# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_c1a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'Co3 Cl4 C42 N12 H40' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 14.0472(12) _cell_length_b 12.9062(14) _cell_length_c 11.2407(5) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 2037.9(3) _cell_formula_units_Z 2 _cell_measurement_reflns_used 2491 _cell_measurement_temperature 293.4(9) _cell_measurement_pressure 0.0(0) _cell_measurement_theta_max 28.4724 _cell_measurement_theta_min 1.8080 _exptl_absorpt_coefficient_mu 1.520 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.80087 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.65 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description prism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.1612 _exptl_crystal_size_mid 0.1166 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0648 _diffrn_reflns_av_unetI/netI 0.0948 _diffrn_reflns_Laue_measured_fraction_full 0.584 _diffrn_reflns_Laue_measured_fraction_max 0.500 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_number 8911 _diffrn_reflns_point_group_measured_fraction_full 0.575 _diffrn_reflns_point_group_measured_fraction_max 0.478 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 28.535 _diffrn_reflns_theta_min 2.143 _diffrn_ambient_temperature 293.4(9) _diffrn_ambient_pressure 0.0(0) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.584 _diffrn_measured_fraction_theta_max 0.500 _diffrn_measurement_details ; #__ type_ start__ end____ width___ exp.time_ 1 omega -31.00 -4.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.7556 114.0000 135.0000 27 #__ type_ start__ end____ width___ exp.time_ 2 omega -11.00 39.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.7556 -57.0000 -150.0000 50 #__ type_ start__ end____ width___ exp.time_ 3 omega -34.00 -9.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 53.0000 162.0000 25 #__ type_ start__ end____ width___ exp.time_ 4 omega -38.00 14.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 26.0000 -7.0000 52 #__ type_ start__ end____ width___ exp.time_ 5 omega -1.00 27.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 -97.0000 35.0000 28 #__ type_ start__ end____ width___ exp.time_ 6 omega 4.00 78.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.7556 -114.0000 45.0000 74 #__ type_ start__ end____ width___ exp.time_ 7 omega -32.00 5.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.7556 97.0000 -35.0000 37 #__ type_ start__ end____ width___ exp.time_ 8 omega -38.00 44.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 38.0000 150.0000 82 #__ type_ start__ end____ width___ exp.time_ 9 omega -13.00 24.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 -81.0000 29.0000 37 ; _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 0.0338927000 _diffrn_orient_matrix_UB_12 0.0407277000 _diffrn_orient_matrix_UB_13 -0.0013760000 _diffrn_orient_matrix_UB_21 0.0237021000 _diffrn_orient_matrix_UB_22 -0.0245559000 _diffrn_orient_matrix_UB_23 -0.0480592000 _diffrn_orient_matrix_UB_31 -0.0289838000 _diffrn_orient_matrix_UB_32 0.0275229000 _diffrn_orient_matrix_UB_33 -0.0408681000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.821 _reflns_Friedel_fraction_full 0.565 _reflns_Friedel_fraction_max 0.454 _reflns_number_gt 1449 _reflns_number_total 2480 _reflns_odcompleteness_completeness 63.57 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 20.77 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _computing_structure_solution ; XS, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.440 _refine_diff_density_min -0.466 _refine_diff_density_rms 0.084 _refine_ls_abs_structure_details ; Classical Flack method preferred over Parsons because s.u. lower. ; _refine_ls_abs_structure_Flack -0.09(6) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 2480 _refine_ls_number_restraints 583 _refine_ls_R_factor_all 0.1209 _refine_ls_R_factor_gt 0.0558 _refine_ls_restrained_S_all 1.013 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.0657P)^2^+0.3478P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.1194 _refine_ls_wR_factor_ref 0.1530 _refine_special_details ; ? ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups 2. Restrained distances Cl2B-C21B 1.79 with sigma of 0.05 C21B-Cl3B 1.79 with sigma of 0.05 Cl3B-Cl2B 2.9 with sigma of 0.1 3. Restrained planarity N1, C1, C2, C3, C4, C5 with sigma of 0.1 N2, C6, C7, C8, C9, C10 with sigma of 0.1 N3, C11, C12, C13, C14, C15 with sigma of 0.1 N4, C16, C17, C18, C19, C20 with sigma of 0.1 4. Uiso/Uaniso restraints and constraints C21A \\sim C21B \\sim Cl2A \\sim Cl3B \\sim Cl3A \\sim Cl2B: within 5A with sigma of 0.03 and sigma for terminal atoms of 0.03 5. Same fragment restrains {N2, C6, C7, C8, C9, C10} {N3, C11, C12, C13, C14, C15} {N4, C16, C17, C18, C19, C20} {N1, C5, C4, C3, C2, C1} {C1, C2, C3, C4, C5, N1} as {N1, C1, C2, C3, C4, C5} 6. Others 0.5*Sof(C21A)=0.5*Sof(H21A)=0.5*Sof(H21B)=0.5*Sof(Cl2A)=0.5*Sof(Cl3A)=1-0.5* Sof(C21B)=1-0.5*Sof(H21C)=1-0.5*Sof(H21D)=1-0.5*Sof(Cl2B)=1-0.5*Sof(Cl3B) 7.a Secondary CH2 refined with riding coordinates: C21A(H21A,H21B), C21B(H21C,H21D) 7.b Aromatic/amide H refined with riding coordinates: C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19) ; _atom_sites_solution_hydrogens geom _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5345(7) 0.6737(8) -0.1600(7) 0.036(3) Uiso 1 1 d D . . . . C1 C 0.4586(9) 0.6194(9) -0.1994(9) 0.035(3) Uiso 1 1 d D . . . . C2 C 0.4267(10) 0.6301(11) -0.3160(10) 0.054(4) Uiso 1 1 d D . . . . H2 H 0.3740 0.5929 -0.3419 0.065 Uiso 1 1 calc R U . . . C3 C 0.4728(10) 0.6952(11) -0.3923(10) 0.055(4) Uiso 1 1 d D . . . . H3 H 0.4519 0.7030 -0.4703 0.066 Uiso 1 1 calc R U . . . C4 C 0.5503(11) 0.7487(13) -0.3519(11) 0.063(4) Uiso 1 1 d D . . . . H4 H 0.5824 0.7932 -0.4030 0.076 Uiso 1 1 calc R U . . . C5 C 0.5809(9) 0.7378(10) -0.2382(10) 0.045(4) Uiso 1 1 d D . . . . H5 H 0.6342 0.7744 -0.2128 0.054 Uiso 1 1 calc R U . . . N2 N 0.4717(8) 0.7202(10) 0.0692(8) 0.041(3) Uiso 1 1 d D . . . . C6 C 0.4026(8) 0.6606(10) 0.1191(9) 0.042(4) Uiso 1 1 d D . . . . C7 C 0.3212(9) 0.7100(12) 0.1589(10) 0.049(4) Uiso 1 1 d D . . . . H7 H 0.2726 0.6704 0.1917 0.059 Uiso 1 1 calc R U . . . C8 C 0.3099(11) 0.8141(12) 0.1517(12) 0.064(5) Uiso 1 1 d D . . . . H8 H 0.2560 0.8453 0.1836 0.076 Uiso 1 1 calc R U . . . C9 C 0.3778(10) 0.8729(11) 0.0978(11) 0.055(4) Uiso 1 1 d D . . . . H9 H 0.3704 0.9442 0.0895 0.066 Uiso 1 1 calc R U . . . C10 C 0.4575(10) 0.8232(11) 0.0561(11) 0.055(4) Uiso 1 1 d D . . . . H10 H 0.5038 0.8621 0.0172 0.066 Uiso 1 1 calc R U . . . N3 N 0.6931(8) 0.5675(9) -0.0609(8) 0.047(3) Uiso 1 1 d D . . . . C11 C 0.7848(10) 0.5989(12) -0.0421(10) 0.061(5) Uiso 1 1 d D . . . . H11 H 0.7968 0.6585 0.0019 0.074 Uiso 1 1 calc R U . . . C12 C 0.8599(11) 0.5422(13) -0.0886(13) 0.078(6) Uiso 1 1 d D . . . . H12 H 0.9224 0.5629 -0.0752 0.093 Uiso 1 1 calc R U . . . C13 C 0.8412(12) 0.4564(14) -0.1538(14) 0.086(6) Uiso 1 1 d D . . . . H13 H 0.8916 0.4199 -0.1873 0.104 Uiso 1 1 calc R U . . . C14 C 0.7502(10) 0.4217(12) -0.1716(12) 0.061(4) Uiso 1 1 d D . . . . H14 H 0.7385 0.3626 -0.2167 0.073 Uiso 1 1 calc R U . . . C15 C 0.6754(9) 0.4776(11) -0.1202(10) 0.042(4) Uiso 1 1 d D . . . . N4 N 0.6226(8) 0.6089(9) 0.1702(8) 0.040(3) Uiso 1 1 d D . . . . C16 C 0.6502(10) 0.6813(11) 0.2507(10) 0.058(4) Uiso 1 1 d D . . . . H16 H 0.6519 0.7504 0.2276 0.070 Uiso 1 1 calc R U . . . C17 C 0.6756(11) 0.6563(12) 0.3645(11) 0.061(4) Uiso 1 1 d D . . . . H17 H 0.6960 0.7071 0.4173 0.073 Uiso 1 1 calc R U . . . C18 C 0.6704(11) 0.5548(11) 0.3988(11) 0.056(4) Uiso 1 1 d D . . . . H18 H 0.6848 0.5366 0.4768 0.067 Uiso 1 1 calc R U . . . C19 C 0.6443(10) 0.4803(11) 0.3202(10) 0.052(4) Uiso 1 1 d D . . . . H19 H 0.6443 0.4110 0.3431 0.062 Uiso 1 1 calc R U . . . C20 C 0.6173(10) 0.5080(10) 0.2038(10) 0.039(3) Uiso 1 1 d D . . . . N6 N 0.5804(8) 0.4451(11) 0.1196(9) 0.038(3) Uiso 1 1 d . . . . . N5 N 0.5819(9) 0.4445(11) -0.1195(9) 0.038(3) Uiso 1 1 d . . . . . Cl1 Cl 0.6838(2) 0.8156(3) 0.0065(4) 0.0509(9) Uani 1 1 d . . . . . Co1 Co 0.58787(11) 0.65413(13) 0.00484(18) 0.0361(5) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 0.0011(2) 0.0317(6) Uani 1 2 d S T P . . C21A C 0.040(4) 0.500(5) 0.312(5) 0.066(12) Uiso 0.443(11) 1 d . U P A -1 H21A H 0.0408 0.4353 0.3561 0.079 Uiso 0.443(11) 1 calc R U P A -1 H21B H 0.0677 0.5534 0.3609 0.079 Uiso 0.443(11) 1 calc R U P A -1 Cl2A Cl 0.1081(9) 0.4854(12) 0.1774(11) 0.096(5) Uiso 0.443(11) 1 d . U P A -1 Cl3A Cl -0.0800(14) 0.5330(17) 0.2768(13) 0.112(5) Uiso 0.443(11) 1 d . U P A -1 C21B C 0.093(14) 0.550(10) 0.26(3) 0.09(2) Uiso 0.057(11) 1 d D U P A -2 H21C H 0.0939 0.5853 0.1786 0.103 Uiso 0.057(11) 1 calc R U P A -2 H21D H 0.1372 0.5837 0.3091 0.103 Uiso 0.057(11) 1 calc R U P A -2 Cl2B Cl 0.114(8) 0.414(9) 0.242(9) 0.091(18) Uiso 0.057(11) 1 d D U P A -2 Cl3B Cl -0.026(11) 0.542(8) 0.316(10) 0.074(18) Uiso 0.057(11) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.049(3) 0.042(3) 0.0616(15) 0.001(3) 0.002(3) -0.0111(13) Co1 0.0367(16) 0.0314(16) 0.0403(7) -0.0002(12) 0.0002(12) 0.0011(6) Co2 0.0294(19) 0.028(2) 0.0378(10) 0.000 0.000 0.0001(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 N1 C1 1.350(12) . ? N1 C5 1.372(12) . ? N1 Co1 2.015(9) . ? C1 C2 1.392(13) . ? C1 N5 1.346(16) 2_665 ? C2 C3 1.363(13) . ? C3 C4 1.368(14) . ? C4 C5 1.356(13) . ? N2 C6 1.360(13) . ? N2 C10 1.352(13) . ? N2 Co1 1.978(11) . ? C6 C7 1.382(14) . ? C6 N6 1.384(16) 2_665 ? C7 C8 1.356(14) . ? C8 C9 1.361(14) . ? C9 C10 1.373(14) . ? N3 C11 1.366(13) . ? N3 C15 1.361(13) . ? N3 Co1 1.996(12) . ? C11 C12 1.387(15) . ? C12 C13 1.354(15) . ? C13 C14 1.369(14) . ? C14 C15 1.400(14) . ? C15 N5 1.382(17) . ? N4 C16 1.358(13) . ? N4 C20 1.358(12) . ? N4 Co1 2.008(10) . ? C16 C17 1.366(13) . ? C17 C18 1.368(14) . ? C18 C19 1.356(13) . ? C19 C20 1.408(13) . ? C20 N6 1.350(17) . ? N6 C6 1.384(16) 2_665 ? N6 Co2 1.885(11) . ? N5 C1 1.346(16) 2_665 ? N5 Co2 1.917(11) . ? Cl1 Co1 2.482(4) . ? Co1 Co2 2.3414(17) . ? Co2 N6 1.885(11) 2_665 ? Co2 N5 1.917(11) 2_665 ? Co2 Co1 2.3414(17) 2_665 ? C21A Cl2A 1.80(6) . ? C21A Cl3A 1.78(5) . ? C21B Cl2B 1.80(7) . ? C21B Cl3B 1.81(7) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 N1 C5 118.6(9) . . ? C1 N1 Co1 122.0(7) . . ? C5 N1 Co1 119.2(7) . . ? N1 C1 C2 120.8(11) . . ? N5 C1 N1 115.7(10) 2_665 . ? N5 C1 C2 123.6(11) 2_665 . ? C3 C2 C1 120.0(12) . . ? C2 C3 C4 118.7(11) . . ? C5 C4 C3 120.9(13) . . ? C4 C5 N1 121.0(11) . . ? C6 N2 Co1 119.7(10) . . ? C10 N2 C6 119.7(11) . . ? C10 N2 Co1 120.4(8) . . ? N2 C6 C7 117.5(13) . . ? N2 C6 N6 115.8(11) . 2_665 ? C7 C6 N6 126.5(12) . 2_665 ? C8 C7 C6 122.3(13) . . ? C7 C8 C9 119.8(14) . . ? C8 C9 C10 117.6(14) . . ? N2 C10 C9 122.9(12) . . ? C11 N3 Co1 118.3(9) . . ? C15 N3 C11 120.1(11) . . ? C15 N3 Co1 121.6(9) . . ? N3 C11 C12 120.2(14) . . ? C13 C12 C11 119.2(15) . . ? C12 C13 C14 121.9(15) . . ? C13 C14 C15 118.1(14) . . ? N3 C15 C14 120.3(12) . . ? N3 C15 N5 115.7(11) . . ? N5 C15 C14 123.9(13) . . ? C16 N4 C20 119.3(10) . . ? C16 N4 Co1 119.1(9) . . ? C20 N4 Co1 121.5(8) . . ? N4 C16 C17 122.5(13) . . ? C16 C17 C18 118.4(13) . . ? C19 C18 C17 120.7(12) . . ? C18 C19 C20 119.9(13) . . ? N4 C20 C19 119.2(11) . . ? N6 C20 N4 113.7(10) . . ? N6 C20 C19 127.0(13) . . ? C6 N6 Co2 118.1(8) 2_665 . ? C20 N6 C6 121.9(11) . 2_665 ? C20 N6 Co2 120.0(11) . . ? C1 N5 C15 126.0(11) 2_665 . ? C1 N5 Co2 116.6(9) 2_665 . ? C15 N5 Co2 117.4(9) . . ? N1 Co1 Cl1 95.9(3) . . ? N1 Co1 Co2 83.9(3) . . ? N2 Co1 N1 88.6(4) . . ? N2 Co1 N3 171.2(5) . . ? N2 Co1 N4 89.3(4) . . ? N2 Co1 Cl1 94.8(4) . . ? N2 Co1 Co2 86.4(4) . . ? N3 Co1 N1 90.3(4) . . ? N3 Co1 N4 90.0(4) . . ? N3 Co1 Cl1 94.1(4) . . ? N3 Co1 Co2 84.7(3) . . ? N4 Co1 N1 167.9(4) . . ? N4 Co1 Cl1 96.1(3) . . ? N4 Co1 Co2 84.1(3) . . ? Co2 Co1 Cl1 178.77(12) . . ? N6 Co2 N6 90.1(7) 2_665 . ? N6 Co2 N5 90.0(4) . . ? N6 Co2 N5 179.8(7) 2_665 . ? N6 Co2 N5 179.8(7) . 2_665 ? N6 Co2 N5 90.0(4) 2_665 2_665 ? N6 Co2 Co1 89.1(4) . 2_665 ? N6 Co2 Co1 89.5(4) 2_665 2_665 ? N6 Co2 Co1 89.5(4) . . ? N6 Co2 Co1 89.1(4) 2_665 . ? N5 Co2 N5 90.0(7) . 2_665 ? N5 Co2 Co1 90.7(4) . 2_665 ? N5 Co2 Co1 90.8(4) 2_665 2_665 ? N5 Co2 Co1 90.7(4) 2_665 . ? N5 Co2 Co1 90.8(4) . . ? Co1 Co2 Co1 177.95(16) 2_665 . ? Cl3A C21A Cl2A 110(3) . . ? Cl2B C21B Cl3B 97(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 N1 C1 C2 C3 0.7(18) . . . . ? C1 N1 C5 C4 2(2) . . . . ? C1 C2 C3 C4 0(2) . . . . ? C2 C3 C4 C5 0(3) . . . . ? C3 C4 C5 N1 -1(2) . . . . ? C5 N1 C1 C2 -1.6(16) . . . . ? C5 N1 C1 N5 178.0(13) . . . 2_665 ? N2 C6 C7 C8 -1.4(17) . . . . ? C6 N2 C10 C9 4.1(18) . . . . ? C6 C7 C8 C9 4(2) . . . . ? C6 N6 Co2 N6 122.7(11) 2_665 . . 