# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Garcia-Espana, Enrique' 'Clares, Ma Paz' 'Blasco, Salvador' 'Inclan, Mario' 'Verdejo, Begona' 'del Castillo, Lucas' 'Soriano, Conxa' 'Domenech, Antonio' 'Latorre, Julio' _publ_contact_author_name 'Garcia-Espana, Enrique' _publ_contact_author_email enrique.garcia-es@uv.es _publ_section_title ; Manganese(II) complexes of scorpiand-like azamacrocycles as MnSOD mimics ; # Attachment '- esi.cif' data_mnpytren4q _database_code_depnum_ccdc_archive 'CCDC 810034' #TrackingRef '- esi.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common '[Mn(pytren-4Q)](ClO4)2(H2O)' _chemical_melting_point ? _chemical_formula_moiety 'C23 H32 Mn N6 O, 2(Cl O4)' _chemical_formula_sum 'C23 H32 Cl2 Mn N6 O9' _chemical_formula_weight 662.39 _chemical_absolute_configuration ad 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' 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' 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21' _symmetry_space_group_name_Hall 'P 2yb' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 8.7809(4) _cell_length_b 15.2321(6) _cell_length_c 10.2323(5) _cell_angle_alpha 90.00 _cell_angle_beta 94.030(5) _cell_angle_gamma 90.00 _cell_volume 1365.20(11) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 1292 _cell_measurement_theta_min 3.1629 _cell_measurement_theta_max 29.0457 _exptl_crystal_description leaf _exptl_crystal_colour colorless _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.611 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 686 _exptl_absorpt_coefficient_mu 0.743 _exptl_absorpt_correction_T_min 0.9321 _exptl_absorpt_correction_T_max 0.9853 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'SuperNova (Mo) X-ray Source' _diffrn_radiation_monochromator mirror _diffrn_measurement_device_type 'SuperNova, Single source at offset), Sapphire3' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.0267 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5548 _diffrn_reflns_av_R_equivalents 0.0456 _diffrn_reflns_av_sigmaI/netI 0.1165 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.17 _diffrn_reflns_theta_max 27.50 _diffrn_measurement_details ; #__ type_ start__ end____ width___ exp.time_ 1 omega -88.00 12.00 1.0000 300.0000 omega____ theta____ kappa____ phi______ frames - -17.7276 -77.0000 -120.0000 100 #__ type_ start__ end____ width___ exp.time_ 2 omega -52.00 48.00 1.0000 300.0000 omega____ theta____ kappa____ phi______ frames - 18.3526 -77.0000 90.0000 100 ; _reflns_number_total 4042 _reflns_number_gt 2567 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0633P)^2^+1.6398P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.00(5) _refine_ls_number_reflns 4042 _refine_ls_number_parameters 371 _refine_ls_number_restraints 13 _refine_ls_R_factor_all 0.1278 _refine_ls_R_factor_gt 0.0746 _refine_ls_wR_factor_ref 0.1806 _refine_ls_wR_factor_gt 0.1488 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.038 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.26082(15) 0.10092(10) 0.75548(14) 0.0311(4) Uani 1 1 d . . . O1 O 0.2746(11) -0.0278(5) 0.6890(7) 0.074(3) Uani 1 1 d D . . H1C H 0.2282 -0.0612 0.7381 0.089 Uiso 1 1 calc RD . . H1D H 0.3564 -0.0479 0.6614 0.089 Uiso 1 1 d RD . . N1 N 0.2982(9) 0.1583(5) 0.5610(8) 0.033(2) Uani 1 1 d . . . N2 N 0.5030(10) 0.1625(7) 0.7707(10) 0.056(3) Uani 1 1 d . . . H2 H 0.5662 0.1260 0.8233 0.067 Uiso 1 1 calc R . . N3 N 0.2234(10) 0.2304(5) 0.8577(9) 0.041(2) Uani 1 1 d . . . N4 N 0.0230(9) 0.1460(6) 0.6612(10) 0.047(2) Uani 1 1 d . . . H4 H -0.0509 0.1063 0.6844 0.057 Uiso 1 1 calc R . . N5 N 0.2331(8) 0.0528(5) 0.9639(7) 0.0307(19) Uani 1 1 d . . . H5 H 0.1658 0.0056 0.9588 0.037 Uiso 1 1 calc R . . C19 C 0.6107(15) -0.0463(8) 1.4810(11) 0.058(3) Uani 1 1 d . . . H19 H 0.6012 -0.0661 1.5681 0.070 Uiso 1 1 calc R . . C1 C 0.5627(12) 0.1648(7) 0.6398(12) 0.047(3) Uani 1 1 d . . . H1A H 0.6076 0.1070 0.6206 0.057 Uiso 1 1 calc R . . H1B H 0.6445 0.2094 0.6386 0.057 Uiso 1 1 calc R . . C2 C 0.4982(19) 0.2429(13) 0.8319(14) 0.099(6) Uani 1 1 d U . . H2A H 0.5678 0.2831 0.7888 0.119 Uiso 1 1 calc R . . H2B H 0.5398 0.2354 0.9237 0.119 Uiso 1 1 calc R . . C3 C 0.355(2) 0.2842(9) 0.8338(17) 0.100(5) Uani 1 1 d U . . H3A H 0.3342 0.3140 0.7485 0.120 Uiso 1 1 calc R . . H3B