17 C18 -1.6(4) . . . . ? C30 C16 C17 C18 179.9(2) . . . . ? C16 C17 C18 C19 0.8(4) . . . . ? C17 C18 C19 C20 0.2(4) . . . . ? C18 C19 C20 C15 -0.3(4) . . . . ? C18 C19 C20 C21 174.3(2) . . . . ? O2 C15 C20 C19 177.5(2) . . . . ? C16 C15 C20 C19 -0.5(4) . . . . ? O2 C15 C20 C21 3.2(4) . . . . ? C16 C15 C20 C21 -174.9(2) . . . . ? C19 C20 C21 N3 -177.9(2) . . . . ? C15 C20 C21 N3 -3.4(4) . . . . ? C20 C21 N3 C22 179.3(2) . . . . ? C20 C21 N3 Mn2 -3.1(4) . . . . ? O2 Mn2 N3 C21 -173.0(2) 3_757 . . . ? O2 Mn2 N3 C21 6.9(2) . . . . ? O3 Mn2 N3 C21 99.72(19) 3_757 . . . ? O3 Mn2 N3 C21 -80.29(19) . . . . ? O2 Mn2 N3 C22 4.48(18) 3_757 . . . ? O2 Mn2 N3 C22 -175.52(18) . . . . ? O3 Mn2 N3 C22 -82.75(18) 3_757 . . . ? O3 Mn2 N3 C22 97.24(18) . . . . ? C21 N3 C22 C23 97.7(2) . . . . ? Mn2 N3 C22 C23 -80.0(2) . . . . ? N3 C22 C23 C24 -59.6(3) . . . . ? C22 C23 C24 N4 89.4(3) . . . . ? C22 C23 C24 C25 -88.3(3) . . . . ? N4 C24 C25 C26 0.2(4) . . . . ? C23 C24 C25 C26 177.8(2) . . . . ? C24 C25 C26 C27 -0.1(4) . . . . ? C25 C26 C27 C28 -0.1(4) . . . . ? C26 C27 C28 N4 0.3(4) . . . . ? C27 C28 N4 C24 -0.2(4) . . . . ? C25 C24 N4 C28 0.0(4) . . . . ? C23 C24 N4 C28 -177.8(2) . . . . ? 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 O3 H1O3 N4 0.85(3) 1.96(3) 2.799(3) 171(3) . O3 H2O3 O4 0.76(3) 2.20(3) 2.939(3) 164(3) 3_657 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.641 _refine_diff_density_min -0.500 _refine_diff_density_rms 0.084