2_665 ? C6 N6 Co2 N5 -57.5(8) 2_665 . . . ? C6 N6 Co2 Co1 33.2(8) 2_665 . . 2_665 ? C6 N6 Co2 Co1 -148.2(8) 2_665 . . . ? C7 C8 C9 C10 -2(2) . . . . ? C8 C9 C10 N2 -2(2) . . . . ? C10 N2 C6 C7 -2.5(14) . . . . ? C10 N2 C6 N6 174.6(10) . . . 2_665 ? N3 C11 C12 C13 0.8(18) . . . . ? N3 C15 N5 C1 157.1(13) . . . 2_665 ? N3 C15 N5 Co2 -19.4(14) . . . . ? C11 N3 C15 C14 -5.9(17) . . . . ? C11 N3 C15 N5 170.7(10) . . . . ? C11 C12 C13 C14 -2(2) . . . . ? C12 C13 C14 C15 0(2) . . . . ? C13 C14 C15 N3 4(2) . . . . ? C13 C14 C15 N5 -172.1(13) . . . . ? C14 C15 N5 C1 -26(2) . . . 2_665 ? C14 C15 N5 Co2 157.1(11) . . . . ? C15 N3 C11 C12 3.3(15) . . . . ? N4 C16 C17 C18 -1.9(17) . . . . ? N4 C20 N6 C6 158.1(11) . . . 2_665 ? N4 C20 N6 Co2 -23.9(15) . . . . ? C16 N4 C20 C19 -2.6(18) . . . . ? C16 N4 C20 N6 174.0(11) . . . . ? C16 C17 C18 C19 3(2) . . . . ? C17 C18 C19 C20 -4(2) . . . . ? C18 C19 C20 N4 3(2) . . . . ? C18 C19 C20 N6 -172.6(14) . . . . ? C19 C20 N6 C6 -26(2) . . . 2_665 ? C19 C20 N6 Co2 152.4(12) . . . . ? C20 N4 C16 C17 1.8(17) . . . . ? C20 N6 Co2 N6 -55.4(8) . . . 2_665 ? C20 N6 Co2 N5 124.5(11) . . . . ? C20 N6 Co2 Co1 33.7(10) . . . . ? C20 N6 Co2 Co1 -144.9(10) . . . 2_665 ? N6 C6 C7 C8 -178.2(11) 2_665 . . . ? N5 C1 C2 C3 -178.8(14) 2_665 . . . ? Co1 N1 C1 C2 -176.2(9) . . . . ? Co1 N1 C1 N5 3.3(15) . . . 2_665 ? Co1 N1 C5 C4 176.4(11) . . . . ? Co1 N2 C6 C7 -177.7(8) . . . . ? Co1 N2 C6 N6 -0.6(13) . . . 2_665 ? Co1 N2 C10 C9 179.3(11) . . . . ? Co1 N3 C11 C12 -178.5(10) . . . . ? Co1 N3 C15 C14 176.1(9) . . . . ? Co1 N3 C15 N5 -7.3(15) . . . . ? Co1 N4 C16 C17 -179.4(10) . . . . ? Co1 N4 C20 C19 178.8(10) . . . . ? Co1 N4 C20 N6 -4.7(16) . . . . ? _shelx_estimated_absorpt_T_max ? _shelx_estimated_absorpt_T_min ? _shelx_hkl_checksum 7445 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelxl_version_number 2013-2 _database_code_depnum_ccdc_archive 'CCDC 952402' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_c2a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'Co3 Cl2 C40 N12 H40' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 13.7147(15) _cell_length_b 12.7050(6) _cell_length_c 10.8427(17) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1889.3(4) _cell_formula_units_Z 2 _cell_measurement_reflns_used 2180 _cell_measurement_temperature 293.0(9) _cell_measurement_pressure 740000(40000) _cell_measurement_theta_max 28.4153 _cell_measurement_theta_min 1.5990 _exptl_absorpt_coefficient_mu 1.639 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.67959 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.37.1t (release 26-07-2012 CrysAlis171 .NET) (compiled Aug 1 2012,17:32:42) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.783 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description prism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.1612 _exptl_crystal_size_mid 0.1166 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0818 _diffrn_reflns_av_unetI/netI 0.1207 _diffrn_reflns_Laue_measured_fraction_full 0.584 _diffrn_reflns_Laue_measured_fraction_max 0.499 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_number 7040 _diffrn_reflns_point_group_measured_fraction_full 0.571 _diffrn_reflns_point_group_measured_fraction_max 0.470 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 28.491 _diffrn_reflns_theta_min 2.185 _diffrn_ambient_temperature 293.0(9) _diffrn_ambient_pressure 740000(40000) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.5537 _diffrn_measured_fraction_theta_max 0.7432 _diffrn_measurement_details ; #__ type_ start__ end____ width___ exp.time_ 1 omega -21.00 31.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.5994 -26.0000 7.0000 52 #__ type_ start__ end____ width___ exp.time_ 2 omega -14.00 12.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.5994 46.0000 -11.0000 26 #__ type_ start__ end____ width___ exp.time_ 3 omega 37.00 64.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.5994 -99.0000 60.0000 27 #__ type_ start__ end____ width___ exp.time_ 4 omega 68.00 106.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.5994 -178.0000 -90.0000 38 #__ type_ start__ end____ width___ exp.time_ 5 omega -3.00 22.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.5369 -114.0000 -135.0000 25 #__ type_ start__ end____ width___ exp.time_ 6 omega -32.00 6.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.5994 97.0000 143.0000 38 #__ type_ start__ end____ width___ exp.time_ 7 omega -55.00 28.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.5369 39.0000 -12.0000 83 #__ type_ start__ end____ width___ exp.time_ 8 omega -29.00 26.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.5369 -39.0000 -167.0000 55 #__ type_ start__ end____ width___ exp.time_ 9 omega 3.00 39.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.5369 -114.0000 45.0000 36 ; _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 -0.0312663000 _diffrn_orient_matrix_UB_12 -0.0018054000 _diffrn_orient_matrix_UB_13 0.0520219000 _diffrn_orient_matrix_UB_21 -0.0343326000 _diffrn_orient_matrix_UB_22 0.0319421000 _diffrn_orient_matrix_UB_23 -0.0314746000 _diffrn_orient_matrix_UB_31 -0.0227299000 _diffrn_orient_matrix_UB_32 -0.0457279000 _diffrn_orient_matrix_UB_33 -0.0240484000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.793 _reflns_Friedel_fraction_full 0.556 _reflns_Friedel_fraction_max 0.438 _reflns_number_gt 1432 _reflns_number_total 2255 _reflns_odcompleteness_completeness 55.37 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 26.32 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.37.1t (release 26-07-2012 CrysAlis171 .NET) (compiled Aug 1 2012,17:32:42) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.37.1t (release 26-07-2012 CrysAlis171 .NET) (compiled Aug 1 2012,17:32:42) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.37.1t (release 26-07-2012 CrysAlis171 .NET) (compiled Aug 1 2012,17:32:42) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.595 _refine_diff_density_min -0.513 _refine_diff_density_rms 0.094 _refine_ls_abs_structure_details ; Flack x determined using 475 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). ; _refine_ls_abs_structure_Flack 0.000(2) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 2255 _refine_ls_number_restraints 588 _refine_ls_R_factor_all 0.1185 _refine_ls_R_factor_gt 0.0588 _refine_ls_restrained_S_all 0.991 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.0391P)^2^+2.6811P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.1059 _refine_ls_wR_factor_ref 0.1403 _refine_special_details ; ? ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups 2. Restrained distances Cl2B-C21B 1.79 with sigma of 0.05 C21B-Cl3B 1.79 with sigma of 0.05 Cl2A-C21A 1.79 with sigma of 0.05 C21A-Cl3A 1.79 with sigma of 0.05 Cl3B-Cl2B 2.9 with sigma of 0.2 3. Restrained planarity N1, C1, C2, C3, C4, C5 with sigma of 0.1 N2, C6, C7, C8, C9, C10 with sigma of 0.1 N3, C11, C12, C13, C14, C15 with sigma of 0.1 N4, C16, C17, C18, C19, C20 with sigma of 0.1 4. Uiso/Uaniso restraints and constraints C21A \\sim C21B \\sim Cl2A \\sim Cl3B \\sim Cl3A \\sim Cl2B: within 5A with sigma of 0.03 and sigma for terminal atoms of 0.06 5. Same fragment restrains {N2, C6, C7, C8, C9, C10} {N3, C11, C12, C13, C14, C15} {N4, C16, C17, C18, C19, C20} {N1, C5, C4, C3, C2, C1} {C1, C2, C3, C4, C5, N1} as {N1, C1, C2, C3, C4, C5} {C21B, Cl2B, Cl3B} as {C21A, Cl2A, Cl3A} 6. Others 0.5*Sof(C21A)=0.5*Sof(H21A)=0.5*Sof(H21B)=0.5*Sof(Cl2A)=0.5*Sof(Cl3A)=1-0.5* Sof(C21B)=1-0.5*Sof(H21C)=1-0.5*Sof(H21D)=1-0.5*Sof(Cl2B)=1-0.5*Sof(Cl3B) 7.a Secondary CH2 refined with riding coordinates: C21A(H21A,H21B), C21B(H21C,H21D) 7.b Aromatic/amide H refined with riding coordinates: C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19) ; _atom_sites_solution_hydrogens geom _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5338(8) 0.6778(7) -0.1588(11) 0.031(3) Uiso 1 1 d D . . . . C1 C 0.4552(9) 0.6219(8) -0.2017(13) 0.024(3) Uiso 1 1 d D . . . . C2 C 0.4235(9) 0.6349(9) -0.3207(13) 0.032(4) Uiso 1 1 d D . . . . H2 H 0.3694 0.5972 -0.3479 0.039 Uiso 1 1 calc R U . . . C3 C 0.4696(10) 0.7020(10) -0.4001(15) 0.046(5) Uiso 1 1 d D . . . . H3 H 0.4495 0.7083 -0.4817 0.055 Uiso 1 1 calc R U . . . C4 C 0.5466(12) 0.7599(11) -0.3557(15) 0.050(5) Uiso 1 1 d D . . . . H4 H 0.5764 0.8098 -0.4059 0.059 Uiso 1 1 calc R U . . . C5 C 0.5793(10) 0.7446(9) -0.2387(14) 0.037(4) Uiso 1 1 d D . . . . H5 H 0.6344 0.7809 -0.2124 0.044 Uiso 1 1 calc R U . . . N2 N 0.4702(8) 0.7232(7) 0.0795(11) 0.028(3) Uiso 1 1 d D . . . . C6 C 0.3998(8) 0.6633(8) 0.1341(13) 0.024(3) Uiso 1 1 d D . . . . C7 C 0.3171(9) 0.7104(8) 0.1787(14) 0.032(4) Uiso 1 1 d D . . . . H7 H 0.2704 0.6693 0.2180 0.038 Uiso 1 1 calc R U . . . C8 C 0.3012(10) 0.8170(8) 0.1669(15) 0.036(4) Uiso 1 1 d D . . . . H8 H 0.2432 0.8474 0.1933 0.043 Uiso 1 1 calc R U . . . C9 C 0.3739(10) 0.8775(10) 0.1148(16) 0.039(4) Uiso 1 1 d D . . . . H9 H 0.3676 0.9502 0.1108 0.047 Uiso 1 1 calc R U . . . C10 C 0.4556(11) 0.8290(8) 0.0691(14) 0.035(4) Uiso 1 1 d D . . . . H10 H 0.5027 0.8696 0.0297 0.041 Uiso 1 1 calc R U . . . N3 N 0.6950(8) 0.5709(7) -0.0518(11) 0.027(3) Uiso 1 1 d D . . . . C11 C 0.7880(9) 0.6000(9) -0.0296(14) 0.036(4) Uiso 1 1 d D . . . . H11 H 0.7990 0.6600 0.0176 0.043 Uiso 1 1 calc R U . . . C12 C 0.8679(11) 0.5450(10) -0.0734(16) 0.049(5) Uiso 1 1 d D . . . . H12 H 0.9311 0.5670 -0.0562 0.059 Uiso 1 1 calc R U . . . C13 C 0.8502(10) 0.4561(10) -0.1437(16) 0.047(4) Uiso 1 1 d D . . . . H13 H 0.9023 0.4179 -0.1755 0.057 Uiso 1 1 calc R U . . . C14 C 0.7576(9) 0.4242(9) -0.1667(15) 0.028(3) Uiso 1 1 d D . . . . H14 H 0.7461 0.3654 -0.2156 0.033 Uiso 1 1 calc R U . . . C15 C 0.6804(9) 0.4799(9) -0.1169(14) 0.027(3) Uiso 1 1 d D . . . . N4 N 0.6216(8) 0.6126(7) 0.1811(11) 0.024(3) Uiso 1 1 d D . . . . C16 C 0.6494(9) 0.6867(10) 0.2656(14) 0.040(4) Uiso 1 1 d D . . . . H16 H 0.6517 0.7567 0.2409 0.048 Uiso 1 1 calc R U . . . C17 C 0.6738(10) 0.6632(9) 0.3839(14) 0.039(4) Uiso 1 1 d D . . . . H17 H 0.6915 0.7159 0.4390 0.047 Uiso 1 1 calc R U . . . C18 C 0.6715(12) 0.5596(9) 0.4197(14) 0.046(5) Uiso 1 1 d D . . . . H18 H 0.6879 0.5409 0.5000 0.055 Uiso 1 1 calc R U . . . C19 C 0.6448(10) 0.4839(10) 0.3365(14) 0.038(4) Uiso 1 1 d D . . . . H19 H 0.6436 0.4138 0.3610 0.045 Uiso 1 1 calc R U . . . C20 C 0.6197(11) 0.5095(9) 0.2167(14) 0.027(4) Uiso 1 1 d D . . . . N6 N 0.5834(8) 0.4431(9) 0.1307(14) 0.023(3) Uiso 1 1 d . . . . . N5 N 0.5840(9) 0.4481(9) -0.1172(14) 0.029(3) Uiso 1 1 d . . . . . Cl1 Cl 0.6849(2) 0.8216(2) 0.0145(5) 0.0349(10) Uani 1 1 d . . . . . Co1 Co 0.58702(12) 0.65657(11) 0.0126(3) 0.0256(5) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 0.0080(4) 0.0246(7) Uani 1 2 d S T P . . C21A C 0.029(3) 0.491(7) 0.317(4) 0.056(18) Uiso 0.418(13) 1 d D U P A -1 H21A H 0.0241 0.4217 0.3556 0.067 Uiso 0.418(13) 1 calc R U P A -1 H21B H 0.0557 0.5386 0.3783 0.067 Uiso 0.418(13) 1 calc R U P A -1 Cl2A Cl 0.1097(11) 0.4829(10) 0.192(2) 0.075(5) Uiso 0.418(13) 1 d D U P A -1 Cl3A Cl -0.0877(13) 0.5333(15) 0.275(2) 0.073(5) Uiso 0.418(13) 1 d D U P A -1 C21B C 0.070(7) 0.516(11) 0.32(3) 0.06(3) Uiso 0.082(13) 1 d D U P A -2 H21C H 0.0957 0.5744 0.2734 0.070 Uiso 0.082(13) 1 calc R U P A -2 H21D H 0.0904 0.5267 0.4064 0.070 Uiso 0.082(13) 1 calc R U P A -2 Cl2B Cl 0.122(5) 0.399(7) 0.267(10) 0.10(3) Uiso 0.082(13) 1 d D U P A -2 Cl3B Cl -0.058(6) 0.519(8) 0.315(9) 0.045(18) Uiso 0.082(13) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.037(3) 0.0328(14) 0.035(4) 0.000(3) -0.001(2) -0.0074(13) Co1 0.0254(14) 0.0234(8) 0.028(2) -0.0010(14) 0.0012(10) -0.0017(7) Co2 0.0241(18) 0.0228(10) 0.027(3) 0.000 0.000 -0.0010(9) _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 N1 C1 1.373(12) . ? N1 C5 1.364(13) . ? N1 Co1 2.015(12) . ? C1 C2 1.371(14) . ? C1 N5 1.385(19) 2_665 ? C2 C3 1.367(14) . ? C3 C4 1.373(14) . ? C4 C5 1.359(15) . ? N2 C6 1.365(13) . ? N2 C10 1.363(12) . ? N2 Co1 1.952(11) . ? C6 C7 1.371(13) . ? C6 N6 1.373(14) 2_665 ? C7 C8 1.378(13) . ? C8 C9 1.379(14) . ? C9 C10 1.372(14) . ? N3 C11 1.350(13) . ? N3 C15 1.369(13) . ? N3 Co1 1.966(11) . ? C11 C12 1.383(14) . ? C12 C13 1.385(14) . ? C13 C14 1.356(13) . ? C14 C15 1.383(13) . ? C15 N5 1.382(17) . ? N4 C16 1.368(13) . ? N4 C20 1.366(12) . ? N4 Co1 1.969(12) . ? C16 C17 1.358(15) . ? C17 C18 1.374(14) . ? C18 C19 1.368(14) . ? C19 C20 1.382(14) . ? C20 N6 1.352(18) . ? N6 C6 1.373(14) 2_665 ? N6 Co2 1.897(14) . ? N5 C1 1.385(19) 2_665 ? N5 Co2 1.899(15) . ? Cl1 Co1 2.489(3) . ? Co1 Co2 2.3203(14) . ? Co2 N6 1.897(14) 2_665 ? Co2 N5 1.899(15) 2_665 ? Co2 Co1 2.3203(14) 2_665 ? C21A Cl2A 1.75(4) . ? C21A Cl3A 1.75(4) . ? C21B Cl2B 1.76(4) . ? C21B Cl3B 1.76(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 N1 Co1 121.8(9) . . ? C5 N1 C1 117.8(12) . . ? C5 N1 Co1 120.3(9) . . ? N1 C1 N5 114.4(12) . 