H 0.3639 0.3305 0.9019 0.120 Uiso 1 1 calc R . . C4 C 0.088(2) 0.2732(10) 0.7933(17) 0.123(8) Uani 1 1 d . . . H4A H 0.0317 0.2998 0.8637 0.148 Uiso 1 1 calc R . . H4B H 0.1262 0.3225 0.7415 0.148 Uiso 1 1 calc R . . C5 C -0.0092(18) 0.2324(10) 0.719(2) 0.134(9) Uani 1 1 d U . . H5A H -0.0383 0.2722 0.6445 0.160 Uiso 1 1 calc R . . H5B H -0.1012 0.2250 0.7681 0.160 Uiso 1 1 calc R . . C6 C 0.0307(14) 0.1437(9) 0.5192(14) 0.067(4) Uani 1 1 d . . . H6A H -0.0530 0.1799 0.4779 0.081 Uiso 1 1 calc R . . H6B H 0.0154 0.0826 0.4881 0.081 Uiso 1 1 calc R . . C7 C 0.1792(13) 0.1768(7) 0.4770(11) 0.051(3) Uani 1 1 d . . . C8 C 0.1977(18) 0.2268(9) 0.3649(13) 0.074(4) Uani 1 1 d . . . H8 H 0.1117 0.2438 0.3090 0.088 Uiso 1 1 calc R . . C9 C 0.3417(19) 0.2511(9) 0.3371(13) 0.074(4) Uani 1 1 d . . . H9 H 0.3571 0.2800 0.2568 0.088 Uiso 1 1 calc R . . C10 C 0.4645(16) 0.2341(7) 0.4241(11) 0.056(4) Uani 1 1 d . . . H10 H 0.5639 0.2543 0.4082 0.067 Uiso 1 1 calc R . . C11 C 0.4386(12) 0.1862(6) 0.5363(9) 0.039(3) Uani 1 1 d . . . C12 C 0.2191(16) 0.2121(8) 0.9949(11) 0.059(3) Uani 1 1 d . . . H12A H 0.1568 0.2579 1.0343 0.071 Uiso 1 1 calc R . . H12B H 0.3242 0.2168 1.0362 0.071 Uiso 1 1 calc R . . C13 C 0.1574(14) 0.1257(7) 1.0273(11) 0.053(3) Uani 1 1 d . . . H13A H 0.1689 0.1174 1.1234 0.064 Uiso 1 1 calc R . . H13B H 0.0470 0.1243 1.0002 0.064 Uiso 1 1 calc R . . C14 C 0.3758(10) 0.0227(7) 1.0316(9) 0.037(2) Uani 1 1 d . . . H14A H 0.4511 0.0711 1.0316 0.045 Uiso 1 1 calc R . . H14B H 0.4162 -0.0265 0.9809 0.045 Uiso 1 1 calc R . . C15 C 0.3638(12) -0.0077(6) 1.1720(9) 0.035(2) Uani 1 1 d . . . C16 C 0.2302(12) -0.0370(6) 1.2174(9) 0.037(2) Uani 1 1 d . . . H16 H 0.1415 -0.0415 1.1591 0.044 Uiso 1 1 calc R . . C17 C 0.2229(15) -0.0606(7) 1.3509(11) 0.044(3) Uani 1 1 d . . . H17 H 0.1264 -0.0756 1.3813 0.053 Uiso 1 1 calc R . . N6 N 0.3422(11) -0.0629(5) 1.4337(8) 0.041(2) Uani 1 1 d . . . C18 C 0.4789(13) -0.0397(6) 1.3919(9) 0.038(3) Uani 1 1 d . . . C20 C 0.7471(15) -0.0247(7) 1.4417(11) 0.057(3) Uani 1 1 d . . . H20 H 0.8341 -0.0287 1.5021 0.068 Uiso 1 1 calc R . . C21 C 0.7658(14) 0.0040(7) 1.3122(12) 0.056(3) Uani 1 1 d . . . H21 H 0.8647 0.0180 1.2863 0.067 Uiso 1 1 calc R . . C22 C 0.6437(12) 0.0114(6) 1.2257(9) 0.040(3) Uani 1 1 d . . . H22 H 0.6566 0.0316 1.1394 0.048 Uiso 1 1 calc R . . C23 C 0.4973(12) -0.0105(6) 1.2623(9) 0.037(2) Uani 1 1 d . . . Cl1 Cl 0.1850(3) 0.47445(17) 0.1299(2) 0.0409(6) Uani 1 1 d . . . O11 O 0.1155(13) 0.4500(9) 0.2442(10) 0.116(4) Uani 1 1 d . . . O12 O 0.3248(10) 0.4321(7) 0.1240(9) 0.088(3) Uani 1 1 d . . . O13 O 0.2040(11) 0.5655(6) 0.1369(13) 0.106(4) Uani 1 1 d . . . O14 O 0.0902(9) 0.4557(6) 0.0157(7) 0.063(2) Uani 1 1 d . . . Cl2 Cl 0.7608(3) 0.26350(18) 0.1566(3) 0.0554(8) Uani 1 1 d . . . O21 O 0.6211(10) 0.2192(8) 0.1422(10) 0.103(4) Uani 1 1 d . . . O22 O 0.7975(11) 0.2847(6) 0.2996(10) 0.089(3) Uani 1 1 d . . . O23 O 0.8719(13) 0.2061(8) 0.1302(14) 0.128(5) Uani 1 1 d . . . O24 O 0.7595(17) 0.3389(7) 0.0884(14) 0.147(6) 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 0.0348(8) 0.0314(7) 0.0265(7) 0.0064(7) -0.0006(6) 0.0021(7) O1 0.157(9) 0.026(4) 0.042(5) 0.012(4) 0.036(6) 0.012(5) N1 0.042(5) 0.028(4) 0.026(4) 0.009(4) -0.013(4) -0.018(4) N2 0.035(5) 0.085(8) 0.047(6) 0.036(6) -0.012(5) -0.021(5) N3 0.047(5) 0.027(4) 0.048(6) 0.004(4) -0.008(4) 0.007(4) N4 0.030(4) 0.040(5) 0.069(7) -0.013(5) -0.015(5) 0.001(4) N5 0.024(4) 0.039(5) 0.027(5) -0.001(4) -0.005(4) -0.002(4) C19 0.091(10) 0.051(8) 0.029(6) 0.008(6) -0.014(6) -0.021(7) C1 0.033(6) 0.044(6) 0.066(8) 0.006(6) 0.019(6) 0.002(5) C2 0.101(10) 0.150(18) 0.048(8) -0.029(10) 0.015(9) -0.097(10) C3 0.167(15) 0.048(9) 0.083(11) -0.010(8) 0.001(13) -0.037(11) C4 0.154(16) 0.083(11) 0.117(14) -0.050(10) -0.100(12) 0.094(12) C5 0.080(11) 0.065(10) 0.24(2) -0.083(13) -0.089(13) 0.042(8) C6 0.055(8) 0.065(8) 0.077(10) 0.011(8) -0.024(7) -0.014(7) C7 0.062(7) 0.044(7) 0.044(7) 0.010(6) -0.026(6) -0.026(6) C8 0.098(11) 0.074(10) 0.045(8) 0.007(7) -0.027(8) -0.027(9) C9 0.121(12) 0.063(9) 0.034(7) 0.006(7) -0.011(8) -0.039(9) C10 0.093(10) 0.037(6) 0.039(7) -0.012(6) 0.012(7) -0.035(7) C11 0.062(7) 0.031(5) 0.022(5) -0.006(4) 0.000(5) -0.012(6) C12 0.100(10) 0.041(7) 0.037(7) -0.005(6) 0.013(7) 0.007(7) C13 0.067(7) 