2_665 ? C2 C1 N1 120.4(11) . . ? C2 C1 N5 125.2(12) . 2_665 ? C3 C2 C1 121.4(13) . . ? C2 C3 C4 118.0(14) . . ? C5 C4 C3 120.3(13) . . ? C4 C5 N1 122.0(13) . . ? C6 N2 Co1 120.0(8) . . ? C10 N2 C6 118.8(11) . . ? C10 N2 Co1 121.1(9) . . ? N2 C6 C7 119.7(10) . . ? N2 C6 N6 114.8(11) . 2_665 ? C7 C6 N6 125.4(11) . 2_665 ? C6 C7 C8 121.8(12) . . ? C7 C8 C9 118.1(12) . . ? C10 C9 C8 119.3(11) . . ? N2 C10 C9 122.2(12) . . ? C11 N3 C15 117.5(10) . . ? C11 N3 Co1 119.8(8) . . ? C15 N3 Co1 122.7(9) . . ? N3 C11 C12 123.3(12) . . ? C11 C12 C13 117.6(13) . . ? C14 C13 C12 120.5(13) . . ? C13 C14 C15 119.5(12) . . ? N3 C15 C14 121.4(11) . . ? N3 C15 N5 112.9(11) . . ? N5 C15 C14 125.5(11) . . ? C16 N4 Co1 119.6(8) . . ? C20 N4 C16 118.4(11) . . ? C20 N4 Co1 122.0(9) . . ? C17 C16 N4 123.4(12) . . ? C16 C17 C18 118.2(13) . . ? C19 C18 C17 119.5(13) . . ? C18 C19 C20 121.4(12) . . ? N4 C20 C19 119.1(12) . . ? N6 C20 N4 114.2(12) . . ? N6 C20 C19 126.4(11) . . ? C6 N6 Co2 119.7(10) 2_665 . ? C20 N6 C6 122.3(13) . 2_665 ? C20 N6 Co2 117.9(8) . . ? C1 N5 Co2 117.4(10) 2_665 . ? C15 N5 C1 124.1(13) . 2_665 ? C15 N5 Co2 118.5(10) . . ? N1 Co1 Cl1 95.2(3) . . ? N1 Co1 Co2 84.8(3) . . ? N2 Co1 N1 89.3(5) . . ? N2 Co1 N3 172.1(4) . . ? N2 Co1 N4 88.6(5) . . ? N2 Co1 Cl1 94.2(3) . . ? N2 Co1 Co2 87.6(3) . . ? N3 Co1 N1 91.1(5) . . ? N3 Co1 N4 89.5(5) . . ? N3 Co1 Cl1 93.6(3) . . ? N3 Co1 Co2 84.6(3) . . ? N4 Co1 N1 169.0(4) . . ? N4 Co1 Cl1 95.8(3) . . ? N4 Co1 Co2 84.3(3) . . ? Co2 Co1 Cl1 178.18(14) . . ? N6 Co2 N6 91.0(9) 2_665 . ? N6 Co2 N5 177.9(7) 2_665 . ? N6 Co2 N5 90.2(4) . . ? N6 Co2 N5 177.9(7) . 2_665 ? N6 Co2 N5 90.2(4) 2_665 2_665 ? N6 Co2 Co1 88.2(4) . 2_665 ? N6 Co2 Co1 90.1(4) 2_665 2_665 ? N6 Co2 Co1 88.2(4) 2_665 . ? N6 Co2 Co1 90.1(4) . . ? N5 Co2 N5 88.7(9) 2_665 . ? N5 Co2 Co1 90.1(4) 2_665 2_665 ? N5 Co2 Co1 91.7(4) . 2_665 ? N5 Co2 Co1 90.1(4) . . ? N5 Co2 Co1 91.7(4) 2_665 . ? Co1 Co2 Co1 177.5(3) . 2_665 ? Cl3A C21A Cl2A 113(3) . . ? Cl2B C21B Cl3B 114(4) . . ? 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 C1 C2 C3 1.0(17) . . . . ? C1 N1 C5 C4 2.8(19) . . . . ? C1 C2 C3 C4 -3(2) . . . . ? C1 N5 Co2 N6 120.6(11) 2_665 . . . ? C1 N5 Co2 N5 -57.6(9) 2_665 . . 2_665 ? C1 N5 Co2 Co1 -149.3(10) 2_665 . . . ? C1 N5 Co2 Co1 32.4(10) 2_665 . . 2_665 ? C2 C3 C4 C5 5(2) . . . . ? C3 C4 C5 N1 -5(2) . . . . ? C5 N1 C1 C2 -0.9(15) . . . . ? C5 N1 C1 N5 176.9(11) . . . 2_665 ? N2 C6 C7 C8 2.0(19) . . . . ? C6 N2 C10 C9 2(2) . . . . ? C6 C7 C8 C9 -4(2) . . . . ? C6 N6 Co2 N6 121.1(12) 2_665 . . 2_665 ? C6 N6 Co2 N5 -60.6(11) 2_665 . . . ? C6 N6 Co2 Co1 31.1(11) 2_665 . . 2_665 ? C6 N6 Co2 Co1 -150.7(11) 2_665 . . . ? C7 C8 C9 C10 5(2) . . . . ? C8 C9 C10 N2 -4(3) . . . . ? C10 N2 C6 C7 -1.0(17) . . . . ? C10 N2 C6 N6 174.4(14) . . . 2_665 ? N3 C11 C12 C13 0.2(17) . . . . ? N3 C15 N5 C1 161.1(13) . . . 2_665 ? N3 C15 N5 Co2 -20.7(16) . . . . ? C11 N3 C15 C14 -5.1(18) . . . . ? C11 N3 C15 N5 170.0(11) . . . . ? C11 C12 C13 C14 -1(2) . . . . ? C12 C13 C14 C15 -1(2) . . . . ? C13 C14 C15 N3 5(2) . . . . ? C13 C14 C15 N5 -169.9(14) . . . . ? C14 C15 N5 C1 -24(2) . . . 2_665 ? C14 C15 N5 Co2 154.2(12) . . . . ? C15 N3 C11 C12 2.7(15) . . . . ? C15 N5 Co2 N6 -57.8(10) . . . . ? C15 N5 Co2 N5 124.0(12) . . . 2_665 ? C15 N5 Co2 Co1 -146.0(10) . . . 2_665 ? C15 N5 Co2 Co1 32.3(10) . . . . ? N4 C16 C17 C18 0.8(18) . . . . ? N4 C20 N6 C6 161.3(12) . . . 2_665 ? N4 C20 N6 Co2 -22.7(17) . . . . ? C16 N4 C20 C19 0.6(19) . . . . ? C16 N4 C20 N6 174.5(12) . . . . ? C16 C17 C18 C19 0(2) . . . . ? C17 C18 C19 C20 0(2) . . . . ? C18 C19 C20 N4 0(2) . . . . ? C18 C19 C20 N6 -173.1(16) . . . . ? C19 C20 N6 C6 -25(2) . . . 2_665 ? C19 C20 N6 Co2 150.8(12) . . . . ? C20 N4 C16 C17 -1.0(16) . . . . ? C20 N6 Co2 N6 -55.0(10) . . . 2_665 ? C20 N6 Co2 N5 123.3(12) . . . . ? C20 N6 Co2 Co1 33.2(11) . . . . ? C20 N6 Co2 Co1 -145.0(11) . . . 2_665 ? N6 C6 C7 C8 -172.9(16) 2_665 . . . ? N5 C1 C2 C3 -176.6(12) 2_665 . . . ? Co1 N1 C1 C2 -177.1(9) . . . . ? Co1 N1 C1 N5 0.7(14) . . . 2_665 ? Co1 N1 C5 C4 179.0(11) . . . . ? Co1 N2 C6 C7 -178.7(10) . . . . ? Co1 N2 C6 N6 -3.3(16) . . . 2_665 ? Co1 N2 C10 C9 179.6(13) . . . . ? Co1 N3 C11 C12 -178.9(11) . . . . ? Co1 N3 C15 C14 176.5(10) . . . . ? Co1 N3 C15 N5 -8.3(17) . . . . ? Co1 N4 C16 C17 179.5(10) . . . . ? Co1 N4 C20 C19 -180.0(10) . . . . ? Co1 N4 C20 N6 -6.0(17) . . . . ? loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist _exptl_oxdiff_crystal_face_indexfrac_h _exptl_oxdiff_crystal_face_indexfrac_k _exptl_oxdiff_crystal_face_indexfrac_l _exptl_oxdiff_crystal_face_x _exptl_oxdiff_crystal_face_y _exptl_oxdiff_crystal_face_z 10 -15 3 0.0551 10.0137 -14.9973 3.0452 -0.1276 -0.9187 0.3850 -12 -1 12 0.0250 -11.7006 -0.5843 12.1701 1.0000 0.0000 0.0000 12 1 -12 0.0250 11.7006 0.5843 -12.1701 -1.0000 0.0000 0.0000 -5 17 0 0.0697 -5.0059 16.9830 -0.0443 0.1236 0.7157 -0.6617 16 2 8 0.0766 16.0244 1.9677 8.0093 -0.0879 -0.7394 -0.6468 9 15 6 0.0524 9.0151 14.9637 5.9707 0.0017 -0.0195 -1.0328 -17 0 -8 0.0318 -17.0257 0.0297 -8.0140 0.1154 0.8377 0.5784 _shelx_estimated_absorpt_T_max ? _shelx_estimated_absorpt_T_min ? _shelx_hkl_checksum 43606 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelxl_version_number 2013-2 _database_code_depnum_ccdc_archive 'CCDC 952403' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_c3a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'C40 H40 N12 Cl4 Co3' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 13.502(2) _cell_length_b 12.5615(13) _cell_length_c 10.381(4) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1760.7(7) _cell_formula_units_Z 2 _cell_measurement_reflns_used 2009 _cell_measurement_temperature 292.4(6) _cell_measurement_pressure 2170000(50000) _cell_measurement_theta_max 25.6446 _cell_measurement_theta_min 1.5051 _exptl_absorpt_coefficient_mu 1.756 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.42054 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.900 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description prism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.1612 _exptl_crystal_size_mid 0.1166 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0844 _diffrn_reflns_av_unetI/netI 0.1257 _diffrn_reflns_Laue_measured_fraction_full 0.519 _diffrn_reflns_Laue_measured_fraction_max 0.499 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_number 4005 _diffrn_reflns_point_group_measured_fraction_full 0.465 _diffrn_reflns_point_group_measured_fraction_max 0.445 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 25.700 _diffrn_reflns_theta_min 2.214 _diffrn_ambient_temperature 292.4(6) _diffrn_ambient_pressure 2170000(50000) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.519 _diffrn_measured_fraction_theta_max 0.499 _diffrn_measurement_details ; #__ type_ start__ end____ width___ exp.time_ 1 omega -1.00 36.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 12.6171 -39.0000 -167.0000 37 #__ type_ start__ end____ width___ exp.time_ 2 omega 14.00 40.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -13.4764 -135.0000 -123.0000 26 #__ type_ start__ end____ width___ exp.time_ 3 omega -52.00 -22.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -13.4764 57.0000 150.0000 30 #__ type_ start__ end____ width___ exp.time_ 4 omega -6.00 21.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -13.4764 57.0000 150.0000 27 #__ type_ start__ end____ width___ exp.time_ 5 omega 2.00 30.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -13.4764 -67.0000 23.0000 28 #__ type_ start__ end____ width___ exp.time_ 6 omega -46.00 7.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 12.6171 114.0000 -45.0000 53 #__ type_ start__ end____ width___ exp.time_ 7 omega 16.00 85.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 12.6171 -135.0000 57.0000 69 #__ type_ start__ end____ width___ exp.time_ 8 omega -114.00 -49.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -13.4764 0.0000 -90.0000 65 #__ type_ start__ end____ width___ exp.time_ 9 omega -2.00 37.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -13.4764 -99.0000 30.0000 39 ; _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 0.0293319000 _diffrn_orient_matrix_UB_12 0.0022245000 _diffrn_orient_matrix_UB_13 0.0566494000 _diffrn_orient_matrix_UB_21 0.0361945000 _diffrn_orient_matrix_UB_22 -0.0327151000 _diffrn_orient_matrix_UB_23 -0.0298098000 _diffrn_orient_matrix_UB_31 0.0242901000 _diffrn_orient_matrix_UB_32 0.0459498000 _diffrn_orient_matrix_UB_33 -0.0239227000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.685 _reflns_Friedel_fraction_full 0.404 _reflns_Friedel_fraction_max 0.385 _reflns_number_gt 997 _reflns_number_total 1496 _reflns_odcompleteness_completeness 58.05 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 23.21 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.617 _refine_diff_density_min -0.735 _refine_diff_density_rms 0.164 _refine_ls_abs_structure_details ; Flack x determined using 295 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). ; _refine_ls_abs_structure_Flack 0.000(6) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.070 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 1496 _refine_ls_number_restraints 589 _refine_ls_R_factor_all 0.1315 _refine_ls_R_factor_gt 0.0756 _refine_ls_restrained_S_all 0.953 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.1256P)^2^+4.3791P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.1870 _refine_ls_wR_factor_ref 0.2406 _refine_special_details ; ? ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups 2. Restrained distances C21A-Cl3A = C21A-Cl2A 1.77 with sigma of 0.08 Cl2A-Cl3A 2.95 with sigma of 0.1 C21B-Cl3B = C21B-Cl2B 1.77 with sigma of 0.08 Cl2B-Cl3B 2.95 with sigma of 0.1 3. Restrained planarity N1, C1, C2, C3, C4, C5 with sigma of 0.1 N2, C6, C7, C8, C9, C10 with sigma of 0.1 N3, C11, C12, C13, C14, C15 with sigma of 0.1 N4, C16, C17, C18, C19, C20 with sigma of 0.1 4. Uiso/Uaniso restraints and constraints Cl3A \\sim C21A \\sim Cl3B \\sim C21B \\sim Cl2A \\sim Cl2B: within 4A with sigma of 0.03 and sigma for terminal atoms of 0.06 5. Same fragment restrains {N2, C6, C7, C8, C9, C10} {N3, C11, C12, C13, C14, C15} {N4, C16, C17, C18, C19, C20} {N1, C5, C4, C3, C2, C1} {C1, C2, C3, C4, C5, N1} as {N1, C1, C2, C3, C4, C5} {C21B, Cl2B, Cl3B} as {C21A, Cl2A, Cl3A} 6. Others 0.5*Sof(C21A)=0.5*Sof(H21A)=0.5*Sof(H21B)=0.5*Sof(Cl2A)=0.5*Sof(Cl3A)=1-0.5* Sof(C21B)=1-0.5*Sof(H21C)=1-0.5*Sof(H21D)=1-0.5*Sof(Cl2B)=1-0.5*Sof(Cl3B) 7.a Secondary CH2 refined with riding coordinates: C21A(H21A,H21B), C21B(H21C,H21D) 7.b Aromatic/amide H refined with riding coordinates: C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19) ; _atom_sites_solution_hydrogens geom _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5317(13) 0.6795(13) -0.1724(19) 0.033(5) Uiso 1 1 d D . . . . C1 C 0.4540(14) 0.6226(14) -0.221(2) 0.037(6) Uiso 1 1 d D . . . . C2 C 0.4216(16) 0.6367(16) -0.344(2) 0.046(8) Uiso 1 1 d D . . . . H2 H 0.3672 0.5981 -0.3727 0.055 Uiso 1 1 calc R U . . . C3 C 0.4671(17) 0.7062(17) -0.425(2) 0.048(8) Uiso 1 1 d D . . . . H3 H 0.4469 0.7121 -0.5102 0.058 Uiso 1 1 calc R U . . . C4 C 0.5433(18) 0.767(2) -0.378(2) 0.054(8) Uiso 1 1 d D . . . . H4 H 0.5724 0.8195 -0.4296 0.065 Uiso 1 1 calc R U . . . C5 C 0.5754(15) 0.7505(17) -0.256(2) 0.036(7) Uiso 1 1 d D . . . . H5 H 0.6299 0.7889 -0.2266 0.043 Uiso 1 1 calc R U . . . N2 N 0.4698(11) 0.7261(12) 0.0724(17) 0.020(4) Uiso 1 1 d D . . . . C6 C 0.3976(12) 0.6663(13) 0.1292(19) 0.019(5) Uiso 1 1 d D . . . . C7 C 0.3124(14) 0.7129(13) 0.177(2) 0.033(7) Uiso 1 1 d D . . . . H7 H 0.2637 0.6712 0.2156 0.039 Uiso 1 1 calc R U . . . C8 C 0.3003(14) 0.8211(13) 0.168(3) 0.030(6) Uiso 1 1 d D . . . . H8 H 0.2429 0.8533 0.1982 0.036 Uiso 1 1 calc R U . . . C9 C 0.3735(15) 0.8807(15) 0.114(3) 0.041(7) Uiso 1 1 d D . . . . H9 H 0.3676 0.9544 0.1111 0.050 Uiso 1 1 calc R U . . . C10 C 0.4549(17) 0.8332(14) 0.063(2) 0.038(8) Uiso 1 1 d D . . . . H10 H 0.5019 0.8749 0.0215 0.046 Uiso 1 1 calc R U . . . N3 N 0.6989(12) 0.5717(12) -0.061(2) 0.033(6) Uiso 1 1 d D . . . . C11 C 0.7934(12) 0.5977(14) -0.028(2) 0.032(6) Uiso 1 1 d D . . . . H11 H 0.8046 0.6565 0.0246 0.039 Uiso 1 1 calc R U . . . C12 C 0.8726(15) 0.5390(16) -0.071(2) 0.041(7) Uiso 1 1 d D . . . . H12 H 0.9368 0.5566 -0.0463 0.049 Uiso 1 1 calc R U . . . C13 C 0.8552(14) 0.4541(16) -0.150(3) 0.043(7) Uiso 1 1 d D . . . . H13 H 0.9080 0.4156 -0.1838 0.052 Uiso 1 1 calc R U . . . C14 C 0.7605(13) 0.4259(15) -0.179(3) 0.033(6) Uiso 1 1 d D . . . . H14 H 0.7490 0.3693 -0.2348 0.039 Uiso 1 1 calc