0.057(8) 0.038(6) 0.010(6) 0.019(6) 0.020(6) C14 0.032(5) 0.051(7) 0.028(5) -0.006(5) -0.003(4) 0.005(5) C15 0.062(7) 0.022(5) 0.021(5) 0.008(4) 0.001(5) 0.011(5) C16 0.057(7) 0.027(5) 0.025(5) 0.003(4) -0.006(5) 0.002(5) C17 0.077(8) 0.025(5) 0.031(6) 0.002(5) 0.000(6) -0.003(6) N6 0.064(6) 0.032(5) 0.027(5) 0.005(4) -0.003(5) -0.012(5) C18 0.067(7) 0.024(5) 0.021(5) -0.004(4) -0.011(5) -0.012(5) C20 0.088(9) 0.047(7) 0.031(6) 0.001(6) -0.029(6) -0.016(7) C21 0.073(8) 0.036(6) 0.055(8) -0.003(6) -0.018(6) -0.012(6) C22 0.061(7) 0.035(6) 0.023(5) 0.002(5) -0.004(5) 0.005(6) C23 0.066(7) 0.020(5) 0.023(5) 0.002(4) -0.002(5) 0.006(5) Cl1 0.0415(14) 0.0492(16) 0.0309(13) -0.0031(13) -0.0063(11) -0.0040(13) O11 0.116(9) 0.178(12) 0.055(7) 0.036(7) 0.019(6) -0.017(9) O12 0.058(6) 0.132(9) 0.073(7) 0.000(6) 0.000(5) 0.042(6) O13 0.083(7) 0.060(6) 0.164(12) -0.008(6) -0.076(7) -0.013(5) O14 0.065(5) 0.076(6) 0.043(5) -0.022(5) -0.029(4) 0.006(5) Cl2 0.0398(16) 0.0431(17) 0.084(2) 0.0005(17) 0.0057(16) 0.0021(15) O21 0.063(6) 0.145(10) 0.096(8) 0.041(8) -0.028(6) -0.029(7) O22 0.092(7) 0.092(8) 0.079(7) -0.021(6) -0.022(6) 0.011(6) O23 0.091(8) 0.129(10) 0.165(13) -0.060(9) 0.003(8) 0.043(8) O24 0.213(14) 0.055(6) 0.160(13) 0.040(8) -0.087(11) -0.037(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 O1 2.081(7) . ? Mn1 N1 2.220(8) . ? Mn1 N3 2.267(9) . ? Mn1 N5 2.285(8) . ? Mn1 N2 2.319(9) . ? Mn1 N4 2.341(8) . ? O1 H1C 0.8400 . ? O1 H1D 0.8473 . ? N1 C7 1.335(12) . ? N1 C11 1.344(12) . ? N2 C2 1.377(19) . ? N2 C1 1.472(14) . ? N2 H2 0.9300 . ? N3 C12 1.434(13) . ? N3 C3 1.453(17) . ? N3 C4 1.468(14) . ? N4 C6 1.459(15) . ? N4 C5 1.476(15) . ? N4 H4 0.9300 . ? N5 C14 1.463(11) . ? N5 C13 1.468(12) . ? N5 H5 0.9300 . ? C19 C20 1.331(16) . ? C19 C18 1.425(15) . ? C19 H19 0.9500 . ? C1 C11 1.501(15) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 C3 1.41(2) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 C5 1.271(17) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C6 C7 1.489(16) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C7 C8 1.396(16) . ? C8 C9 1.367(18) . ? C8 H8 0.9500 . ? C9 C10 1.374(18) . ? C9 H9 0.9500 . ? C10 C11 1.392(14) . ? C10 H10 0.9500 . ? C12 C13 1.471(15) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 H13A 0.9900 . ? C13 H13B 0.9900 . ? C14 C15 1.520(12) . ? C14 H14A 0.9900 . ? C14 H14B 0.9900 . ? C15 C16 1.367(14) . ? C15 C23 1.442(14) . ? C16 C17 1.419(13) . ? C16 H16 0.9500 . ? C17 N6 1.300(14) . ? C17 H17 0.9500 . ? N6 C18 1.350(13) . ? C18 C23 1.418(12) . ? C20 C21 1.416(15) . ? C20 H20 0.9500 . ? C21 C22 1.346(14) . ? C21 H21 0.9500 . ? C22 C23 1.404(14) . ? C22 H22 0.9500 . ? Cl1 O12 1.391(9) . ? Cl1 O13 1.398(9) . ? Cl1 O11 1.407(9) . ? Cl1 O14 1.415(7) . ? Cl2 O24 1.343(11) . ? Cl2 O23 1.351(10) . ? Cl2 O21 1.398(9) . ? Cl2 O22 1.511(10) . ? 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 N1 93.6(3) . . ? O1 Mn1 N3 169.7(3) . . ? N1 Mn1 N3 96.1(3) . . ? O1 Mn1 N5 90.9(3) . . ? N1 Mn1 N5 174.8(3) . . ? N3 Mn1 N5 79.6(3) . . ? O1 Mn1 N2 109.2(4) . . ? N1 Mn1 N2 73.0(3) . . ? N3 Mn1 N2 77.2(4) . . ? N5 Mn1 N2 103.0(3) . . ? O1 Mn1 N4 102.3(3) . . ? N1 Mn1 N4 72.5(3) . . ? N3 Mn1 N4 77.3(3) . . ? N5 Mn1 N4 109.2(3) . . ? N2 Mn1 N4 134.1(3) . . ? Mn1 O1 H1C 109.5 . . ? Mn1 O1 H1D 121.3 . . ? H1C O1 H1D 116.0 . . ? C7 N1 C11 120.0(9) . . ? C7 N1 Mn1 120.1(7) . . ? C11 N1 Mn1 119.2(6) . . ? C2 N2 C1 114.7(10) . . ? C2 N2 Mn1 109.5(8) . . ? C1 N2 Mn1 109.4(7) . . ? C2 N2 H2 107.7 . . ? C1 N2 H2 107.7 . . ? Mn1 N2 H2 107.7 . . ? C12 N3 C3 110.5(11) . . ? C12 N3 C4 116.7(11) . . ? C3 N3 C4 107.6(12) . . ? C12 N3 Mn1 107.3(6) . . ? C3 N3 Mn1 105.6(8) . . ? C4 N3 Mn1 108.5(7) . . ? C6 N4 C5 116.1(13) . . ? C6 N4 Mn1 107.5(7) . . ? C5 N4 Mn1 106.7(7) . . ? C6 N4 H4 108.8 . . ? C5 N4 H4 108.8 . . ? Mn1 N4 H4 108.8 . . ? C14 N5 C13 115.4(8) . . ? C14 N5 Mn1 113.5(6) . . ? C13 N5 Mn1 104.5(6) . . ? C14 N5 H5 107.7 . . ? C13 N5 H5 107.7 . . ? Mn1 N5 H5 107.7 . . ? C20 C19 C18 119.8(10) . . ? C20 C19 H19 120.1 . . ? C18 C19 H19 120.1 . . ? N2 C1 C11 111.1(8) . . ? N2 C1 H1A 109.4 . . ? C11 C1 H1A 109.4 . . ? N2 C1 H1B 109.4 . . ? C11 C1 H1B 109.4 . . ? H1A C1 H1B 108.0 . . ? N2 C2 C3 117.4(12) . . ? N2 C2 H2A 108.0 . . ? C3 C2 H2A 108.0 . . ? N2 C2 H2B 108.0 . . ? C3 