R U . . . C15 C 0.6814(14) 0.4801(15) -0.127(3) 0.040(7) Uiso 1 1 d D . . . . N4 N 0.6224(14) 0.6161(12) 0.1786(18) 0.034(5) Uiso 1 1 d D . . . . C16 C 0.6510(14) 0.6926(15) 0.264(2) 0.039(7) Uiso 1 1 d D . . . . H16 H 0.6524 0.7636 0.2387 0.047 Uiso 1 1 calc R U . . . C17 C 0.6771(17) 0.6658(16) 0.385(2) 0.052(8) Uiso 1 1 d D . . . . H17 H 0.6977 0.7181 0.4428 0.062 Uiso 1 1 calc R U . . . C18 C 0.6735(18) 0.5626(15) 0.424(2) 0.044(8) Uiso 1 1 d D . . . . H18 H 0.6884 0.5451 0.5084 0.053 Uiso 1 1 calc R U . . . C19 C 0.6482(17) 0.4846(16) 0.339(2) 0.046(7) Uiso 1 1 d D . . . . H19 H 0.6498 0.4136 0.3640 0.055 Uiso 1 1 calc R U . . . C20 C 0.6203(17) 0.5118(14) 0.217(2) 0.033(7) Uiso 1 1 d D . . . . N6 N 0.5843(14) 0.4438(16) 0.127(3) 0.027(5) Uiso 1 1 d . . . . . N5 N 0.5837(14) 0.4483(16) -0.130(2) 0.026(5) Uiso 1 1 d . . . . . Cl1 Cl 0.6863(4) 0.8227(4) 0.0036(11) 0.0375(18) Uani 1 1 d . . . . . Co1 Co 0.58737(18) 0.6578(2) 0.0035(5) 0.0278(11) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 -0.0031(8) 0.0297(14) Uani 1 2 d S T P . . C21A C 0.019(6) 0.472(10) 0.321(10) 0.06(3) Uiso 0.290(18) 1 d D U P A -1 H21A H 0.0048 0.3976 0.3363 0.075 Uiso 0.290(18) 1 calc R U P A -1 H21B H 0.0429 0.5027 0.4009 0.075 Uiso 0.290(18) 1 calc R U P A -1 Cl2A Cl 0.116(2) 0.483(2) 0.200(4) 0.064(10) Uiso 0.290(18) 1 d D U P A -1 Cl3A Cl -0.090(3) 0.537(2) 0.275(4) 0.052(10) Uiso 0.290(18) 1 d D U P A -1 C21B C 0.081(6) 0.514(7) 0.28(3) 0.07(3) Uiso 0.210(18) 1 d D U P A -2 H21C H 0.1044 0.5454 0.3638 0.084 Uiso 0.210(18) 1 calc R U P A -2 H21D H 0.1036 0.5576 0.2132 0.084 Uiso 0.210(18) 1 calc R U P A -2 Cl2B Cl 0.132(3) 0.380(3) 0.268(5) 0.066(14) Uiso 0.210(18) 1 d D U P A -2 Cl3B Cl -0.048(3) 0.510(3) 0.285(5) 0.039(11) Uiso 0.210(18) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.039(4) 0.032(3) 0.042(7) 0.004(5) 0.004(4) -0.010(2) Co1 0.026(2) 0.0269(16) 0.031(4) 0.001(2) 0.0001(19) 0.0003(12) Co2 0.027(3) 0.027(2) 0.036(5) 0.000 0.000 0.0004(17) _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 N1 C1 1.365(16) . ? N1 C5 1.375(16) . ? N1 Co1 1.993(19) . ? C1 C2 1.360(18) . ? C1 N5 1.39(3) 2_665 ? C2 C3 1.360(17) . ? C3 C4 1.373(17) . ? C4 C5 1.363(18) . ? N2 C6 1.365(16) . ? N2 C10 1.364(15) . ? N2 Co1 1.941(15) . ? C6 C7 1.383(17) . ? C6 N6 1.40(2) 2_665 ? C7 C8 1.372(16) . ? C8 C9 1.362(17) . ? C9 C10 1.354(17) . ? N3 C11 1.361(16) . ? N3 C15 1.362(16) . ? N3 Co1 1.971(17) . ? C11 C12 1.373(17) . ? C12 C13 1.367(17) . ? C13 C14 1.361(16) . ? C14 C15 1.376(17) . ? C15 N5 1.38(3) . ? N4 C16 1.363(17) . ? N4 C20 1.369(16) . ? N4 Co1 1.95(2) . ? C16 C17 1.351(17) . ? C17 C18 1.356(17) . ? C18 C19 1.359(17) . ? C19 C20 1.366(17) . ? C20 N6 1.35(3) . ? N6 C6 1.40(2) 2_665 ? N6 Co2 1.90(2) . ? N5 C1 1.39(3) 2_665 ? N5 Co2 1.85(2) . ? Cl1 Co1 2.465(5) . ? Co1 Co2 2.308(2) . ? Co2 N6 1.90(2) 2_665 ? Co2 N5 1.85(2) 2_665 ? Co2 Co1 2.308(2) 2_665 ? C21A Cl2A 1.82(7) . ? C21A Cl3A 1.74(6) . ? C21B Cl2B 1.82(7) . ? C21B Cl3B 1.74(6) . ? 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 C1 N1 C5 116.0(17) . . ? C1 N1 Co1 123.7(14) . . ? C5 N1 Co1 120.1(13) . . ? N1 C1 N5 111.5(19) . 2_665 ? C2 C1 N1 121.6(18) . . ? C2 C1 N5 126.9(19) . 2_665 ? C3 C2 C1 121.3(19) . . ? C2 C3 C4 118.7(19) . . ? C5 C4 C3 118.6(18) . . ? C4 C5 N1 123.5(18) . . ? C6 N2 Co1 120.0(11) . . ? C10 N2 C6 117.8(15) . . ? C10 N2 Co1 122.1(12) . . ? N2 C6 C7 121.2(14) . . ? N2 C6 N6 114.2(16) . 2_665 ? C7 C6 N6 124.5(16) . 2_665 ? C8 C7 C6 119.5(16) . . ? C9 C8 C7 119.2(17) . . ? C10 C9 C8 120.4(17) . . ? C9 C10 N2 121.8(17) . . ? C11 N3 C15 119.5(15) . . ? C11 N3 Co1 120.0(12) . . ? C15 N3 Co1 120.1(12) . . ? N3 C11 C12 121.4(17) . . ? C13 C12 C11 118.7(17) . . ? C14 C13 C12 119.8(17) . . ? C13 C14 C15 120.9(17) . . ? N3 C15 C14 118.7(16) . . ? N3 C15 N5 114.9(17) . . ? C14 C15 N5 126.3(16) . . ? C16 N4 C20 119.5(16) . . ? C16 N4 Co1 119.1(13) . . ? C20 N4 Co1 121.5(14) . . ? C17 C16 N4 120.3(17) . . ? C16 C17 C18 120.1(19) . . ? C17 C18 C19 120.6(18) . . ? C18 C19 C20 119.3(18) . . ? C19 C20 N4 120.2(18) . . ? N6 C20 N4 114.4(19) . . ? N6 C20 C19 125.4(18) . . ? C6 N6 Co2 118.7(17) 2_665 . ? C20 N6 C6 123(2) . 2_665 ? C20 N6 Co2 117.9(14) . . ? C1 N5 Co2 118.8(15) 2_665 . ? C15 N5 C1 123(2) . 2_665 ? C15 N5 Co2 117.8(16) . . ? N1 Co1 Cl1 95.2(5) . . ? N1 Co1 Co2 84.1(5) . . ? N2 Co1 N1 88.2(8) . . ? N2 Co1 N3 172.9(7) . . ? N2 Co1 N4 88.5(8) . . ? N2 Co1 Cl1 94.1(5) . . ? N2 Co1 Co2 88.4(5) . . ? N3 Co1 N1 93.0(8) . . ? N3 Co1 Cl1 92.7(5) . . ? N3 Co1 Co2 84.8(5) . . ? N4 Co1 N1 169.1(7) . . ? N4 Co1 N3 89.0(8) . . ? N4 Co1 Cl1 95.4(5) . . ? N4 Co1 Co2 85.5(5) . . ? Co2 Co1 Cl1 177.4(3) . . ? N6 Co2 N6 89.4(15) 2_665 . ? N6 Co2 Co1 88.0(6) . 2_665 ? N6 Co2 Co1 89.6(6) 2_665 2_665 ? N6 Co2 Co1 88.0(6) 2_665 . ? N6 Co2 Co1 89.6(6) . . ? N5 Co2 N6 90.6(8) 2_665 2_665 ? N5 Co2 N6 178.6(10) . 2_665 ? N5 Co2 N6 178.6(10) 2_665 . ? N5 Co2 N6 90.6(8) . . ? N5 Co2 N5 89.4(15) . 2_665 ? N5 Co2 Co1 91.8(6) . 2_665 ? N5 Co2 Co1 91.8(6) 2_665 . ? N5 Co2 Co1 90.6(6) . . ? N5 Co2 Co1 90.6(6) 2_665 2_665 ? Co1 Co2 Co1 176.6(4) . 2_665 ? Cl3A C21A Cl2A 113(5) . . ? Cl3B C21B Cl2B 111(5) . . ? 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 C1 C2 C3 2(2) . . . . ? C1 N1 C5 C4 2(3) . . . . ? C1 C2 C3 C4 -4(3) . . . . ? C1 N5 Co2 N6 121.4(19) 2_665 . . . ? C1 N5 Co2 N5 -57.2(16) 2_665 . . 2_665 ? C1 N5 Co2 Co1 33.4(17) 2_665 . . 2_665 ? C1 N5 Co2 Co1 -149.0(17) 2_665 . . . ? C2 C3 C4 C5 5(4) . . . . ? C3 C4 C5 N1 -4(4) . . . . ? C5 N1 C1 C2 -1(2) . . . . ? C5 N1 C1 N5 179(2) . . . 2_665 ? N2 C6 C7 C8 0(2) . . . . ? C6 N2 C10 C9 3(3) . . . . ? C6 C7 C8 C9 -1(3) . . . . ? C7 C8 C9 C10 4(4) . . . . ? C8 C9 C10 N2 -4(4) . . . . ? C10 N2 C6 C7 -1(2) . . . . ? C10 N2 C6 N6 176(2) . . . 2_665 ? N3 C11 C12 C13 1(2) . . . . ? N3 C15 N5 C1 160(2) . . . 2_665 ? N3 C15 N5 Co2 -21(3) . . . . ? C11 N3 C15 C14 -12(3) . . . . ? C11 N3 C15 N5 166(2) . . . . ? C11 C12 C13 C14 -4(3) . . . . ? C12 C13 C14 C15 -2(4) . . . . ? C13 C14 C15 N3 9(4) . . . . ? C13 C14 C15 N5 -168(2) . . . . ? C14 C15 N5 C1 -23(4) . . . 2_665 ? C14 C15 N5 Co2 155(2) . . . . ? C15 N3 C11 C12 6(2) . . . . ? C15 N5 Co2 N6 -56.7(17) . . . . ? C15 N5 Co2 N5 125(2) . . . 2_665 ? C15 N5 Co2 Co1 32.8(18) . . . . ? C15 N5 Co2 Co1 -144.8(17) . . . 2_665 ? N4 C16 C17 C18 -1(2) . . . . ? N4 C20 N6 C6 160(2) . . . 2_665 ? N4 C20 N6 Co2 -23(3) . . . . ? C16 N4 C20 C19 -1(3) . . . . ? C16 N4 C20 N6 175.6(19) . . . . ? C16 C17 C18 C19 3(3) . . . . ? C17 C18 C19 C20 -4(4) . . . . ? C18 C19 C20 N4 3(4) . . . . ? C18 C19 C20 N6 -173(3) . . . . ? C19 C20 N6 C6 -23(4) . . . 2_665 ? C19 C20 N6 Co2 154(2) . . . . ? C20 N4 C16 C17 0(2) . . . . ? N6 C6 C7 C8 -176(3) 2_665 . . . ? N5 C1 C2 C3 -178(2) 2_665 . . . ? Co1 N1 C1 C2 -176.8(15) . . . . ? Co1 N1 C1 N5 3(2) . . . 2_665 ? Co1 N1 C5 C4 178(2) . . . . ? Co1 N2 C6 C7 -179.0(15) . . . . ? Co1 N2 C6 N6 -2(2) . . . 2_665 ? Co1 N2 C10 C9 -179(2) . . . . ? Co1 N3 C11 C12 179.7(16) . . . . ? Co1 N3 C15 C14 175.2(18) . . . . ? Co1 N3 C15 N5 -8(3) . . . . ? Co1 N4 C16 C17 -178.9(15) . . . . ? Co1 N4 C20 C19 177.9(17) . . . . ? Co1 N4 C20 N6 -5(3) . . . . ? _shelx_estimated_absorpt_T_max ? _shelx_estimated_absorpt_T_min ? _shelx_hkl_checksum 45362 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelxl_version_number 2013-2 _database_code_depnum_ccdc_archive 'CCDC 952404' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_c4a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'C40 H40 N12 Cl4 Co3' 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' Co Co 0.3494 0.9721 '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' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 13.3971(13) _cell_length_b 12.4500(6) _cell_length_c 10.192(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1700.0(4) _cell_formula_units_Z 2 _cell_measurement_reflns_used 1621 _cell_measurement_temperature 292.57(10) _cell_measurement_pressure 3200000(100000) _cell_measurement_theta_max 28.3829 _cell_measurement_theta_min 1.6323 _exptl_absorpt_coefficient_mu 1.820 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.72425 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.980 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description prism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.1612 _exptl_crystal_size_mid 0.1166 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0848 _diffrn_reflns_av_unetI/netI 0.1249 _diffrn_reflns_Laue_measured_fraction_full 0.556 _diffrn_reflns_Laue_measured_fraction_max 0.476 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_number 5186 _diffrn_reflns_point_group_measured_fraction_full 0.527 _diffrn_reflns_point_group_measured_fraction_max 0.436 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 28.445 _diffrn_reflns_theta_min 2.233 _diffrn_ambient_temperature 292.57(10) _diffrn_ambient_pressure 3200000(100000) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.556 _diffrn_measured_fraction_theta_max 0.476 _diffrn_measurement_details ; #__ type_ start__ end____ width___ exp.time_ 1 omega 65.00 106.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.9119 178.0000 -90.0000 41 #__ type_ start__ end____ width___ exp.time_ 2 omega 21.00 54.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.9119 -39.0000 12.0000 33 #__ type_ start__ end____ width___ exp.time_ 3 omega -17.00 29.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.9119 -19.0000 -180.0000 46 #__ type_ start__ end____ width___ exp.time_ 4 omega -47.00 -17.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.9119 135.0000 -57.0000 30 #__ type_ start__ end____ width___ exp.time_ 5 omega -81.00 -49.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.9119 0.0000 -90.0000 32 #__ type_ start__ end____ width___ exp.time_ 6 omega -25.00 13.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - 18.9119 81.0000 151.0000 38 #__ type_ start__ end____ width___ exp.time_ 7 omega -6.00 31.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 -97.0000 -143.0000 37 #__ type_ start__ end____ width___ exp.time_ 8 omega -29.00 -4.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 -39.0000 -167.0000 25 #__ type_ start__ end____ width___ exp.time_ 9 omega -79.00 7.00 1.0000 80.0000 omega____ theta____ kappa____ phi______ frames - -19.6931 114.0000 -45.0000 86 ; _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 0.0302831000 _diffrn_orient_matrix_UB_12 0.0016119000 _diffrn_orient_matrix_UB_13 0.0575296000 _diffrn_orient_matrix_UB_21 0.0358430000 _diffrn_orient_matrix_UB_22 -0.0330393000 _diffrn_orient_matrix_UB_23 -0.0311575000 _diffrn_orient_matrix_UB_31 0.0245370000 _diffrn_orient_matrix_UB_32 0.0461879000 _diffrn_orient_matrix_UB_33 -0.0242746000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.735 _reflns_Friedel_fraction_full 0.494 _reflns_Friedel_fraction_max 0.390 _reflns_number_gt 1112 _reflns_number_total 1870 _reflns_odcompleteness_completeness 52.09 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 26.32 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.527 _refine_diff_density_min -0.530 _refine_diff_density_rms 0.116 _refine_ls_abs_structure_details ; Flack x determined using 360 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). ; _refine_ls_abs_structure_Flack 0.001(5) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.051 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 1870 _refine_ls_number_restraints 32 _refine_ls_R_factor_all 0.1355 _refine_ls_R_factor_gt 0.0710 _refine_ls_restrained_S_all 1.046 _refine_ls_shift/su_max 0.017 _refine_ls_shift/su_mean 0.001 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.0884P)^2^+1.7852P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.1538 _refine_ls_wR_factor_ref 0.1983 _refine_special_details ; ? ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H,H) groups 2. Restrained distances Cl2A-C21A 1.7 with sigma of 0.09 C21A-Cl3A 1.7 with sigma of 0.09 Cl3B-C21B 1.7 with sigma of 0.09 C21B-Cl2B 1.7 with sigma of 0.09 3. Restrained planarity N1, C1, C2, C3, C4, C5 with sigma of 0.1 N2, C6, C7, C8, C9, C10 with sigma of 0.1 N3, C11, C12, C13, C14, C15 with sigma of 0.1 N4, C16, C17, C18, C19, C20 with sigma of 0.1 4. Uiso/Uaniso restraints and constraints C21A \\sim C21B \\sim Cl2A \\sim Cl3A \\sim Cl2B \\sim Cl3B: within 5A with sigma of 0.03 and sigma for terminal atoms of 0.05 5. Others 1-0.5*Sof(C21B)=1-0.5*Sof(H21A)=1-0.5*Sof(H21B)=0.5*Sof(Cl2A)=0.5*Sof(Cl3A)= 0.5*Sof(C21A)=0.5*Sof(H21C)=0.5*Sof(H21D)=1-0.5*Sof(Cl2B)=1-0.5*Sof(Cl3B) Fixed Uiso: H2(0.05) H3(0.053) H4(0.067) H5(0.045) H7(0.042) H8(0.043) H9(0.061) H10(0.033) H11(0.048) H12(0.065) H13(0.052) H14(0.047) H16(0.07) H17(0.068) H18(0.072) H19(0.049) Fixed X: H2(0.365901) H3(0.443) H4(0.5709) H5(0.6355) H7(0.263901) H8(0.242399) H9(0.3655) H10(0.501901) H11(0.8041) H12(0.9382) H13(0.9084) H14(0.751901) H16(0.6505) H17(0.701) H18(0.6946) H19(0.6447) Co2(0.5) Fixed Y: H2(0.603201) H3(0.723101) H4(0.8265) H5(0.7876) H7(0.6725) H8(0.853901) H9(0.9575) H10(0.874599) H11(0.657301) H12(0.5585) H13(0.413301) H14(0.365301) H16(0.7627) H17(0.718) H18(0.544399) H19(0.4127) Co2(0.5) Fixed Z: H2(-0.380099) H3(-0.5169) H4(-0.4336) H5(-0.234099) H7(0.222301) H8(0.2042) H9(0.110901) H10(0.021601) H11(0.0262) H12(-0.0446) H13(-0.176299) H14(-0.236) H16(0.2415) H17(0.4452) H18(0.517) H19(0.3718) 6.a Secondary CH2 refined with riding coordinates: C21B(H21A,H21B), C21A(H21C,H21D) ; _atom_sites_solution_hydrogens mixed _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5348(11) 0.6799(10) -0.171(2) 0.032(4) Uiso 1 1 d . . . . . C1 C 0.4533(12) 0.6257(12) -0.221(2) 0.025(4) Uiso 1 1 d . . . . . C2 C 0.4219(16) 0.6419(14) -0.342(3) 0.045(6) Uiso 1 1 d . . . . . H2 H 0.3659 0.6032 -0.3801 0.050 Uiso 1 1 d . U . . . C3 C 0.4629(18) 0.7124(17) -0.425(3) 0.050(6) Uiso 1 1 d . . . . . H3 H 0.4430 0.7231 -0.5169 0.053 Uiso 1 1 d . U . . . C4 C 0.541(2) 0.7736(19) -0.379(3) 0.061(7) Uiso 1 1 d . . . . . H4 H 0.5709 0.8265 -0.4336 0.067 Uiso 1 1 d . U . . . C5 C 0.5778(15) 0.7516(16) -0.260(3) 0.041(6) Uiso 1 1 d . . . . . H5 H 0.6355 0.7876 -0.2341 0.045 Uiso 1 1 d . U . . . N2 N 0.4708(11) 0.7253(12) 0.0772(16) 0.028(4) Uiso 1 1 d . . . . . C6 C 0.3968(14) 0.6654(13) 0.138(2) 0.034(5) Uiso 1 1 d . . . . . C7 C 0.3127(15) 0.7134(14) 0.188(2) 0.038(5) Uiso 1 1 d . . . . . H7 H 0.2639 0.6725 0.2223 0.042 Uiso 1 1 d . U . . . C8 C 0.3020(17) 0.8236(16) 0.178(3) 0.046(6) Uiso 1 1 d . . . . . H8 H 0.2424 0.8539 0.2042 0.043 Uiso 1 1 d . U . . . C9 C 0.3704(15) 0.8832(15) 0.120(3) 0.041(5) Uiso 1 1 d . . . . . H9 H 0.3655 0.9575 0.1109 0.061 Uiso 1 1 d . U . . . C10 C 0.4553(15) 0.8324(12) 0.071(2) 0.028(5) Uiso 1 1 d . . . . . H10 H 0.5019 0.8746 0.0216 0.033 Uiso 1 1 d . U . . . N3 N 0.6976(13) 0.5725(11) -0.0550(18) 0.034(4) Uiso 1 1 d . . . . . C11 C 0.7918(14) 0.5967(12) -0.023(2) 0.037(5) Uiso 1 1 d . . . . . H11 H 0.8041 0.6573 0.0262 0.048 Uiso 1 1 d . U . . . C12 C 0.8712(18) 0.5411(16) -0.062(2) 0.049(6) Uiso 1 1 d . . . . . H12 H 0.9382 0.5585 -0.0446 0.065 Uiso 1 1 d . U . . . C13 C 0.8529(16) 0.4510(14) -0.139(3) 0.043(5) Uiso 1 1 d . . . . . H13 H 0.9084 0.4133 -0.1763 0.052 Uiso 1 1 d . U . . . C14 C 0.7646(13) 0.4226(12) -0.177(3) 0.031(5) Uiso 1 1 d . . . . . H14 H 0.7519 0.3653 -0.2360 0.047 Uiso 1 1 d . U . . . C15 C 0.6801(15) 0.4806(14) -0.124(3) 0.038(5) Uiso 1 1 d . . . . . N4 N 0.6200(12) 0.6151(10) 0.1874(19) 0.031(4) Uiso 1 1 d . . . . . C16 C 0.6513(14) 0.6900(17) 0.276(3) 0.054(6) Uiso 1 1 d . . . . . H16 H 0.6505 0.7627 0.2415 0.070 Uiso 1 1 d . U . . . C17 C 0.6779(16) 0.6644(18) 0.393(3) 0.055(7) Uiso 1 1 d . . . . . H17 H 0.7010 0.7180 0.4452 0.068 Uiso 1 1 d . U . . . C18 C 0.675(2) 0.5645(18) 0.438(3) 0.059(7) Uiso 1 1 d . . . . . H18 H 0.6946 0.5444 0.5170 0.072 Uiso 1 1 d . U . . . C19 C 0.6474(15) 0.4825(15) 0.348(3) 0.046(5) Uiso 1 1 d . . . . . H19 H 0.6447 0.4127 0.3718 0.049 Uiso 1 1 d . U . . . C20 C 0.6201(14) 0.5122(14) 0.222(2) 0.029(5) Uiso 1 1 d . . . . . N6 N 0.5822(11) 0.4412(11) 0.133(2) 0.022(4) Uiso 1 1 d . . . . . N5 N 0.5849(13) 0.4482(12) -0.133(2) 0.033(5) Uiso 1 1 d . . . . . Cl1 Cl 0.6872(3) 0.8225(3) 0.0112(9) 0.0380(15) Uani 1 1 d . . . . . Co1 Co 0.58734(16) 0.65850(15) 0.0094(4) 0.0298(9) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 0.0025(7) 0.0292(11) Uani 1 2 d S T P . . C21B C 0.056(6) 0.494(5) 0.234(12) 0.034(18) Uiso 0.284(14) 1 d D U P A -2 H21A H 0.0956 0.5573 0.2530 0.040 Uiso 0.284(14) 1 calc R U P A -2 H21B H 0.0450 0.4932 0.1403 0.040 Uiso 0.284(14) 1 calc R U P A -2 Cl2A Cl 0.122(3) 0.486(2) 0.204(5) 0.053(10) Uiso 0.216(14) 1 d D U P A -1 Cl3A Cl -0.096(4) 0.537(3) 0.267(7) 0.071(12) Uiso 0.216(14) 1 d D U P A -1 C21A C 0.012(8) 0.488(13) 0.324(10) 0.03(2) Uiso 0.216(14) 1 d D U P A -1 H21C H 0.0009 0.4155 0.3549 0.034 Uiso 0.216(14) 1 calc R U P A -1 H21D H 0.0318 0.5307 0.4000 0.034 Uiso 0.216(14) 1 calc R U P A -1 Cl2B Cl 0.1354(17) 0.3783(17) 0.271(3) 0.066(8) Uiso 0.284(14) 1 d D U P A -2 Cl3B Cl -0.055(3) 0.515(3) 0.302(5) 0.068(10) Uiso 0.284(14) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.034(3) 0.033(2) 0.048(6) 0.003(4) 0.001(3) -0.0074(17) Co1 0.0303(18) 0.0249(10) 0.034(3) -0.001(2) -0.0004(15) 0.0004(9) Co2 0.030(2) 0.0255(14) 0.032(4) 0.000 0.000 -0.0010(13) _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 N1 C1 1.38(2) . ? N1 C5 1.39(3) . ? N1 Co1 1.99(2) . ? C1 C2 1.32(3) . ? C1 N5 1.38(3) 2_665 ? C2 C3 1.34(3) . ? C3 C4 1.37(3) . ? C4 C5 1.34(4) . ? N2 C6 1.39(3) . ? N2 C10 1.35(2) . ? N2 Co1 1.899(15) . ? C6 C7 1.37(3) . ? C6 N6 1.36(2) 2_665 ? C7 C8 1.38(3) . ? C8 C9 1.32(3) . ? C9 C10 1.39(3) . ? N3 C11 1.34(2) . ? N3 C15 1.37(3) . ? N3 Co1 1.939(17) . ? C11 C12 1.33(3) . ? C12 C13 1.39(3) . ? C13 C14 1.30(3) . ? C14 C15 1.45(3) . ? C15 N5 1.34(3) . ? N4 C16 1.37(3) . ? N4 C20 1.33(2) . ? N4 Co1 1.943(19) . ? C16 C17 1.28(4) . ? C17 C18 1.33(3) . ? C18 C19 1.42(4) . ? C19 C20 1.39(3) . ? C20 N6 1.36(3) . ? N6 C6 1.36(2) 2_665 ? N6 Co2 1.876(19) . ? N5 C1 1.38(3) 2_665 ? N5 Co2 1.91(2) . ? Cl1 Co1 2.442(4) . ? Co1 Co2 2.295(2) . ? Co2 N6 1.876(19) 2_665 ? Co2 N5 1.91(2) 2_665 ? Co2 Co1 2.295(2) 2_665 ? C21B Cl2B 1.83(7) . ? C21B Cl3B 1.66(8) . ? Cl2A C21A 1.92(9) . ? Cl3A C21A 1.68(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 C1 N1 C5 114(2) . . ? C1 N1 Co1 123.5(14) . . ? C5 N1 Co1 122.5(14) . . ? C2 C1 N1 121.2(18) . . ? C2 C1 N5 126(2) . 2_665 ? N5 C1 N1 113(2) 2_665 . ? C1 C2 C3 124(2) . . ? C2 C3 C4 117(3) . . ? C5 C4 C3 118(2) . . ? C4 C5 N1 124(2) . . ? C6 N2 Co1 121.0(12) . . ? C10 N2 C6 116.2(16) . . ? C10 N2 Co1 122.8(13) . . ? C7 C6 N2 121.2(15) . . ? N6 C6 N2 111.1(17) 2_665 . ? N6 C6 C7 127.6(19) 2_665 . ? C6 C7 C8 119.2(19) . . ? C9 C8 C7 121(2) . . ? C8 C9 C10 118.2(17) . . ? N2 C10 C9 123.7(18) . . ? C11 N3 C15 118.4(16) . . ? C11 N3 Co1 120.9(13) . . ? C15 N3 Co1 120.5(13) . . ? C12 C11 N3 124.6(19) . . ? C11 C12 C13 116(2) . . ? C14 C13 C12 123.4(19) . . ? C13 C14 C15 117.7(19) . . ? N3 C15 C14 118.5(17) . . ? N5 C15 N3 116.8(18) . . ? N5 C15 C14 124.6(18) . . ? C16 N4 Co1 119.9(14) . . ? C20 N4 C16 119(2) . . ? C20 N4 Co1 120.9(15) . . ? C17 C16 N4 122(2) . . ? C16 C17 C18 123(3) . . ? C17 C18 C19 117(3) . . ? C20 C19 C18 118.5(19) . . ? N4 C20 C19 120(2) . . ? N4 C20 N6 117(2) . . ? N6 C20 C19 122.6(16) . . ? C6 N6 C20 122.1(19) 2_665 . ? C6 N6 Co2 122.1(16) 2_665 . ? C20 N6 Co2 115.8(11) . . ? C1 N5 Co2 118.2(14) 2_665 . ? C15 N5 C1 126.8(19) . 2_665 ? C15 N5 Co2 114.5(15) . . ? N1 Co1 Cl1 95.1(5) . . ? N1 Co1 Co2 84.6(5) . . ? N2 Co1 N1 89.3(7) . . ? N2 Co1 N3 172.5(7) . . ? N2 Co1 N4 88.1(7) . . ? N2 Co1 Cl1 94.7(5) . . ? N2 Co1 Co2 88.2(5) . . ? N3 Co1 N1 91.7(7) . . ? N3 Co1 N4 89.5(7) . . ? N3 Co1 Cl1 92.7(5) . . ? N3 Co1 Co2 84.5(5) . . ? N4 Co1 N1 168.9(6) . . ? N4 Co1 Cl1 95.9(5) . . ? N4 Co1 Co2 84.5(4) . . ? Co2 Co1 Cl1 177.10(19) . . ? N6 Co2 N6 89.6(12) 2_665 . ? N6 Co2 N5 91.9(6) . . ? N6 Co2 N5 176.8(8) 2_665 . ? N6 Co2 N5 91.9(6) 2_665 2_665 ? N6 Co2 N5 176.8(8) . 2_665 ? N6 Co2 Co1 86.7(5) 2_665 . ? N6 Co2 Co1 86.7(5) . 2_665 ? N6 Co2 Co1 90.8(5) 2_665 2_665 ? N6 Co2 Co1 90.8(5) . . ? N5 Co2 N5 86.7(13) . 2_665 ? N5 Co2 Co1 92.0(5) 2_665 . ? N5 Co2 Co1 90.5(5) . . ? N5 Co2 Co1 90.5(5) 2_665 2_665 ? N5 Co2 Co1 92.0(5) . 2_665 ? Co1 Co2 Co1 176.5(4) . 2_665 ? Cl3B C21B Cl2B 124(6) . . ? Cl3A C21A Cl2A 117(6) . . ? _shelx_estimated_absorpt_T_max ? _shelx_estimated_absorpt_T_min ? _shelx_hkl_checksum 17079 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelxl_version_number 2013-2 _database_code_depnum_ccdc_archive 'CCDC 952405' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_d1a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'C40 H40 N12 Cl4 Co3' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 13.8547(4) _cell_length_b 12.7941(9) _cell_length_c 11.0243(9) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1954.1(2) _cell_formula_units_Z 2 _cell_measurement_reflns_used 5268 _cell_measurement_temperature 293(2) _cell_measurement_pressure 320000(30000) _cell_measurement_theta_max 28.5354 _cell_measurement_theta_min 1.4668 _exptl_absorpt_coefficient_mu 1.582 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.84555 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.712 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description prism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0888 _diffrn_reflns_av_unetI/netI 0.0685 _diffrn_reflns_Laue_measured_fraction_full 0.571 _diffrn_reflns_Laue_measured_fraction_max 0.498 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_number 20518 _diffrn_reflns_point_group_measured_fraction_full 0.579 _diffrn_reflns_point_group_measured_fraction_max 0.494 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 28.598 _diffrn_reflns_theta_min 2.167 _diffrn_ambient_temperature 293(2) _diffrn_ambient_pressure 320000(30000) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.571 _diffrn_measured_fraction_theta_max 0.498 _diffrn_measurement_details ; #__ type_ start__ end____ width___ exp.time_ 1 omega -6.00 49.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 -39.0000 -167.0000 55 #__ type_ start__ end____ width___ exp.time_ 2 omega 94.00 119.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 0.0000 -90.0000 25 #__ type_ start__ end____ width___ exp.time_ 3 omega -26.00 2.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 39.0000 -12.0000 28 #__ type_ start__ end____ width___ exp.time_ 4 omega 3.00 30.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 81.0000 151.0000 27 #__ type_ start__ end____ width___ exp.time_ 5 omega 46.00 72.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 -114.0000 -135.0000 26 #__ type_ start__ end____ width___ exp.time_ 6 omega -32.00 -7.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 97.0000 -35.0000 25 #__ type_ start__ end____ width___ exp.time_ 7 omega -49.00 -23.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 57.0000 150.0000 26 #__ type_ start__ end____ width___ exp.time_ 8 omega 55.00 80.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 178.0000 -60.0000 25 #__ type_ start__ end____ width___ exp.time_ 9 omega -56.00 -30.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 97.0000 143.0000 26 #__ type_ start__ end____ width___ exp.time_ 10 omega -19.00 7.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 19.0000 -30.0000 26 #__ type_ start__ end____ width___ exp.time_ 11 omega -36.00 -2.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 53.0000 162.0000 34 #__ type_ start__ end____ width___ exp.time_ 12 omega -18.00 16.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 -53.0000 17.0000 34 #__ type_ start__ end____ width___ exp.time_ 13 omega 9.00 35.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 -114.0000 45.0000 26 #__ type_ start__ end____ width___ exp.time_ 14 omega -40.00 -8.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 114.0000 -45.0000 32 #__ type_ start__ end____ width___ exp.time_ 15 omega -23.00 64.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 -39.0000 12.0000 87 #__ type_ start__ end____ width___ exp.time_ 16 omega -53.00 -8.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 135.0000 123.0000 45 #__ type_ start__ end____ width___ exp.time_ 17 omega -24.00 26.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 -39.0000 -167.0000 50 #__ type_ start__ end____ width___ exp.time_ 18 omega -64.00 8.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 81.0000 151.0000 72 #__ type_ start__ end____ width___ exp.time_ 19 omega -23.00 26.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 -39.0000 12.0000 49 #__ type_ start__ end____ width___ exp.time_ 20 omega -64.00 -39.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 81.0000 -29.0000 25 #__ type_ start__ end____ width___ exp.time_ 21 omega 3.00 31.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 -99.0000 30.0000 28 #__ type_ start__ end____ width___ exp.time_ 22 omega -92.00 -8.