C2 H2B 108.0 . . ? H2A C2 H2B 107.2 . . ? C2 C3 N3 118.2(12) . . ? C2 C3 H3A 107.8 . . ? N3 C3 H3A 107.8 . . ? C2 C3 H3B 107.8 . . ? N3 C3 H3B 107.8 . . ? H3A C3 H3B 107.1 . . ? C5 C4 N3 122.8(13) . . ? C5 C4 H4A 106.6 . . ? N3 C4 H4A 106.6 . . ? C5 C4 H4B 106.6 . . ? N3 C4 H4B 106.6 . . ? H4A C4 H4B 106.6 . . ? C4 C5 N4 122.4(12) . . ? C4 C5 H5A 106.7 . . ? N4 C5 H5A 106.7 . . ? C4 C5 H5B 106.7 . . ? N4 C5 H5B 106.7 . . ? H5A C5 H5B 106.6 . . ? N4 C6 C7 112.6(10) . . ? N4 C6 H6A 109.1 . . ? C7 C6 H6A 109.1 . . ? N4 C6 H6B 109.1 . . ? C7 C6 H6B 109.1 . . ? H6A C6 H6B 107.8 . . ? N1 C7 C8 120.8(11) . . ? N1 C7 C6 113.8(10) . . ? C8 C7 C6 125.3(11) . . ? C9 C8 C7 118.7(13) . . ? C9 C8 H8 120.6 . . ? C7 C8 H8 120.6 . . ? C8 C9 C10 120.7(12) . . ? C8 C9 H9 119.7 . . ? C10 C9 H9 119.7 . . ? C9 C10 C11 117.8(12) . . ? C9 C10 H10 121.1 . . ? C11 C10 H10 121.1 . . ? N1 C11 C10 121.7(10) . . ? N1 C11 C1 115.4(8) . . ? C10 C11 C1 122.9(10) . . ? N3 C12 C13 115.5(10) . . ? N3 C12 H12A 108.4 . . ? C13 C12 H12A 108.4 . . ? N3 C12 H12B 108.4 . . ? C13 C12 H12B 108.4 . . ? H12A C12 H12B 107.5 . . ? N5 C13 C12 113.1(9) . . ? N5 C13 H13A 109.0 . . ? C12 C13 H13A 109.0 . . ? N5 C13 H13B 109.0 . . ? C12 C13 H13B 109.0 . . ? H13A C13 H13B 107.8 . . ? N5 C14 C15 115.4(8) . . ? N5 C14 H14A 108.4 . . ? C15 C14 H14A 108.4 . . ? N5 C14 H14B 108.4 . . ? C15 C14 H14B 108.4 . . ? H14A C14 H14B 107.5 . . ? C16 C15 C23 116.8(8) . . ? C16 C15 C14 122.6(9) . . ? C23 C15 C14 120.5(9) . . ? C15 C16 C17 120.6(10) . . ? C15 C16 H16 119.7 . . ? C17 C16 H16 119.7 . . ? N6 C17 C16 123.0(11) . . ? N6 C17 H17 118.5 . . ? C16 C17 H17 118.5 . . ? C17 N6 C18 118.7(9) . . ? N6 C18 C23 122.7(10) . . ? N6 C18 C19 118.6(10) . . ? C23 C18 C19 118.7(10) . . ? C19 C20 C21 121.7(11) . . ? C19 C20 H20 119.2 . . ? C21 C20 H20 119.2 . . ? C22 C21 C20 120.1(12) . . ? C22 C21 H21 119.9 . . ? C20 C21 H21 119.9 . . ? C21 C22 C23 120.4(10) . . ? C21 C22 H22 119.8 . . ? C23 C22 H22 119.8 . . ? C22 C23 C18 119.3(9) . . ? C22 C23 C15 122.7(8) . . ? C18 C23 C15 117.9(9) . . ? O12 Cl1 O13 111.1(7) . . ? O12 Cl1 O11 110.4(7) . . ? O13 Cl1 O11 106.1(8) . . ? O12 Cl1 O14 109.9(5) . . ? O13 Cl1 O14 107.7(6) . . ? O11 Cl1 O14 111.6(6) . . ? O24 Cl2 O23 115.4(10) . . ? O24 Cl2 O21 112.5(7) . . ? O23 Cl2 O21 107.9(8) . . ? O24 Cl2 O22 108.3(7) . . ? O23 Cl2 O22 102.9(7) . . ? O21 Cl2 O22 109.3(6) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O1 Mn1 N1 C7 91.2(8) . . . . ? N3 Mn1 N1 C7 -85.2(8) . . . . ? N2 Mn1 N1 C7 -159.9(9) . . . . ? N4 Mn1 N1 C7 -10.6(8) . . . . ? O1 Mn1 N1 C11 -98.6(7) . . . . ? N3 Mn1 N1 C11 85.0(7) . . . . ? N2 Mn1 N1 C11 10.4(7) . . . . ? N4 Mn1 N1 C11 159.6(8) . . . . ? O1 Mn1 N2 C2 -171.5(9) . . . . ? N1 Mn1 N2 C2 100.6(10) . . . . ? N3 Mn1 N2 C2 0.1(9) . . . . ? N5 Mn1 N2 C2 -76.0(10) . . . . ? N4 Mn1 N2 C2 57.9(11) . . . . ? O1 Mn1 N2 C1 62.1(8) . . . . ? N1 Mn1 N2 C1 -25.8(7) . . . . ? N3 Mn1 N2 C1 -126.3(8) . . . . ? N5 Mn1 N2 C1 157.7(7) . . . . ? N4 Mn1 N2 C1 -68.5(9) . . . . ? O1 Mn1 N3 C12 29(2) . . . . ? N1 Mn1 N3 C12 -171.3(8) . . . . ? N5 Mn1 N3 C12 5.7(7) . . . . ? N2 Mn1 N3 C12 -100.2(8) . . . . ? N4 Mn1 N3 C12 118.3(8) . . . . ? O1 Mn1 N3 C3 147(2) . . . . ? N1 Mn1 N3 C3 -53.4(9) . . . . ? N5 Mn1 N3 C3 123.6(9) . . . . ? N2 Mn1 N3 C3 17.7(8) . . . . ? N4 Mn1 N3 C3 -123.8(9) . . . . ? O1 Mn1 N3 C4 -98(2) . . . . ? N1 Mn1 N3 C4 61.8(10) . . . . ? N5 Mn1 N3 C4 -121.2(11) . . . . ? N2 Mn1 N3 C4 132.8(11) . . . . ? N4 Mn1 N3 C4 -8.6(10) . . . . ? O1 Mn1 N4 C6 -63.3(7) . . . . ? N1 Mn1 N4 C6 26.6(7) . . . . ? N3 Mn1 N4 C6 127.3(8) . . . . ? N5 Mn1 N4 C6 -158.6(7) . . . . ? N2 Mn1 N4 C6 69.5(9) . . . . ? O1 Mn1 N4 C5 171.5(11) . . . . ? N1 Mn1 N4 C5 -98.6(11) . . . . ? N3 Mn1 N4 C5 2.1(11) . . . . ? N5 Mn1 N4 C5 76.2(11) . . . . ? N2 Mn1 N4 C5 -55.7(13) . . . . ? O1 Mn1 N5 C14 76.4(7) . . . . ? N3 Mn1 N5 C14 -107.7(7) . . . . ? N2 Mn1 N5 C14 -33.5(7) . . . . ? N4 Mn1 N5 C14 179.7(6) . . . . ? O1 Mn1 N5 C13 -157.1(7) . . . . ? N3 Mn1 N5 C13 18.8(7) . . . . ? N2 Mn1 N5 C13 93.0(7) . . . . ? N4 Mn1 N5 C13 -53.7(7) . . . . ? C2 N2 C1 C11 -85.5(13) . . . . ? Mn1 N2 C1 C11 37.9(10) . . . . ? C1 N2 C2 C3 103.3(14) . . . . ? Mn1 N2 C2 C3 -20.0(17) . . . . ? N2 C2 C3 N3 41(2) . . . . ? C12 N3 C3 C2 79.2(16) . . . . ? C4 N3 C3 C2 -152.3(14) . . . . ? Mn1 