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - -19.5586 135.0000 -57.0000 84 #__ type_ start__ end____ width___ exp.time_ 23 omega -6.00 49.00 1.0000 70.0000 omega____ theta____ kappa____ phi______ frames - 18.7774 -39.0000 -167.0000 55 ; _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 -0.0002307000 _diffrn_orient_matrix_UB_12 0.0370090000 _diffrn_orient_matrix_UB_13 -0.0479780000 _diffrn_orient_matrix_UB_21 0.0085459000 _diffrn_orient_matrix_UB_22 -0.0406884000 _diffrn_orient_matrix_UB_23 -0.0423245000 _diffrn_orient_matrix_UB_31 -0.0504536000 _diffrn_orient_matrix_UB_32 -0.0070648000 _diffrn_orient_matrix_UB_33 -0.0069243000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.890 _reflns_Friedel_fraction_full 0.589 _reflns_Friedel_fraction_max 0.490 _reflns_number_gt 1774 _reflns_number_total 2470 _reflns_odcompleteness_completeness 53.82 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 26.32 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.335 _refine_diff_density_min -0.353 _refine_diff_density_rms 0.076 _refine_ls_abs_structure_details ; Flack x determined using 716 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). ; _refine_ls_abs_structure_Flack -0.0003(13) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 2470 _refine_ls_number_restraints 42 _refine_ls_R_factor_all 0.0883 _refine_ls_R_factor_gt 0.0479 _refine_ls_restrained_S_all 1.052 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.0288P)^2^+3.7012P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0867 _refine_ls_wR_factor_ref 0.1017 _refine_special_details ; ? ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups 2. Restrained distances C21A-Cl3A = C21A-Cl2A 1.7 with sigma of 0.5 Cl2A-Cl3A 2.95 with sigma of 0.5 C21B-Cl3B = C21B-Cl2B 1.7 with sigma of 0.5 Cl2B-Cl3B 2.95 with sigma of 0.8 3. Restrained planarity N1, C1, C2, C3, C4, C5 with sigma of 0.1 N2, C6, C7, C8, C9, C10 with sigma of 0.1 N3, C11, C12, C13, C14, C15 with sigma of 0.1 N4, C16, C17, C18, C19, C20 with sigma of 0.1 4. Uiso/Uaniso restraints and constraints C21A \\sim C21B \\sim Cl2A \\sim Cl2B \\sim Cl3A \\sim Cl3B: within 5A with sigma of 0.02 and sigma for terminal atoms of 0.03 5. Same fragment restrains {N1, C5, C4, C3, C2, C1} as {N1, C1, C2, C3, C4, C5} {C21B, Cl2B, Cl3B} as {C21A, Cl2A, Cl3A} 6. Others 0.5*Sof(C21A)=0.5*Sof(H21A)=0.5*Sof(H21B)=0.5*Sof(Cl2A)=0.5*Sof(Cl3A)=1-0.5* Sof(C21B)=1-0.5*Sof(H21C)=1-0.5*Sof(H21D)=1-0.5*Sof(Cl2B)=1-0.5*Sof(Cl3B) 7.a Secondary CH2 refined with riding coordinates: C21A(H21A,H21B), C21B(H21C,H21D) 7.b Aromatic/amide H refined with riding coordinates: C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19) ; _atom_sites_solution_hydrogens geom _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5351(5) 0.6742(6) -0.1648(8) 0.025(2) Uiso 1 1 d D . . . . C1 C 0.4557(6) 0.6210(8) -0.2051(11) 0.029(2) Uiso 1 1 d D . . . . C2 C 0.4246(7) 0.6334(9) -0.3238(11) 0.041(3) Uiso 1 1 d D . . . . H2 H 0.3708 0.5964 -0.3502 0.049 Uiso 1 1 calc R U . . . C3 C 0.4710(7) 0.6984(9) -0.4030(13) 0.047(3) Uiso 1 1 d D . . . . H3 H 0.4512 0.7042 -0.4833 0.057 Uiso 1 1 calc R U . . . C4 C 0.5488(7) 0.7555(10) -0.3588(12) 0.046(3) Uiso 1 1 d D . . . . H4 H 0.5802 0.8033 -0.4087 0.056 Uiso 1 1 calc R U . . . C5 C 0.5790(7) 0.7413(8) -0.2422(11) 0.034(3) Uiso 1 1 d D . . . . H5 H 0.6319 0.7792 -0.2148 0.041 Uiso 1 1 calc R U . . . N2 N 0.4709(5) 0.7228(7) 0.0691(8) 0.028(2) Uiso 1 1 d . . . . . C6 C 0.4010(6) 0.6596(8) 0.1242(10) 0.026(2) Uiso 1 1 d . . . . . C7 C 0.3165(7) 0.7099(9) 0.1659(11) 0.035(3) Uiso 1 1 d . . . . . H7 H 0.2670 0.6705 0.1999 0.042 Uiso 1 1 calc R U . . . C8 C 0.3069(7) 0.8149(10) 0.1570(12) 0.046(3) Uiso 1 1 d . . . . . H8 H 0.2520 0.8465 0.1885 0.056 Uiso 1 1 calc R U . . . C9 C 0.3767(7) 0.8765(10) 0.1023(13) 0.043(3) Uiso 1 1 d . . . . . H9 H 0.3694 0.9485 0.0954 0.051 Uiso 1 1 calc R U . . . C10 C 0.4560(7) 0.8268(10) 0.0593(10) 0.039(3) Uiso 1 1 d . . . . . H10 H 0.5030 0.8667 0.0207 0.046 Uiso 1 1 calc R U . . . N3 N 0.6941(5) 0.5702(7) -0.0603(8) 0.030(2) Uiso 1 1 d . . . . . C11 C 0.7868(6) 0.5983(9) -0.0416(10) 0.035(3) Uiso 1 1 d . . . . . H11 H 0.7983 0.6578 0.0045 0.042 Uiso 1 1 calc R U . . . C12 C 0.8644(9) 0.5457(10) -0.0854(12) 0.051(4) Uiso 1 1 d . . . . . H12 H 0.9267 0.5690 -0.0698 0.061 Uiso 1 1 calc R U . . . C13 C 0.8488(8) 0.4564(10) -0.1541(12) 0.047(3) Uiso 1 1 d . . . . . H13 H 0.9003 0.4188 -0.1860 0.056 Uiso 1 1 calc R U . . . C14 C 0.7550(6) 0.4246(8) -0.1739(11) 0.037(3) Uiso 1 1 d . . . . . H14 H 0.7429 0.3659 -0.2213 0.044 Uiso 1 1 calc R U . . . C15 C 0.6778(6) 0.4804(9) -0.1228(11) 0.029(3) Uiso 1 1 d . . . . . N4 N 0.6236(5) 0.6119(7) 0.1701(9) 0.028(2) Uiso 1 1 d . . . . . C16 C 0.6493(6) 0.6854(10) 0.2542(13) 0.042(3) Uiso 1 1 d . . . . . H16 H 0.6495 0.7554 0.2315 0.050 Uiso 1 1 calc R U . . . C17 C 0.6745(8) 0.6600(12) 0.3696(14) 0.059(4) Uiso 1 1 d . . . . . H17 H 0.6931 0.7123 0.4233 0.071 Uiso 1 1 calc R U . . . C18 C 0.6726(8) 0.5570(12) 0.4080(14) 0.053(4) Uiso 1 1 d . . . . . H18 H 0.6901 0.5387 0.4867 0.063 Uiso 1 1 calc R U . . . C19 C 0.6437(7) 0.4824(10) 0.3245(12) 0.039(3) Uiso 1 1 d . . . . . H19 H 0.6408 0.4127 0.3480 0.047 Uiso 1 1 calc R U . . . C20 C 0.6186(6) 0.5097(9) 0.2043(11) 0.026(2) Uiso 1 1 d . . . . . N6 N 0.5822(5) 0.4446(8) 0.1211(10) 0.026(2) Uiso 1 1 d . . . . . N5 N 0.5833(6) 0.4453(8) -0.1224(10) 0.025(2) Uiso 1 1 d . . . . . Cl1 Cl 0.68451(14) 0.81959(19) 0.0065(4) 0.0381(7) Uani 1 1 d . . . . . Co1 Co 0.58718(7) 0.65539(10) 0.0043(2) 0.0256(3) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 -0.0003(3) 0.0237(4) Uani 1 2 d S T P . . C21A C 0.0311(18) 0.495(4) 0.304(4) 0.064(11) Uiso 0.443(9) 1 d D U P A -1 H21A H 0.0268 0.4279 0.3448 0.077 Uiso 0.443(9) 1 calc R U P A -1 H21B H 0.0592 0.5442 0.3603 0.077 Uiso 0.443(9) 1 calc R U P A -1 Cl2A Cl 0.1096(7) 0.4812(9) 0.1810(13) 0.081(3) Uiso 0.443(9) 1 d D U P A -1 Cl3A Cl -0.0838(8) 0.5356(13) 0.270(2) 0.091(4) Uiso 0.443(9) 1 d D U P A -1 C21B C 0.061(7) 0.513(9) 0.30(5) 0.068(18) Uiso 0.057(9) 1 d D U P A -2 H21C H 0.0869 0.5465 0.3733 0.081 Uiso 0.057(9) 1 calc R U P A -2 H21D H 0.0776 0.5564 0.2327 0.081 Uiso 0.057(9) 1 calc R U P A -2 Cl2B Cl 0.121(5) 0.394(8) 0.284(9) 0.090(18) Uiso 0.057(9) 1 d D U P A -2 Cl3B Cl -0.062(5) 0.511(8) 0.314(9) 0.040(14) Uiso 0.057(9) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.0389(10) 0.031(2) 0.044(3) 0.0005(18) -0.001(2) -0.0080(9) Co1 0.0231(5) 0.0220(10) 0.0316(12) -0.0009(8) 0.0003(9) -0.0002(4) Co2 0.0219(6) 0.0199(13) 0.0294(17) 0.000 0.000 -0.0001(6) _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 N1 C1 1.368(11) . ? N1 C5 1.354(12) . ? N1 Co1 2.013(9) . ? C1 C2 1.386(14) . ? C1 N5 1.358(14) 2_665 ? C2 C3 1.366(14) . ? C3 C4 1.390(14) . ? C4 C5 1.364(15) . ? N2 C6 1.400(12) . ? N2 C10 1.351(14) . ? N2 Co1 1.962(8) . ? C6 C7 1.412(13) . ? C6 N6 1.354(12) 2_665 ? C7 C8 1.353(15) . ? C8 C9 1.385(16) . ? C9 C10 1.355(15) . ? N3 C11 1.349(11) . ? N3 C15 1.359(15) . ? N3 Co1 1.971(8) . ? C11 C12 1.358(15) . ? C12 C13 1.388(18) . ? C13 C14 1.378(14) . ? C14 C15 1.405(14) . ? C15 N5 1.383(12) . ? N4 C16 1.368(14) . ? N4 C20 1.363(13) . ? N4 Co1 1.977(10) . ? C16 C17 1.358(18) . ? C17 C18 1.38(2) . ? C18 C19 1.386(17) . ? C19 C20 1.413(17) . ? C20 N6 1.338(14) . ? N6 C6 1.354(12) 2_665 ? N6 Co2 1.895(10) . ? N5 C1 1.358(14) 2_665 ? N5 Co2 1.906(10) . ? Cl1 Co1 2.497(3) . ? Co1 Co2 2.3268(12) . ? Co2 N6 1.895(10) 2_665 ? Co2 N5 1.906(10) 2_665 ? Co2 Co1 2.3267(12) 2_665 ? C21A Cl2A 1.74(4) . ? C21A Cl3A 1.72(3) . ? C21B Cl2B 1.74(5) . ? C21B Cl3B 1.71(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 N1 Co1 122.0(7) . . ? C5 N1 C1 118.1(10) . . ? C5 N1 Co1 119.9(7) . . ? N1 C1 C2 120.0(10) . . ? N5 C1 N1 114.4(10) 2_665 . ? N5 C1 C2 125.6(9) 2_665 . ? C3 C2 C1 121.8(11) . . ? C2 C3 C4 117.4(14) . . ? C5 C4 C3 119.8(11) . . ? N1 C5 C4 122.8(9) . . ? C6 N2 Co1 118.2(7) . . ? C10 N2 C6 119.8(8) . . ? C10 N2 Co1 122.0(7) . . ? N2 C6 C7 116.9(9) . . ? N6 C6 N2 116.0(8) 2_665 . ? N6 C6 C7 126.8(9) 2_665 . ? C8 C7 C6 120.7(10) . . ? C7 C8 C9 121.9(11) . . ? C10 C9 C8 116.8(12) . . ? N2 C10 C9 123.9(11) . . ? C11 N3 C15 117.4(9) . . ? C11 N3 Co1 120.9(8) . . ? C15 N3 Co1 121.7(6) . . ? N3 C11 C12 124.6(11) . . ? C11 C12 C13 118.6(11) . . ? C14 C13 C12 118.4(12) . . ? C13 C14 C15 120.3(11) . . ? N3 C15 C14 120.4(8) . . ? N3 C15 N5 115.4(9) . . ? N5 C15 C14 123.9(10) . . ? C16 N4 Co1 120.0(9) . . ? C20 N4 C16 119.0(12) . . ? C20 N4 Co1 120.9(7) . . ? C17 C16 N4 122.5(13) . . ? C16 C17 C18 120.7(14) . . ? C17 C18 C19 117.2(15) . . ? C18 C19 C20 121.6(14) . . ? N4 C20 C19 118.9(9) . . ? N6 C20 N4 115.3(11) . . ? N6 C20 C19 125.6(11) . . ? C6 N6 Co2 119.3(7) 2_665 . ? C20 N6 C6 122.1(10) . 2_665 ? C20 N6 Co2 118.6(8) . . ? C1 N5 C15 125.2(10) 2_665 . ? C1 N5 Co2 117.5(7) 2_665 . ? C15 N5 Co2 117.1(8) . . ? N1 Co1 Cl1 95.8(2) . . ? N1 Co1 Co2 84.0(2) . . ? N2 Co1 N1 89.4(3) . . ? N2 Co1 N3 172.4(4) . . ? N2 Co1 N4 89.8(4) . . ? N2 Co1 Cl1 94.0(3) . . ? N2 Co1 Co2 87.5(3) . . ? N3 Co1 N1 90.1(4) . . ? N3 Co1 N4 89.2(3) . . ? N3 Co1 Cl1 93.6(3) . . ? N3 Co1 Co2 84.8(3) . . ? N4 Co1 N1 169.0(3) . . ? N4 Co1 Cl1 95.2(3) . . ? N4 Co1 Co2 84.9(3) . . ? Co2 Co1 Cl1 178.43(10) . . ? N6 Co2 N6 90.2(6) 2_665 . ? N6 Co2 N5 179.5(5) . 2_665 ? N6 Co2 N5 89.8(3) 2_665 2_665 ? N6 Co2 N5 89.8(3) . . ? N6 Co2 N5 179.5(5) 2_665 . ? N6 Co2 Co1 88.7(3) . 2_665 ? N6 Co2 Co1 89.6(3) 2_665 2_665 ? N6 Co2 Co1 89.6(3) . . ? N6 Co2 Co1 88.7(3) 2_665 . ? N5 Co2 N5 90.1(6) 2_665 . ? N5 Co2 Co1 90.8(3) 2_665 2_665 ? N5 Co2 Co1 90.9(3) . 2_665 ? N5 Co2 Co1 90.8(3) . . ? N5 Co2 Co1 90.9(3) 2_665 . ? Co1 Co2 Co1 177.54(19) 2_665 . ? Cl3A C21A Cl2A 116(3) . . ? Cl3B C21B Cl2B 118(5) . . ? 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 C1 C2 C3 -0.4(14) . . . . ? C1 N1 C5 C4 -1.8(15) . . . . ? C1 C2 C3 C4 -2.5(17) . . . . ? C2 C3 C4 C5 3.3(17) . . . . ? C3 C4 C5 N1 -1.2(16) . . . . ? C5 N1 C1 C2 2.6(13) . . . . ? C5 N1 C1 N5 179.3(10) . . . 2_665 ? N2 C6 C7 C8 -2.8(14) . . . . ? C6 N2 C10 C9 1.4(15) . . . . ? C6 C7 C8 C9 2.9(17) . . . . ? C6 N6 Co2 N6 121.3(9) 2_665 . . 2_665 ? C6 N6 Co2 N5 -59.2(7) 2_665 . . . ? C6 N6 Co2 Co1 -150.0(7) 2_665 . . . ? C6 N6 Co2 Co1 31.7(7) 2_665 . . 2_665 ? C7 C8 C9 C10 -0.9(18) . . . . ? C8 C9 C10 N2 -1.3(18) . . . . ? C10 N2 C6 C7 0.7(12) . . . . ? C10 N2 C6 N6 174.6(9) . . . 2_665 ? N3 C11 C12 C13 -0.3(17) . . . . ? N3 C15 N5 C1 158.8(11) . . . 2_665 ? N3 C15 N5 Co2 -18.1(14) . . . . ? C11 N3 C15 C14 -5.1(16) . . . . ? C11 N3 C15 N5 169.6(9) . . . . ? C11 C12 C13 C14 -0.5(19) . . . . ? C12 C13 C14 C15 -1.6(19) . . . . ? C13 C14 C15 N3 4.5(18) . . . . ? C13 C14 C15 N5 -169.7(11) . . . . ? C14 C15 N5 C1 -26.8(19) . . . 2_665 ? C14 C15 N5 Co2 156.4(10) . . . . ? C15 N3 C11 C12 3.1(14) . . . . ? N4 C16 C17 C18 -1.7(15) . . . . ? N4 C20 N6 C6 159.2(8) . . . 2_665 ? N4 C20 N6 Co2 -23.6(12) . . . . ? C16 N4 C20 C19 -2.4(13) . . . . ? C16 N4 C20 N6 172.5(8) . . . . ? C16 C17 C18 C19 -0.4(17) . . . . ? C17 C18 C19 C20 1.0(17) . . . . ? C18 C19 C20 N4 0.4(15) . . . . ? C18 C19 C20 N6 -174.0(10) . . . . ? C19 C20 N6 C6 -26.3(15) . . . 2_665 ? C19 C20 N6 Co2 150.9(9) . . . . ? C20 N4 C16 C17 3.1(13) . . . . ? C20 N6 Co2 N6 -55.9(7) . . . 2_665 ? C20 N6 Co2 N5 123.6(9) . . . . ? C20 N6 Co2 Co1 32.8(8) . . . . ? C20 N6 Co2 Co1 -145.5(8) . . . 2_665 ? N6 C6 C7 C8 -175.9(10) 2_665 . . . ? N5 C1 C2 C3 -176.8(12) 2_665 . . . ? Co1 N1 C1 C2 -177.5(7) . . . . ? Co1 N1 C1 N5 -0.7(12) . . . 2_665 ? Co1 N1 C5 C4 178.3(8) . . . . ? Co1 N2 C6 C7 -177.7(7) . . . . ? Co1 N2 C6 N6 -3.8(11) . . . 