N3 C3 C2 -36.5(16) . . . . ? C12 N3 C4 C5 -104(2) . . . . ? C3 N3 C4 C5 131(2) . . . . ? Mn1 N3 C4 C5 17(3) . . . . ? N3 C4 C5 N4 -17(4) . . . . ? C6 N4 C5 C4 -113(2) . . . . ? Mn1 N4 C5 C4 7(3) . . . . ? C5 N4 C6 C7 78.9(14) . . . . ? Mn1 N4 C6 C7 -40.4(12) . . . . ? C11 N1 C7 C8 -1.7(17) . . . . ? Mn1 N1 C7 C8 168.5(10) . . . . ? C11 N1 C7 C6 -178.4(10) . . . . ? Mn1 N1 C7 C6 -8.3(13) . . . . ? N4 C6 C7 N1 33.9(15) . . . . ? N4 C6 C7 C8 -142.7(12) . . . . ? N1 C7 C8 C9 5(2) . . . . ? C6 C7 C8 C9 -178.7(13) . . . . ? C7 C8 C9 C10 -6(2) . . . . ? C8 C9 C10 C11 4.4(19) . . . . ? C7 N1 C11 C10 -0.3(15) . . . . ? Mn1 N1 C11 C10 -170.6(8) . . . . ? C7 N1 C11 C1 177.7(10) . . . . ? Mn1 N1 C11 C1 7.5(11) . . . . ? C9 C10 C11 N1 -1.0(16) . . . . ? C9 C10 C11 C1 -178.9(11) . . . . ? N2 C1 C11 N1 -31.1(13) . . . . ? N2 C1 C11 C10 146.9(10) . . . . ? C3 N3 C12 C13 -146.2(12) . . . . ? C4 N3 C12 C13 90.5(13) . . . . ? Mn1 N3 C12 C13 -31.5(13) . . . . ? C14 N5 C13 C12 83.3(12) . . . . ? Mn1 N5 C13 C12 -42.0(11) . . . . ? N3 C12 C13 N5 53.2(15) . . . . ? C13 N5 C14 C15 57.8(11) . . . . ? Mn1 N5 C14 C15 178.4(7) . . . . ? N5 C14 C15 C16 24.0(14) . . . . ? N5 C14 C15 C23 -158.9(8) . . . . ? C23 C15 C16 C17 5.9(13) . . . . ? C14 C15 C16 C17 -177.0(9) . . . . ? C15 C16 C17 N6 -5.7(16) . . . . ? C16 C17 N6 C18 1.6(15) . . . . ? C17 N6 C18 C23 1.9(15) . . . . ? C17 N6 C18 C19 -176.9(10) . . . . ? C20 C19 C18 N6 179.3(10) . . . . ? C20 C19 C18 C23 0.5(16) . . . . ? C18 C19 C20 C21 -0.8(18) . . . . ? C19 C20 C21 C22 1.1(18) . . . . ? C20 C21 C22 C23 -1.0(16) . . . . ? C21 C22 C23 C18 0.7(15) . . . . ? C21 C22 C23 C15 -177.0(9) . . . . ? N6 C18 C23 C22 -179.2(9) . . . . ? C19 C18 C23 C22 -0.4(14) . . . . ? N6 C18 C23 C15 -1.3(14) . . . . ? C19 C18 C23 C15 177.5(9) . . . . ? C16 C15 C23 C22 175.2(9) . . . . ? C14 C15 C23 C22 -2.0(14) . . . . ? C16 C15 C23 C18 -2.6(13) . . . . ? C14 C15 C23 C18 -179.8(9) . . . . ? 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 O1 H1C O24 0.84 2.34 3.081(16) 148.2 2_646 O1 H1D N6 0.85 2.34 2.772(11) 112.4 1_554 N2 H2 O13 0.93 2.23 3.059(13) 148.1 2_646 N4 H4 O11 0.93 2.57 3.390(17) 148.1 2_546 N4 H4 O13 0.93 2.43 3.214(17) 142.5 2_546 N5 H5 O14 0.93 2.40 3.221(11) 146.5 2_546 _diffrn_measured_fraction_theta_max 0.945 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.945 _refine_diff_density_max 0.824 _refine_diff_density_min -0.538 _refine_diff_density_rms 0.096 data_mnpytren2q _database_code_depnum_ccdc_archive 'CCDC 810035' #TrackingRef '- esi.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common '[Mn(pytren-2Q)](ClO4)2' _chemical_melting_point ? _chemical_formula_moiety 'C23 H30 Mn N6, 2(Cl O4), H2 O' _chemical_formula_sum 'C23 H32 Cl2 Mn N6 O9' _chemical_formula_weight 662.39 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' 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' 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 9.329(3) _cell_length_b 17.568(5) _cell_length_c 18.335(5) _cell_angle_alpha 90.00 _cell_angle_beta 105.680(16) _cell_angle_gamma 90.00 _cell_volume 2893.1(14) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 4058 _cell_measurement_theta_min 2.910 _cell_measurement_theta_max 25.028 _exptl_crystal_description blades _exptl_crystal_colour colorless _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.521 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1372 _exptl_absorpt_coefficient_mu 0.701 _exptl_absorpt_correction_type none _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 9 _diffrn_radiation_monochromator 'horizonally mounted graphite crystal' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10150 _diffrn_reflns_av_R_equivalents 0.1246 _diffrn_reflns_av_sigmaI/netI 0.1441 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.00 _diffrn_reflns_theta_max 24.32 _reflns_number_total 4520 _reflns_number_gt 1365 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Bruker AXS BV, 1997-2004)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1831P)^2^+2.2610P] 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 4520 _refine_ls_number_parameters 372 _refine_ls_number_restraints 7 _refine_ls_R_factor_all 0.2763 _refine_ls_R_factor_gt 0.1139 _refine_ls_wR_factor_ref 0.4127 _refine_ls_wR_factor_gt 0.3114 _refine_ls_goodness_of_fit_ref 