2_665 ? Co1 N2 C10 C9 179.7(10) . . . . ? Co1 N3 C11 C12 -178.2(9) . . . . ? Co1 N3 C15 C14 176.2(8) . . . . ? Co1 N3 C15 N5 -9.1(15) . . . . ? Co1 N4 C16 C17 179.7(7) . . . . ? Co1 N4 C20 C19 -178.9(7) . . . . ? Co1 N4 C20 N6 -4.0(11) . . . . ? _shelx_estimated_absorpt_T_max ? _shelx_estimated_absorpt_T_min ? _shelx_hkl_checksum 80746 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelxl_version_number 2013-2 _database_code_depnum_ccdc_archive 'CCDC 952406' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_d2a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'C40 H40 N12 Cl4 Co3' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 13.6906(4) _cell_length_b 12.6908(9) _cell_length_c 10.8131(9) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1878.7(2) _cell_formula_units_Z 2 _cell_measurement_reflns_used 3510 _cell_measurement_temperature 293(2) _cell_measurement_pressure 820000(40000) _cell_measurement_theta_max 28.3898 _cell_measurement_theta_min 1.4844 _exptl_absorpt_coefficient_mu 1.646 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.91653 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.781 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description prism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0750 _diffrn_reflns_av_unetI/netI 0.0759 _diffrn_reflns_Laue_measured_fraction_full 0.539 _diffrn_reflns_Laue_measured_fraction_max 0.466 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_number 11178 _diffrn_reflns_point_group_measured_fraction_full 0.542 _diffrn_reflns_point_group_measured_fraction_max 0.457 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 28.452 _diffrn_reflns_theta_min 2.188 _diffrn_ambient_temperature 293(2) _diffrn_ambient_pressure 820000(40000) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.539 _diffrn_measured_fraction_theta_max 0.466 _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 0.0002353000 _diffrn_orient_matrix_UB_12 -0.0370750000 _diffrn_orient_matrix_UB_13 -0.0490885000 _diffrn_orient_matrix_UB_21 -0.0086161000 _diffrn_orient_matrix_UB_22 0.0412228000 _diffrn_orient_matrix_UB_23 -0.0429487000 _diffrn_orient_matrix_UB_31 0.0510746000 _diffrn_orient_matrix_UB_32 0.0071306000 _diffrn_orient_matrix_UB_33 -0.0070219000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.863 _reflns_Friedel_fraction_full 0.545 _reflns_Friedel_fraction_max 0.446 _reflns_number_gt 1584 _reflns_number_total 2169 _reflns_odcompleteness_completeness 50.61 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 26.32 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.418 _refine_diff_density_min -0.365 _refine_diff_density_rms 0.082 _refine_ls_abs_structure_details ; Classical Flack method preferred over Parsons because s.u. lower. ; _refine_ls_abs_structure_Flack -0.02(5) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.066 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 2169 _refine_ls_number_restraints 42 _refine_ls_R_factor_all 0.0835 _refine_ls_R_factor_gt 0.0488 _refine_ls_restrained_S_all 1.059 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.0365P)^2^+2.0987P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0920 _refine_ls_wR_factor_ref 0.1050 _refine_special_details ; ? ; _atom_sites_solution_hydrogens geom _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5335(5) 0.6765(6) -0.1672(9) 0.019(2) Uiso 1 1 d D . . . . C1 C 0.4543(6) 0.6229(9) -0.2101(12) 0.025(3) Uiso 1 1 d D . . . . C2 C 0.4229(7) 0.6340(10) -0.3312(12) 0.034(3) Uiso 1 1 d D . . . . H2 H 0.3702 0.5946 -0.3594 0.041 Uiso 1 1 calc R U . . . C3 C 0.4695(7) 0.7032(10) -0.4104(13) 0.038(3) Uiso 1 1 d D . . . . H3 H 0.4490 0.7112 -0.4918 0.045 Uiso 1 1 calc R U . . . C4 C 0.5479(7) 0.7602(10) -0.3641(13) 0.037(3) Uiso 1 1 d D . . . . H4 H 0.5802 0.8085 -0.4142 0.045 Uiso 1 1 calc R U . . . C5 C 0.5775(7) 0.7452(9) -0.2441(12) 0.031(3) Uiso 1 1 d D . . . . H5 H 0.6302 0.7841 -0.2147 0.037 Uiso 1 1 calc R U . . . N2 N 0.4701(5) 0.7245(8) 0.0713(9) 0.025(2) Uiso 1 1 d . . . . . C6 C 0.4000(6) 0.6618(9) 0.1262(11) 0.023(3) Uiso 1 1 d . . . . . C7 C 0.3148(7) 0.7103(9) 0.1711(12) 0.031(3) Uiso 1 1 d . . . . . H7 H 0.2660 0.6700 0.2076 0.037 Uiso 1 1 calc R U . . . C8 C 0.3039(7) 0.8166(10) 0.1610(13) 0.034(3) Uiso 1 1 d . . . . . H8 H 0.2479 0.8481 0.1924 0.041 Uiso 1 1 calc R U . . . C9 C 0.3737(7) 0.8788(10) 0.1055(13) 0.035(3) Uiso 1 1 d . . . . . H9 H 0.3657 0.9513 0.0985 0.042 Uiso 1 1 calc R U . . . C10 C 0.4546(7) 0.8300(10) 0.0614(11) 0.030(3) Uiso 1 1 d . . . . . H10 H 0.5019 0.8708 0.0224 0.036 Uiso 1 1 calc R U . . . N3 N 0.6952(5) 0.5717(7) -0.0619(9) 0.022(2) Uiso 1 1 d . . . . . C11 C 0.7889(6) 0.5994(10) -0.0381(11) 0.032(3) Uiso 1 1 d . . . . . H11 H 0.7997 0.6587 0.0106 0.038 Uiso 1 1 calc R U . . . C12 C 0.8688(9) 0.5456(11) -0.0812(13) 0.043(4) Uiso 1 1 d . . . . . H12 H 0.9318 0.5671 -0.0615 0.052 Uiso 1 1 calc R U . . . C13 C 0.8523(8) 0.4578(11) -0.1554(14) 0.042(3) Uiso 1 1 d . . . . . H13 H 0.9047 0.4217 -0.1902 0.051 Uiso 1 1 calc R U . . . C14 C 0.7576(6) 0.4245(9) -0.1770(12) 0.028(3) Uiso 1 1 d . . . . . H14 H 0.7453 0.3657 -0.2259 0.034 Uiso 1 1 calc R U . . . C15 C 0.6794(7) 0.4820(10) -0.1232(12) 0.028(3) Uiso 1 1 d . . . . . N4 N 0.6230(5) 0.6139(8) 0.1731(10) 0.025(2) Uiso 1 1 d . . . . . C16 C 0.6490(7) 0.6877(11) 0.2593(15) 0.037(3) Uiso 1 1 d . . . . . H16 H 0.6494 0.7584 0.2368 0.045 Uiso 1 1 calc R U . . . C17 C 0.6739(8) 0.6617(13) 0.3744(15) 0.052(4) Uiso 1 1 d . . . . . H17 H 0.6925 0.7146 0.4291 0.062 Uiso 1 1 calc R U . . . C18 C 0.6729(9) 0.5591(13) 0.4146(16) 0.052(4) Uiso 1 1 d . . . . . H18 H 0.6913 0.5417 0.4949 0.063 Uiso 1 1 calc R U . . . C19 C 0.6437(7) 0.4826(11) 0.3314(14) 0.035(3) Uiso 1 1 d . . . . . H19 H 0.6406 0.4125 0.3561 0.042 Uiso 1 1 calc R U . . . C20 C 0.6185(6) 0.5107(9) 0.2088(12) 0.022(3) Uiso 1 1 d . . . . . N6 N 0.5834(6) 0.4440(9) 0.1209(11) 0.025(3) Uiso 1 1 d . . . . . N5 N 0.5838(6) 0.4472(8) -0.1267(10) 0.020(2) Uiso 1 1 d . . . . . Cl1 Cl 0.68505(14) 0.8222(2) 0.0062(4) 0.0329(7) Uani 1 1 d . . . . . Co1 Co 0.58698(7) 0.65676(10) 0.0044(2) 0.0224(4) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 -0.0011(3) 0.0211(5) Uani 1 2 d S T P . . C21A C 0.0289(19) 0.493(4) 0.308(4) 0.051(12) Uiso 0.428(12) 1 d D U P A -1 H21A H 0.0228 0.4257 0.3490 0.061 Uiso 0.428(12) 1 calc R U P A -1 H21B H 0.0557 0.5426 0.3674 0.061 Uiso 0.428(12) 1 calc R U P A -1 Cl2A Cl 0.1123(8) 0.4799(10) 0.1860(14) 0.072(4) Uiso 0.428(12) 1 d D U P A -1 Cl3A Cl -0.0868(9) 0.5359(12) 0.267(2) 0.073(4) Uiso 0.428(12) 1 d D U P A -1 C21B C 0.057(7) 0.517(9) 0.27(3) 0.04(3) Uiso 0.072(12) 1 d D U P A -2 H21C H 0.0913 0.5634 0.3311 0.051 Uiso 0.072(12) 1 calc R U P A -2 H21D H 0.0624 0.5469 0.1926 0.051 Uiso 0.072(12) 1 calc R U P A -2 Cl2B Cl 0.118(4) 0.396(7) 0.274(8) 0.09(2) Uiso 0.072(12) 1 d D U P A -2 Cl3B Cl -0.065(4) 0.516(6) 0.316(7) 0.039(15) Uiso 0.072(12) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.0319(10) 0.027(2) 0.039(3) -0.0006(18) -0.002(2) -0.0066(10) Co1 0.0188(5) 0.0180(11) 0.0303(14) -0.0006(9) 0.0016(10) -0.0004(5) Co2 0.0173(7) 0.0163(15) 0.0297(19) 0.000 0.000 0.0006(7) _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 N1 C1 1.361(11) . ? N1 C5 1.348(12) . ? N1 Co1 2.011(10) . ? C1 C2 1.385(14) . ? C1 N5 1.370(15) 2_665 ? C2 C3 1.382(14) . ? C3 C4 1.387(13) . ? C4 C5 1.373(15) . ? N2 C6 1.381(13) . ? N2 C10 1.360(14) . ? N2 Co1 1.955(8) . ? C6 C7 1.406(14) . ? C6 N6 1.364(13) 2_665 ? C7 C8 1.362(16) . ? C8 C9 1.377(16) . ? C9 C10 1.354(15) . ? N3 C11 1.355(12) . ? N3 C15 1.335(16) . ? N3 Co1 1.968(8) . ? C11 C12 1.371(16) . ? C12 C13 1.392(19) . ? C13 C14 1.385(14) . ? C14 C15 1.420(14) . ? C15 N5 1.381(13) . ? N4 C16 1.368(16) . ? N4 C20 1.367(14) . ? N4 Co1 1.966(10) . ? C16 C17 1.33(2) . ? C17 C18 1.37(2) . ? C18 C19 1.383(19) . ? C19 C20 1.416(18) . ? C20 N6 1.360(16) . ? N6 C6 1.364(13) 2_665 ? N6 Co2 1.884(11) . ? N5 C1 1.370(15) 2_665 ? N5 Co2 1.900(10) . ? Cl1 Co1 2.493(3) . ? Co1 Co2 2.3193(12) . ? Co2 N6 1.884(11) 2_665 ? Co2 N5 1.900(10) 2_665 ? Co2 Co1 2.3193(12) 2_665 ? C21A Cl2A 1.75(3) . ? C21A Cl3A 1.73(3) . ? C21B Cl2B 1.75(4) . ? C21B Cl3B 1.73(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 N1 Co1 122.8(8) . . ? C5 N1 C1 118.0(11) . . ? C5 N1 Co1 119.1(7) . . ? N1 C1 C2 121.2(10) . . ? N1 C1 N5 113.8(11) . 2_665 ? N5 C1 C2 124.8(10) 2_665 . ? C3 C2 C1 120.5(11) . . ? C2 C3 C4 117.7(13) . . ? C5 C4 C3 119.8(12) . . ? N1 C5 C4 122.7(10) . . ? C6 N2 Co1 118.3(8) . . ? C10 N2 C6 119.5(8) . . ? C10 N2 Co1 122.1(7) . . ? N2 C6 C7 118.2(10) . . ? N6 C6 N2 115.7(9) 2_665 . ? N6 C6 C7 125.7(10) 2_665 . ? C8 C7 C6 119.8(10) . . ? C7 C8 C9 121.8(11) . . ? C10 C9 C8 117.3(12) . . ? C9 C10 N2 123.4(11) . . ? C11 N3 Co1 120.1(8) . . ? C15 N3 C11 118.0(9) . . ? C15 N3 Co1 121.8(6) . . ? N3 C11 C12 124.2(12) . . ? C11 C12 C13 117.7(11) . . ? C14 C13 C12 119.6(12) . . ? C13 C14 C15 118.7(11) . . ? N3 C15 C14 121.3(9) . . ? N3 C15 N5 116.1(10) . . ? N5 C15 C14 122.5(11) . . ? C16 N4 Co1 120.6(11) . . ? C20 N4 C16 118.3(13) . . ? C20 N4 Co1 121.0(7) . . ? C17 C16 N4 122.2(15) . . ? C16 C17 C18 121.9(15) . . ? C17 C18 C19 117.5(17) . . ? C18 C19 C20 120.2(15) . . ? N4 C20 C19 119.7(10) . . ? N6 C20 N4 114.5(12) . . ? N6 C20 C19 125.7(12) . . ? C6 N6 Co2 120.1(8) 2_665 . ? C20 N6 C6 121.7(11) . 2_665 ? C20 N6 Co2 117.9(9) . . ? C1 N5 C15 125.9(11) 2_665 . ? C1 N5 Co2 118.0(7) 2_665 . ? C15 N5 Co2 116.1(9) . . ? N1 Co1 Cl1 95.7(3) . . ? N1 Co1 Co2 84.0(2) . . ? N2 Co1 N1 89.3(4) . . ? N2 Co1 N3 172.7(4) . . ? N2 Co1 N4 89.1(4) . . ? N2 Co1 Cl1 93.9(3) . . ? N2 Co1 Co2 88.1(3) . . ? N3 Co1 N1 90.4(4) . . ? N3 Co1 Cl1 93.4(3) . . ? N3 Co1 Co2 84.7(3) . . ? N4 Co1 N1 169.1(3) . . ? N4 Co1 N3 89.9(4) . . ? N4 Co1 Cl1 95.2(3) . . ? N4 Co1 Co2 85.2(3) . . ? Co2 Co1 Cl1 178.02(11) . . ? N6 Co2 N6 91.1(7) . 2_665 ? N6 Co2 N5 90.1(3) 2_665 2_665 ? N6 Co2 N5 178.4(6) . 2_665 ? N6 Co2 N5 90.1(3) . . ? N6 Co2 N5 178.4(6) 2_665 . ? N6 Co2 Co1 89.7(3) . . ? N6 Co2 Co1 89.7(3) 2_665 2_665 ? N6 Co2 Co1 88.3(3) . 2_665 ? N6 Co2 Co1 88.3(3) 2_665 . ? N5 Co2 N5 88.8(6) 2_665 . ? N5 Co2 Co1 90.6(3) . . ? N5 Co2 Co1 91.5(3) 2_665 . ? N5 Co2 Co1 91.5(3) . 2_665 ? N5 Co2 Co1 90.6(3) 2_665 2_665 ? Co1 Co2 Co1 177.1(2) . 2_665 ? Cl3A C21A Cl2A 116(2) . . ? Cl3B C21B Cl2B 117(4) . . ? 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 C1 C2 C3 -2.4(14) . . . . ? C1 N1 C5 C4 -2.3(15) . . . . ? C1 C2 C3 C4 0.0(17) . . . . ? C2 C3 C4 C5 1.2(17) . . . . ? C3 C4 C5 N1 0.0(16) . . . . ? C5 N1 C1 C2 3.5(13) . . . . ? C5 N1 C1 N5 178.3(10) . . . 2_665 ? N2 C6 C7 C8 -0.8(15) . . . . ? C6 N2 C10 C9 1.5(15) . . . . ? C6 C7 C8 C9 1.2(18) . . . . ? C6 N6 Co2 N6 120.1(9) 2_665 . . 2_665 ? C6 N6 Co2 N5 -61.1(8) 2_665 . . . ? C6 N6 Co2 Co1 30.4(8) 2_665 . . 2_665 ? C6 N6 Co2 Co1 -151.7(8) 2_665 . . . ? C7 C8 C9 C10 -0.3(19) . . . . ? C8 C9 C10 N2 -1.1(18) . . . . ? C10 N2 C6 C7 -0.5(13) . . . . ? C10 N2 C6 N6 173.4(9) . . . 2_665 ? N3 C11 C12 C13 0.9(17) . . . . ? N3 C15 N5 C1 160.1(12) . . . 2_665 ? N3 C15 N5 Co2 -21.4(15) . . . . ? C11 N3 C15 C14 -8.7(18) . . . . ? C11 N3 C15 N5 169.0(10) . . . . ? C11 C12 C13 C14 -4(2) . . . . ? C12 C13 C14 C15 0(2) . . . . ? C13 C14 C15 N3 5.9(19) . . . . ? C13 C14 C15 N5 -171.6(12) . . . . ? C14 C15 N5 C1 -22(2) . . . 2_665 ? C14 C15 N5 Co2 156.2(10) . . . . ? C15 N3 C11 C12 5.4(15) . . . . ? N4 C16 C17 C18 -1.5(16) . . . . ? N4 C20 N6 C6 160.6(9) . . . 2_665 ? N4 C20 N6 Co2 -25.5(12) . . . . ? C16 N4 C20 C19 -2.2(14) . . . . ? C16 N4 C20 N6 174.2(8) . . . . ? C16 C17 C18 C19 -0.8(18) . . . . ? C17 C18 C19 C20 1.6(17) . . . . ? C18 C19 C20 N4 -0.1(16) . . . . ? C18 C19 C20 N6 -176.0(10) . . . . ? C19 C20 N6 C6 -23.3(16) . . . 2_665 ? C19 C20 N6 Co2 150.7(9) . . . . ? C20 N4 C16 C17 3.0(14) . . . . ? C20 N6 Co2 N6 -54.0(8) . . . 2_665 ? C20 N6 Co2 N5 124.9(10) . . . . ? C20 N6 Co2 Co1 -143.6(9) . . . 2_665 ? C20 N6 Co2 Co1 34.3(9) . . . . ? N6 C6 C7 C8 -174.1(11) 2_665 . . . ? N5 C1 C2 C3 -176.6(12) 2_665 . . . ? Co1 N1 C1 C2 -176.2(7) . . . . ? Co1 N1 C1 N5 -1.4(12) . . . 2_665 ? Co1 N1 C5 C4 177.4(8) . . . . ? Co1 N2 C6 C7 -178.2(8) . . . . ? Co1 N2 C6 N6 -4.3(12) . . . 2_665 ? Co1 N2 C10 C9 179.1(10) . . . . ? Co1 N3 C11 C12 -179.4(9) . . . . ? Co1 N3 C15 C14 176.2(9) . . . . ? Co1 N3 C15 N5 -6.1(17) . . . . ? Co1 N4 C16 C17 -180.0(8) . . . . ? Co1 N4 C20 C19 -179.2(7) . . . . ? Co1 N4 C20 N6 -2.8(12) . . . . ? _shelx_estimated_absorpt_T_max ? _shelx_estimated_absorpt_T_min ? _shelx_hkl_checksum 29176 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelxl_version_number 2013-2 _database_code_depnum_ccdc_archive 'CCDC 952407' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_d3a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C1 H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'Co3 Cl4 C40 N12 H40' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 13.5953(4) _cell_length_b 12.6243(10) _cell_length_c 10.6351(11) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1825.3(2) _cell_formula_units_Z 2 _cell_measurement_reflns_used 4393 _cell_measurement_temperature 292.1(5) _cell_measurement_pressure 1330000(30000) _cell_measurement_theta_max 28.9524 _cell_measurement_theta_min 1.4948 _exptl_absorpt_coefficient_mu 1.694 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.78127 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.833 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description prism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0905 _diffrn_reflns_av_unetI/netI 0.0904 _diffrn_reflns_Laue_measured_fraction_full 0.568 _diffrn_reflns_Laue_measured_fraction_max 0.482 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_number 13131 _diffrn_reflns_point_group_measured_fraction_full 0.575 _diffrn_reflns_point_group_measured_fraction_max 0.476 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 29.016 _diffrn_reflns_theta_min 2.201 _diffrn_ambient_temperature 292.1(5) _diffrn_ambient_pressure 1330000(30000) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.568 _diffrn_measured_fraction_theta_max 0.482 _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 -0.0002471000 _diffrn_orient_matrix_UB_12 -0.0370445000 _diffrn_orient_matrix_UB_13 0.0502447000 _diffrn_orient_matrix_UB_21 0.0086438000 _diffrn_orient_matrix_UB_22 0.0416653000 _diffrn_orient_matrix_UB_23 0.0433025000 _diffrn_orient_matrix_UB_31 -0.0514192000 _diffrn_orient_matrix_UB_32 