1.034 _refine_ls_restrained_S_all 1.040 _refine_ls_shift/su_max 0.027 _refine_ls_shift/su_mean 0.004 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 0.6477(3) 0.29730(14) 0.15344(11) 0.0946(9) Uani 1 1 d . . . N1 N 0.7058(14) 0.3329(6) 0.2702(6) 0.082(3) Uani 1 1 d . . . N2 N 0.5057(14) 0.4057(7) 0.1582(7) 0.104(4) Uani 1 1 d . . . H2 H 0.4128 0.4002 0.1263 0.125 Uiso 1 1 calc R . . N3 N 0.7965(16) 0.3886(7) 0.1230(8) 0.107(4) Uani 1 1 d . . . N4 N 0.8821(14) 0.2488(7) 0.2063(7) 0.101(4) Uani 1 1 d . . . H4 H 0.8841 0.2000 0.1900 0.122 Uiso 1 1 calc R . . N5 N 0.618(2) 0.2809(13) 0.0302(10) 0.188(8) Uani 1 1 d U . . H5 H 0.5395 0.3128 0.0118 0.226 Uiso 1 1 calc R . . N6 N 0.4767(14) 0.2055(7) 0.1241(7) 0.097(3) Uani 1 1 d . . . C1 C 0.496(2) 0.4145(11) 0.2380(11) 0.135(6) Uani 1 1 d . . . H1A H 0.4798 0.4677 0.2472 0.162 Uiso 1 1 calc R . . H1B H 0.4106 0.3861 0.2438 0.162 Uiso 1 1 calc R . . C2 C 0.588(2) 0.4669(10) 0.1296(10) 0.122(6) Uani 1 1 d . . . H2A H 0.5515 0.4673 0.0748 0.147 Uiso 1 1 calc R . . H2B H 0.5596 0.5152 0.1474 0.147 Uiso 1 1 calc R . . C3 C 0.749(3) 0.4652(10) 0.1484(13) 0.151(8) Uani 1 1 d . . . H3A H 0.7900 0.4714 0.2026 0.181 Uiso 1 1 calc R . . H3B H 0.7846 0.5065 0.1229 0.181 Uiso 1 1 calc R . . C4 C 0.953(2) 0.3763(12) 0.1695(12) 0.134(7) Uani 1 1 d . . . H4A H 1.0210 0.4011 0.1454 0.161 Uiso 1 1 calc R . . H4B H 0.9661 0.3989 0.2192 0.161 Uiso 1 1 calc R . . C5 C 0.9881(19) 0.2933(13) 0.1780(10) 0.128(6) Uani 1 1 d . . . H5A H 0.9908 0.2731 0.1292 0.153 Uiso 1 1 calc R . . H5B H 1.0865 0.2871 0.2125 0.153 Uiso 1 1 calc R . . C6 C 0.9135(18) 0.2476(9) 0.2887(9) 0.105(5) Uani 1 1 d . . . H6A H 0.8887 0.1977 0.3043 0.126 Uiso 1 1 calc R . . H6B H 1.0194 0.2554 0.3105 0.126 Uiso 1 1 calc R . . C7 C 0.8324(19) 0.3049(9) 0.3192(9) 0.099(4) Uani 1 1 d . . . C8 C 0.891(2) 0.3334(11) 0.3935(10) 0.122(6) Uani 1 1 d . . . H8 H 0.9788 0.3149 0.4258 0.146 Uiso 1 1 calc R . . C9 C 0.809(3) 0.3898(11) 0.4146(10) 0.118(6) Uani 1 1 d . . . H9 H 0.8449 0.4113 0.4625 0.142 Uiso 1 1 calc R . . C10 C 0.672(3) 0.4175(10) 0.3663(12) 0.123(6) Uani 1 1 d . . . H10 H 0.6147 0.4536 0.3828 0.148 Uiso 1 1 calc R . . C11 C 0.629(2) 0.3882(9) 0.2949(10) 0.098(5) Uani 1 1 d . . . C12 C 0.781(3) 0.3871(13) 0.0404(13) 0.153(8) Uani 1 1 d . . . H12A H 0.7146 0.4282 0.0172 0.184 Uiso 1 1 calc R . . H12B H 0.8775 0.3979 0.0325 0.184 Uiso 1 1 calc R . . C13 C 0.724(3) 0.3164(13) -0.0001(13) 0.192(11) Uani 1 1 d U . . H13A H 0.6799 0.3278 -0.0531 0.230 Uiso 1 1 calc R . . H13B H 0.8068 0.2818 0.0032 0.230 Uiso 1 1 calc R . . C14 C 0.550(3) 0.2128(9) 0.0059(11) 0.141(7) Uani 1 1 d U . . H14A H 0.6270 0.1750 0.0077 0.170 Uiso 1 1 calc R . . H14B H 0.4933 0.2181 -0.0465 0.170 Uiso 1 1 calc R . . C15 C 0.444(2) 0.1825(11) 0.0527(10) 0.117(6) Uani 1 1 d . . . C16 C 0.321(3) 0.1303(13) 0.0201(14) 0.150(10) Uani 1 1 d . . . H16 H 0.3020 0.1160 -0.0305 0.180 Uiso 1 1 calc R . . C17 C 0.242(3) 0.1051(13) 0.059(2) 0.167(12) Uani 1 1 d . . . H17 H 0.1659 0.0708 0.0386 0.200 Uiso 1 1 calc R . . C18 C 0.273(2) 0.1304(10) 0.1345(16) 0.123(7) Uani 1 1 d . . . C19 C 0.177(3) 0.1075(13) 0.183(2) 0.169(12) Uani 1 1 d . . . H19 H 0.0908 0.0795 0.1623 0.203 Uiso 1 1 calc R . . C20 C 0.213(3) 0.1269(10) 0.2541(19) 0.150(10) Uani 1 1 d . . . H20 H 0.1556 0.1080 0.2842 0.180 Uiso 1 1 calc R . . C21 C 0.336(2) 0.1753(11) 0.2890(11) 0.130(7) Uani 1 1 d . . . H21 H 0.3564 0.1879 0.3401 0.157 Uiso 1 1 calc R . . C22 C 0.422(2) 0.2027(10) 0.2448(11) 0.121(6) Uani 1 1 d . . . H22 H 0.5008 0.2357 0.2648 0.145 Uiso 1 1 calc R . . C23 C 0.3883(19) 0.1795(9) 0.1685(10) 0.095(4) Uani 1 1 d . . . Cl1 Cl 0.1796(6) 0.1398(3) 0.4863(3) 0.1126(15) Uani 1 1 d . . . O11 O 0.1854(19) 0.1548(18) 0.5557(11) 0.299(14) Uani 1 1 d . . . O12 O 0.0589(17) 0.1031(10) 0.4391(9) 0.193(7) Uani 1 1 d . . . O13 O 0.3140(18) 0.1179(12) 0.4795(9) 0.210(8) Uani 1 1 d . . . O14 O 0.171(4) 0.2078(13) 0.4552(17) 0.40(2) Uani 1 1 d . . . Cl2 Cl 0.7783(6) 0.0295(3) 0.1442(3) 0.1214(16) Uani 1 1 d . . . O21 O 0.809(2) 0.0830(14) 0.1014(10) 0.252(10) Uani 1 1 d . . . O22 O 0.855(3) -0.0282(12) 0.1420(16) 0.37(2) Uani 1 1 d . . . O23 O 0.835(3) 0.0568(13) 0.2164(10) 0.255(10) Uani 1 1 d . . . O24 O 0.629(2) 0.0076(10) 0.1166(14) 0.259(10) Uani 1 1 d . . . O1 O 0.256(3) 0.5569(17) 0.1435(10) 0.309(13) Uani 1 1 d D . . H1C H 0.207(3) 0.5304(17) 0.1724(12) 0.371 Uiso 1 1 d RD . . H1D H 0.191(3) 0.5742(17) 0.1185(11) 0.371 Uiso 1 1 d RD . . 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 0.0878(19) 0.1071(18) 0.0917(15) 0.0017(13) 0.0292(12) -0.0082(13) N1 0.065(8) 0.082(8) 0.104(8) 0.008(6) 0.030(7) 0.003(6) N2 0.081(10) 0.129(11) 0.103(9) -0.001(8) 0.026(7) 0.004(8) N3 0.092(11) 0.092(10) 0.154(12) 0.035(8) 0.060(9) 0.014(7) N4 0.105(11) 0.088(8) 0.118(10) -0.007(7) 0.042(8) 0.013(7) N5 0.21(2) 0.216(19) 0.159(14) -0.063(14) 0.080(13) -0.073(15) N6 0.101(10) 0.084(8) 0.109(9) -0.013(7) 0.035(8) 0.004(7) C1 0.133(18) 0.143(16) 0.150(16) -0.027(13) 0.073(14) 0.014(13) C2 0.087(15) 0.130(16) 0.147(14) -0.028(12) 0.026(11) 0.001(11) C3 0.131(19) 0.094(14) 0.25(2) 0.018(14) 0.096(17) 0.004(12) C4 0.123(18) 0.120(16) 0.193(18) -0.031(14) 0.100(15) -0.050(13) C5 0.096(14) 0.17(2) 0.130(13) 0.012(13) 0.049(10) -0.002(13) C6 0.095(13) 0.103(12) 0.116(12) -0.006(10) 0.027(9) 0.009(10) C7 0.094(13) 0.105(12) 0.105(11) -0.012(10) 0.041(10) -0.012(10) C8 0.134(17) 0.146(16) 0.096(12) 0.002(11) 0.049(11) 0.003(13) C9 0.148(19) 0.128(16) 0.087(11) 0.001(11) 0.045(12) -0.038(14) C10 0.16(2) 0.114(14) 0.127(15) -0.007(12) 0.087(15) 0.004(13) C11 0.101(14) 0.099(12) 0.101(12) 0.020(10) 0.038(10) 0.009(10) C12 0.17(2) 0.147(19) 0.17(2) 0.042(16) 0.102(16) 0.031(15) C13 0.34(3) 0.127(17) 0.18(2) 0.012(15) 0.19(2) 0.008(17) C14 0.23(2) 0.077(10) 0.130(14) -0.003(10) 0.074(15) 0.044(10) C15 0.107(15) 0.143(16) 0.094(11) 0.006(11) 0.017(10) 0.050(12) C16 0.16(2) 0.089(16) 0.145(19) 0.006(13) -0.056(16) -0.015(14) C17 0.17(3) 0.074(15) 0.20(3) 0.017(17) -0.04(2) -0.022(14) C18 0.066(13) 0.095(14) 0.21(2) 0.029(14) 0.036(14) -0.012(10) C19 0.076(16) 0.096(16) 0.30(4) -0.02(2) -0.01(2) 0.005(11) C20 0.107(19) 0.056(12) 0.31(3) 0.011(16) 0.10(2) -0.018(11) C21 0.16(2) 0.119(15) 0.138(14) 0.026(12) 0.079(14) 0.015(14) C22 0.129(16) 0.098(12) 0.143(15) -0.001(11) 0.051(12) -0.019(11) C23 0.078(12) 0.088(11) 0.115(12) -0.011(9) 0.016(9) 0.006(8) Cl1 0.100(4) 0.124(4) 0.119(3) -0.018(3) 0.039(3) -0.007(3) O11 0.121(14) 0.61(4) 0.192(17) -0.09(2) 0.085(12) -0.08(2) O12 0.122(12) 0.241(18) 0.219(15) -0.091(13) 0.051(10) -0.050(11) O13 0.113(13) 0.34(2) 0.197(14) -0.081(14) 0.078(10) -0.060(14) O14 0.50(5) 0.168(19) 0.38(4) 0.04(2) -0.15(3) 0.12(2) Cl2 0.117(5) 0.127(4) 0.122(4) -0.006(3) 0.037(3) -0.016(3) O21 0.194(18) 0.37(3) 0.198(16) 0.137(17) 0.063(13) -0.011(17) O22 0.37(4) 0.164(18) 0.45(4) -0.11(2) -0.09(3) 0.14(2) O23 0.34(3) 0.28(2) 0.153(14) -0.048(14) 0.069(15) -0.10(2) O24 0.096(14) 0.201(17) 0.47(3) -0.022(17) 0.059(15) -0.045(12) O1 0.25(2) 0.48(4) 0.201(17) 0.09(2) 0.070(16) 0.09(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 N1 2.155(12) . ? Mn1 N5 2.220(17) . ? Mn1 N6 2.229(13) . ? Mn1 N3 2.287(12) . ? Mn1 N4 2.303(12) . ? Mn1 N2 2.335(12) . ? N1 C11 1.356(18) . ? N1 C7 1.367(18) . ? N2 C2 1.496(19) . ? N2 C1 1.498(19) . ? N2 H2 0.9100 . ? N3 C12 1.48(2) . ? N3 C4 1.49(2) . ? N3 C3 1.53(2) . ? N4 C6 1.459(17) . ? N4 C5 1.461(19) . ? N4 H4 0.9100 . ? N5 C14 1.37(2) . ? N5 C13 1.41(3) . ? N5 H5 0.9100 . ? N6 C15 1.324(18) . ? N6 C23 1.383(18) . ? C1 C11 1.46(2) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C2 C3 1.44(2) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 C5 1.49(2) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 C7 1.458(19) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C8 1.41(2) . ? C8 C9 1.37(2) . ? C8 H8 0.9300 . ? C9 C10 1.43(2) . ? C9 H9 0.9300 . ? C10 C11 1.36(2) . ? C10 H10 0.9300 . ? C12 C13 1.47(3) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 C15 1.57(3) . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C15 C16 1.47(3) . ? C16 C17 1.23(3) . ? C16 H16 0.9300 . ? C17 C18 1.41(3) . ? C17 H17 0.9300 . ? C18 C23 1.39(2) . ? C18 C19 1.47(3) . ? C19 C20 1.31(3) . ? C19 H19 0.9300 . ? C20 C21 1.43(3) . ? C20 H20 0.9300 . ? C21 C22 1.37(2) . ? C21 H21 0.9300 . ? C22 C23 1.41(2) . ? C22 H22 0.9300 . ? Cl1 O11 1.287(17) . ? Cl1 O14 1.32(2) . ? Cl1 O13 1.349(16) . ? Cl1 O12 1.381(14) . ? Cl2 O22 1.250(19) . ? Cl2 O21 1.304(16) . ? Cl2 O23 1.373(17) . ? Cl2 O24 1.399(16) . ? O1 H1D 0.7211 . ? O1 H1C 0.9157 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Mn1 N5 168.0(6) . . ? N1 Mn1 N6 114.9(4) . . ? N5 Mn1 N6 77.1(6) . . ? N1 Mn1 N3 91.9(5) . . ? N5 Mn1 N3 76.1(6) . . ? N6 Mn1 N3 152.9(5) . . ? N1 Mn1 N4 74.5(5) . . ? N5 Mn1 N4 103.0(7) . . ? N6 Mn1 N4 111.7(5) . . ? N3 Mn1 N4 78.0(5) . . ? N1 Mn1 N2 73.7(5) . . ? N5 Mn1 N2 103.1(7) . . ? N6 Mn1 N2 102.9(5) . . ? N3 Mn1 N2 79.9(5) . . ? N4 Mn1 N2 140.3(5) . . ? C11 N1 C7 118.7(13) . . ? C11 N1 Mn1 121.7(11) . . ? C7 N1 Mn1 119.3(10) . . ? C2 N2 C1 116.1(13) . . ? C2 N2 Mn1 102.9(9) . . ? C1 N2 Mn1 107.7(10) . . ? C2 N2 H2 109.9 . . ? C1 N2 H2 109.9 . . ? Mn1 N2 H2 109.9 . . ? C12 N3 C4 113.1(13) . . ? C12 N3 C3 111.8(14) . . ? C4 N3 C3 105.9(16) . . ? C12 N3 Mn1 109.8(12) . . ? C4 N3 Mn1 108.8(9) . . ? C3 N3 Mn1 107.2(10) . . ? C6 N4 C5 114.2(13) . . ? C6 N4 Mn1 110.1(8) . . ? C5 N4 Mn1 108.0(10) . . ? C6 N4 H4 108.2 . . ? C5 N4 H4 108.2 . . ? Mn1 N4 H4 108.2 . . ? C14 N5 C13 124.8(19) . . ? C14 N5 Mn1 111.3(14) . . ? C13 N5 Mn1 115.8(16) . . ? C14 N5 H5 99.5 . . ? C13 N5 H5 99.5 . . ? Mn1 N5 H5 99.5 . . ? C15 N6 C23 117.9(14) . . ? C15 N6 Mn1 114.6(12) . . ? C23 N6 Mn1 126.8(10) . . ? C11 C1 N2 113.7(14) . . ? C11 C1 H1A 108.8 . . ? N2 C1 H1A 108.8 . . ? C11 C1 H1B 108.8 . . ? N2 C1 H1B 108.8 . . ? H1A C1 H1B 107.7 . . ? C3 C2 N2 120.0(16) . . ? C3 C2 H2A 107.3 . . ? N2 C2 H2A 107.3 . . ? C3 C2 H2B 107.3 . . ? N2 C2 H2B 107.3 . . ? H2A C2 H2B 106.9 . . ? C2 C3 N3 108.4(16) . . ? C2 C3 H3A 110.0 . . ? N3 C3 H3A 110.0 . . ? C2 C3 H3B 110.0 . . ? N3 C3 H3B 110.0 . . ? H3A C3 H3B 108.4 . . ? C5 C4 N3 110.8(14) . . ? C5 C4 H4A 109.5 . . ? N3 C4 H4A 109.5 . . ? C5 C4 H4B 109.5 . . ? N3 C4 H4B 109.5 . . ? H4A C4 H4B 108.1 . . ? N4 C5 C4 114.1(13) . . ? N4 C5 H5A 108.7 . . ? C4 C5 H5A 108.7 . . ? N4 C5 H5B 108.7 . . ? C4 C5 H5B 108.7 . . ? H5A C5 H5B 107.6 . . ? C7 C6 N4 114.1(13) . . ? C7 C6 H6A 108.7 . . ? N4 C6 H6A 108.7 . . ? C7 C6 H6B 108.7 . . ? N4 C6 H6B 108.7 . . ? H6A C6 H6B 107.6 . . ? N1 C7 C8 123.1(15) . . ? N1 C7 C6 116.2(14) . . ? C8 C7 C6 120.5(17) . . ? C9 C8 C7 115.4(18) . . ? C9 C8 H8 122.3 . . ? C7 C8 H8 122.3 . . ? C8 C9 C10 123.0(17) . . ? C8 C9 H9 118.5 . . ? C10 C9 H9 118.5 . . ? C11 C10 C9 116.6(16) . . ? C11 C10 H10 121.7 . . ? C9 C10 H10 121.7 . . ? N1 C11 C10 123.1(17) . . ? N1 C11 C1 114.3(15) . . ? C10 C11 C1 122.6(18) . . ? C13 C12 N3 117.0(16) . . ? C13 C12 H12A 108.1 . . ? N3 C12 H12A 108.1 . . ? C13 C12 H12B 108.0 . . ? N3 C12 H12B 108.1 . . ? H12A C12 H12B 107.3 . . ? N5 C13 C12 111.8(17) . . ? N5 C13 H13A 109.3 . . ? C12 C13 H13A 109.3 . . ? N5 C13 H13B 109.3 . . ? C12 C13 H13B 109.3 . . ? H13A C13 H13B 107.9 . . ? N5 C14 C15 115.0(15) . . ? N5 C14 H14A 108.5 . . ? C15 C14 H14A 108.5 . . ? N5 C14 H14B 108.5 . . ? C15 C14 H14B 108.5 . . ? H14A C14 H14B 107.5 . . ? N6 C15 C16 122.5(19) . . ? N6 C15 C14 115.4(18) . . ? C16 C15 C14 122.0(19) . . ? C17 C16 C15 121(3) . . ? C17 C16 H16 119.5 . . ? C15 C16 H16 119.5 . . ? C16 C17 C18 117(3) . . ? C16 C17 H17 121.3 . . ? C18 C17 H17 121.3 . . ? C23 C18 C17 124(2) . . ? C23 C18 C19 115(2) . . ? C17 C18 C19 121(2) . . ? C20 C19 C18 120(2) . . ? C20 C19 H19 120.2 . . ? C18 C19 H19 120.2 . . ? C19 C20 C21 124(2) . . ? C19 C20 H20 117.8 . . ? C21 C20 H20 117.8 . . ? C22 C21 C20 118(2) . . ? C22 C21 H21 121.1 . . ? C20 C21 H21 121.1 . . ? C21 C22 C23 118.4(18) . . ? C21 C22 H22 120.8 . . ? C23 C22 H22 120.8 . . ? N6 C23 C18 117.1(17) . . ? N6 C23 C22 118.6(15) . . ? C18 C23 C22 124.3(19) . . ? O11 Cl1 O14 102.8(18) . . ? O11 Cl1 O13 110.9(11) . . ? O14 Cl1 O13 99.8(19) . . ? O11 Cl1 O12 121.6(11) . . ? O14 Cl1 O12 102.0(15) . . ? O13 Cl1 O12 115.6(10) . . ? O22 Cl2 O21 110(2) . . ? O22 Cl2 O23 103.9(16) . . ? O21 Cl2 O23 103.8(14) . . ? O22 Cl2 O24 106.8(16) . . ? O21 Cl2 O24 109.8(13) . . ? O23 Cl2 O24 122.0(14) . . ? H1D O1 H1C 96.5 . . ? H1C O1 H1D 96.5 . . ? 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 O1 H1C O23 0.92 2.23 2.91(3) 131.5 2_655 O1 H1D O12 0.72 2.34 3.03(3) 160.5 2 N2 H2 O11 0.91 2.37 3.25(3) 161.8 4_565 N4 H4 O21 0.91 2.60 3.45(3) 157.8 . N5 H5 O13 0.91 2.36 3.26(3) 168.9 4_565 _diffrn_measured_fraction_theta_max 0.958 _diffrn_reflns_theta_full 24.32 _diffrn_measured_fraction_theta_full 0.958 _refine_diff_density_max 0.589 _refine_diff_density_min -0.330 _refine_diff_density_rms 0.080