0.0071441000 _diffrn_orient_matrix_UB_33 0.0070888000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.877 _reflns_Friedel_fraction_full 0.583 _reflns_Friedel_fraction_max 0.469 _reflns_number_gt 1576 _reflns_number_total 2322 _reflns_odcompleteness_completeness 53.41 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 26.32 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.617 _refine_diff_density_min -0.754 _refine_diff_density_rms 0.107 _refine_ls_abs_structure_details ; Flack x determined using 546 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). ; _refine_ls_abs_structure_Flack 0.000(2) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.241 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 2322 _refine_ls_number_restraints 574 _refine_ls_R_factor_all 0.1292 _refine_ls_R_factor_gt 0.0817 _refine_ls_restrained_S_all 1.150 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.1077P)^2^+5.0668P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.2159 _refine_ls_wR_factor_ref 0.2502 _refine_special_details ; ? ; _atom_sites_solution_hydrogens geom _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5327(9) 0.6772(12) 1.1694(15) 0.027(4) Uiso 1 1 d D . . . . C1 C 0.4537(10) 0.6214(13) 1.2158(17) 0.030(4) Uiso 1 1 d D . . . . C2 C 0.4215(12) 0.6344(15) 1.3371(17) 0.034(5) Uiso 1 1 d D . . . . H2 H 0.3681 0.5953 1.3659 0.040 Uiso 1 1 calc R U . . . C3 C 0.4673(12) 0.7048(16) 1.4164(19) 0.039(5) Uiso 1 1 d D . . . . H3 H 0.4470 0.7125 1.4994 0.047 Uiso 1 1 calc R U . . . C4 C 0.5444(13) 0.7637(17) 1.3691(19) 0.042(5) Uiso 1 1 d D . . . . H4 H 0.5749 0.8142 1.4195 0.050 Uiso 1 1 calc R U . . . C5 C 0.5762(11) 0.7482(15) 1.2489(18) 0.034(5) Uiso 1 1 d D . . . . H5 H 0.6295 0.7874 1.2199 0.041 Uiso 1 1 calc R U . . . N2 N 0.4709(9) 0.7246(12) 0.9267(15) 0.028(4) Uiso 1 1 d D . . . . C6 C 0.3995(10) 0.6637(14) 0.8711(17) 0.028(4) Uiso 1 1 d D . . . . C7 C 0.3153(11) 0.7121(14) 0.826(2) 0.034(5) Uiso 1 1 d D . . . . H7 H 0.2665 0.6708 0.7897 0.040 Uiso 1 1 calc R U . . . C8 C 0.3022(12) 0.8195(14) 0.835(2) 0.037(5) Uiso 1 1 d D . . . . H8 H 0.2460 0.8512 0.8019 0.044 Uiso 1 1 calc R U . . . C9 C 0.3737(11) 0.8798(15) 0.892(2) 0.039(5) Uiso 1 1 d D . . . . H9 H 0.3659 0.9526 0.9005 0.047 Uiso 1 1 calc R U . . . C10 C 0.4561(13) 0.8312(15) 0.937(2) 0.044(6) Uiso 1 1 d D . . . . H10 H 0.5040 0.8721 0.9765 0.053 Uiso 1 1 calc R U . . . N3 N 0.6962(9) 0.5704(13) 1.0610(17) 0.032(4) Uiso 1 1 d D . . . . C11 C 0.7905(10) 0.5989(14) 1.0348(19) 0.036(5) Uiso 1 1 d D . . . . H11 H 0.8017 0.6582 0.9849 0.043 Uiso 1 1 calc R U . . . C12 C 0.8696(13) 0.5432(16) 1.080(2) 0.044(6) Uiso 1 1 d D . . . . H12 H 0.9332 0.5639 1.0588 0.053 Uiso 1 1 calc R U . . . C13 C 0.8543(11) 0.4566(16) 1.155(2) 0.043(6) Uiso 1 1 d D . . . . H13 H 0.9071 0.4199 1.1897 0.052 Uiso 1 1 calc R U . . . C14 C 0.7589(10) 0.4252(15) 1.179(2) 0.035(5) Uiso 1 1 d D . . . . H14 H 0.7472 0.3658 1.2282 0.042 Uiso 1 1 calc R U . . . C15 C 0.6806(11) 0.4809(15) 1.129(2) 0.029(5) Uiso 1 1 d D . . . . N4 N 0.6223(9) 0.6147(12) 0.8245(15) 0.026(4) Uiso 1 1 d D . . . . C16 C 0.6489(11) 0.6903(15) 0.7382(19) 0.040(5) Uiso 1 1 d D . . . . H16 H 0.6494 0.7611 0.7624 0.048 Uiso 1 1 calc R U . . . C17 C 0.6746(14) 0.6648(18) 0.618(2) 0.058(7) Uiso 1 1 d D . . . . H17 H 0.6935 0.7175 0.5621 0.070 Uiso 1 1 calc R U . . . C18 C 0.6723(16) 0.5607(18) 0.581(2) 0.058(7) Uiso 1 1 d D . . . . H18 H 0.6887 0.5422 0.4986 0.070 Uiso 1 1 calc R U . . . C19 C 0.6453(13) 0.4845(16) 0.6665(19) 0.039(5) Uiso 1 1 d D . . . . H19 H 0.6440 0.4138 0.6418 0.047 Uiso 1 1 calc R U . . . C20 C 0.6200(12) 0.5106(14) 0.7887(18) 0.026(4) Uiso 1 1 d D . . . . N6 N 0.5833(10) 0.4427(15) 0.8756(19) 0.026(4) Uiso 1 1 d . . . . . N5 N 0.5853(11) 0.4472(15) 1.1254(19) 0.025(4) Uiso 1 1 d . . . . . Cl1 Cl 0.6853(2) 0.8231(4) 0.9946(9) 0.0363(13) Uani 1 1 d . . . . . Co1 Co 0.58700(12) 0.65754(18) 0.9960(5) 0.0257(8) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 1.0015(6) 0.0252(9) Uani 1 2 d S T P . . C21A C 0.974(4) 0.505(9) 0.694(9) 0.065(17) Uiso 0.40(2) 1 d D U P A -1 H21A H 0.9470 0.4541 0.6342 0.078 Uiso 0.40(2) 1 calc R U P A -1 H21B H 0.9795 0.5718 0.6502 0.078 Uiso 0.40(2) 1 calc R U P A -1 Cl2A Cl 0.8881(14) 0.5206(18) 0.812(3) 0.070(7) Uiso 0.40(2) 1 d D U P A -1 Cl3A Cl 1.0903(17) 0.464(2) 0.731(3) 0.069(7) Uiso 0.40(2) 1 d D U P A -1 C21B C 0.059(14) 0.49(2) 0.66(3) 0.06(3) Uiso 0.10(2) 1 d D U P A -2 H21C H 0.0971 0.5534 0.6798 0.073 Uiso 0.10(2) 1 calc R U P A -2 H21D H 0.0568 0.4856 0.5686 0.073 Uiso 0.10(2) 1 calc R U P A -2 Cl2B Cl 0.123(5) 0.383(7) 0.714(10) 0.07(3) Uiso 0.10(2) 1 d D U P A -2 Cl3B Cl -0.059(6) 0.514(9) 0.710(11) 0.05(2) Uiso 0.10(2) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.0307(16) 0.024(4) 0.054(5) -0.002(3) 0.000(4) -0.0060(16) Co1 0.0186(8) 0.0205(19) 0.038(3) 0.0000(14) -0.0001(15) 0.0008(8) Co2 0.0189(11) 0.020(3) 0.037(4) 0.000 0.000 -0.0004(11) _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 N1 C1 1.376(15) . ? N1 C5 1.366(15) . ? N1 Co1 2.002(17) . ? C1 C2 1.372(16) . ? C1 N5 1.40(3) 2_665 ? C2 C3 1.374(17) . ? C3 C4 1.380(17) . ? C4 C5 1.365(17) . ? N2 C6 1.372(15) . ? N2 C10 1.364(16) . ? N2 Co1 1.937(14) . ? C6 C7 1.382(16) . ? C6 N6 1.36(2) 2_665 ? C7 C8 1.371(17) . ? C8 C9 1.379(17) . ? C9 C10 1.364(17) . ? N3 C11 1.360(15) . ? N3 C15 1.360(16) . ? N3 Co1 1.973(14) . ? C11 C12 1.370(16) . ? C12 C13 1.373(17) . ? C13 C14 1.378(16) . ? C14 C15 1.380(16) . ? C15 N5 1.37(2) . ? N4 C16 1.372(17) . ? N4 C20 1.369(16) . ? N4 Co1 1.962(16) . ? C16 C17 1.361(18) . ? C17 C18 1.374(18) . ? C18 C19 1.377(18) . ? C19 C20 1.384(17) . ? C20 N6 1.36(3) . ? N6 C6 1.36(2) 2_665 ? N6 Co2 1.897(19) . ? N5 C1 1.40(3) 2_665 ? N5 Co2 1.877(19) . ? Cl1 Co1 2.481(5) . ? Co1 Co2 2.315(2) . ? Co2 N6 1.897(19) 2_665 ? Co2 N5 1.877(19) 2_665 ? Co2 Co1 2.315(2) 2_665 ? C21A Cl2A 1.73(7) . ? C21A Cl3A 1.71(6) . ? C21B Cl2B 1.72(8) . ? C21B Cl3B 1.71(7) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 N1 Co1 123.7(12) . . ? C5 N1 C1 116.8(15) . . ? C5 N1 Co1 119.4(11) . . ? N1 C1 N5 111.5(16) . 2_665 ? C2 C1 N1 121.7(15) . . ? C2 C1 N5 126.8(14) . 2_665 ? C1 C2 C3 120.6(15) . . ? C2 C3 C4 118.0(16) . . ? C5 C4 C3 120.3(16) . . ? C4 C5 N1 122.5(15) . . ? C6 N2 Co1 119.7(11) . . ? C10 N2 C6 118.9(13) . . ? C10 N2 Co1 121.3(10) . . ? N2 C6 C7 119.1(14) . . ? N6 C6 N2 114.6(14) 2_665 . ? N6 C6 C7 126.1(14) 2_665 . ? C8 C7 C6 121.5(15) . . ? C7 C8 C9 118.8(15) . . ? C10 C9 C8 119.2(16) . . ? C9 C10 N2 122.4(15) . . ? C11 N3 C15 118.4(13) . . ? C11 N3 Co1 119.4(11) . . ? C15 N3 Co1 122.2(10) . . ? N3 C11 C12 122.2(16) . . ? C11 C12 C13 119.5(16) . . ? C12 C13 C14 118.5(16) . . ? C13 C14 C15 120.7(16) . . ? N3 C15 C14 120.4(14) . . ? N3 C15 N5 113.0(15) . . ? N5 C15 C14 125.8(15) . . ? C16 N4 Co1 119.7(14) . . ? C20 N4 C16 119.2(16) . . ? C20 N4 Co1 121.2(11) . . ? C17 C16 N4 122.0(18) . . ? C16 C17 C18 119.6(18) . . ? C17 C18 C19 118.7(19) . . ? C18 C19 C20 121.5(18) . . ? N4 C20 C19 119.0(15) . . ? N6 C20 N4 115.2(16) . . ? N6 C20 C19 125.5(17) . . ? C6 N6 Co2 120.2(14) 2_665 . ? C20 N6 C6 122.4(17) . 2_665 ? C20 N6 Co2 117.4(14) . . ? C1 N5 Co2 117.9(11) 2_665 . ? C15 N5 C1 122.2(17) . 2_665 ? C15 N5 Co2 119.8(14) . . ? N1 Co1 Cl1 95.7(5) . . ? N1 Co1 Co2 83.9(4) . . ? N2 Co1 N1 89.7(6) . . ? N2 Co1 N3 172.1(7) . . ? N2 Co1 N4 88.1(7) . . ? N2 Co1 Cl1 93.9(5) . . ? N2 Co1 Co2 88.2(5) . . ? N3 Co1 N1 91.4(7) . . ? N3 Co1 Cl1 93.8(5) . . ? N3 Co1 Co2 84.1(4) . . ? N4 Co1 N1 168.8(6) . . ? N4 Co1 N3 89.3(7) . . ? N4 Co1 Cl1 95.5(5) . . ? N4 Co1 Co2 85.0(4) . . ? Co2 Co1 Cl1 177.8(2) . . ? N6 Co2 N6 90.2(12) . 2_665 ? N6 Co2 Co1 87.7(6) 2_665 . ? N6 Co2 Co1 90.3(6) . . ? N6 Co2 Co1 87.7(6) . 2_665 ? N6 Co2 Co1 90.3(6) 2_665 2_665 ? N5 Co2 N6 178.1(9) 2_665 . ? N5 Co2 N6 89.5(6) . . ? N5 Co2 N6 89.5(6) 2_665 2_665 ? N5 Co2 N6 178.1(9) . 2_665 ? N5 Co2 N5 90.9(11) . 2_665 ? N5 Co2 Co1 90.4(6) . . ? N5 Co2 Co1 90.4(6) 2_665 2_665 ? N5 Co2 Co1 91.6(6) . 2_665 ? N5 Co2 Co1 91.6(6) 2_665 . ? Co1 Co2 Co1 177.1(4) 2_665 . ? Cl3A C21A Cl2A 120(5) . . ? Cl3B C21B Cl2B 120(7) . . ? 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 C1 C2 C3 0(2) . . . . ? C1 N1 C5 C4 0(3) . . . . ? C1 C2 C3 C4 2(3) . . . . ? C1 N5 Co2 N6 -122.9(17) 2_665 . . . ? C1 N5 Co2 N5 55.2(13) 2_665 . . 2_665 ? C1 N5 Co2 Co1 146.9(15) 2_665 . . . ? C1 N5 Co2 Co1 -35.2(15) 2_665 . . 2_665 ? C2 C3 C4 C5 -3(3) . . . . ? C3 C4 C5 N1 2(3) . . . . ? C5 N1 C1 C2 -1.5(19) . . . . ? C5 N1 C1 N5 179.1(18) . . . 2_665 ? N2 C6 C7 C8 1(2) . . . . ? C6 N2 C10 C9 -1(3) . . . . ? C6 C7 C8 C9 -2(3) . . . . ? C6 N6 Co2 N6 -121.5(16) 2_665 . . 2_665 ? C6 N6 Co2 N5 60.4(13) 2_665 . . . ? C6 N6 Co2 Co1 -31.2(13) 2_665 . . 2_665 ? C6 N6 Co2 Co1 150.9(13) 2_665 . . . ? C7 C8 C9 C10 1(3) . . . . ? C8 C9 C10 N2 0(3) . . . . ? C10 N2 C6 C7 1(2) . . . . ? C10 N2 C6 N6 -174.1(18) . . . 2_665 ? N3 C11 C12 C13 -1(2) . . . . ? N3 C15 N5 C1 -160(2) . . . 2_665 ? N3 C15 N5 Co2 16(3) . . . . ? C11 N3 C15 C14 5(3) . . . . ? C11 N3 C15 N5 -165.9(17) . . . . ? C11 C12 C13 C14 3(3) . . . . ? C12 C13 C14 C15 -1(4) . . . . ? C13 C14 C15 N3 -3(4) . . . . ? C13 C14 C15 N5 167(2) . . . . ? C14 C15 N5 C1 30(4) . . . 2_665 ? C14 C15 N5 Co2 -154.3(19) . . . . ? C15 N3 C11 C12 -3(2) . . . . ? C15 N5 Co2 N6 60.9(16) . . . . ? C15 N5 Co2 N5 -121.0(19) . . . 2_665 ? C15 N5 Co2 Co1 148.5(16) . . . 2_665 ? C15 N5 Co2 Co1 -29.4(17) . . . . ? N4 C16 C17 C18 1(2) . . . . ? N4 C20 N6 C6 -161.2(15) . . . 2_665 ? N4 C20 N6 Co2 22(2) . . . . ? C16 N4 C20 C19 0(2) . . . . ? C16 N4 C20 N6 -173.5(14) . . . . ? C16 C17 C18 C19 -1(3) . . . . ? C17 C18 C19 C20 0(3) . . . . ? C18 C19 C20 N4 0(3) . . . . ? C18 C19 C20 N6 173.0(18) . . . . ? C19 C20 N6 C6 25(3) . . . 2_665 ? C19 C20 N6 Co2 -151.4(16) . . . . ? C20 N4 C16 C17 -1.0(19) . . . . ? C20 N6 Co2 N6 55.4(13) . . . 2_665 ? C20 N6 Co2 N5 -122.7(16) . . . . ? C20 N6 Co2 Co1 -32.3(14) . . . . ? C20 N6 Co2 Co1 145.7(14) . . . 2_665 ? N6 C6 C7 C8 175(2) 2_665 . . . ? N5 C1 C2 C3 180(2) 2_665 . . . ? Co1 N1 C1 C2 177.3(13) . . . . ? Co1 N1 C1 N5 -2.1(18) . . . 2_665 ? Co1 N1 C5 C4 -178.5(15) . . . . ? Co1 N2 C6 C7 177.6(13) . . . . ? Co1 N2 C6 N6 2.8(19) . . . 2_665 ? Co1 N2 C10 C9 -178.2(18) . . . . ? Co1 N3 C11 C12 178.5(16) . . . . ? Co1 N3 C15 C14 -176.6(17) . . . . ? Co1 N3 C15 N5 13(3) . . . . ? Co1 N4 C16 C17 179.6(12) . . . . ? Co1 N4 C20 C19 179.8(13) . . . . ? Co1 N4 C20 N6 6.0(19) . . . . ? _shelx_estimated_absorpt_T_max ? _shelx_estimated_absorpt_T_min ? _shelx_hkl_checksum 18400 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelxl_version_number 2013-2 _database_code_depnum_ccdc_archive 'CCDC 952408' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_d4a _audit_creation_date 2013-05-22 _audit_creation_method ; Olex2 1.2 (compiled Apr 9 2013 14:10:59, GUI svn.r4458) ; _chemical_name_common ? _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C40 H32 Cl2 Co3 N12, C H2 Cl2' _chemical_formula_sum 'C41 H34 Cl4 Co3 N12' _chemical_formula_weight 1013.45 _chemical_oxdiff_formula 'Co3 Cl4 N12 C40 H44' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _space_group_crystal_system orthorhombic _space_group_IT_number 34 _space_group_name_H-M_alt 'P n n 2' _space_group_name_Hall 'P 2 -2n' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 13.4678(10) _cell_length_b 12.5281(18) _cell_length_c 10.299(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1737.7(4) _cell_formula_units_Z 2 _cell_measurement_reflns_used 1203 _cell_measurement_temperature 292.0(5) _cell_measurement_pressure 2530000(600000) _cell_measurement_theta_max 28.3345 _cell_measurement_theta_min 1.5089 _exptl_absorpt_coefficient_mu 1.780 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.79912 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_colour 'dark green' _exptl_crystal_density_diffrn 1.933 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_description rpism _exptl_crystal_F_000 1026 _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.05 _exptl_special_details ; ? ; _exptl_transmission_factor_max ? _exptl_transmission_factor_min ? _diffrn_reflns_av_R_equivalents 0.0613 _diffrn_reflns_av_unetI/netI 0.1112 _diffrn_reflns_Laue_measured_fraction_full 0.512 _diffrn_reflns_Laue_measured_fraction_max 0.423 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_number 3718 _diffrn_reflns_point_group_measured_fraction_full 0.434 _diffrn_reflns_point_group_measured_fraction_max 0.341 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 28.397 _diffrn_reflns_theta_min 2.220 _diffrn_ambient_temperature 292.0(5) _diffrn_ambient_pressure 2530000(600000) _diffrn_detector_area_resol_mean 10.3590 _diffrn_measured_fraction_theta_full 0.512 _diffrn_measured_fraction_theta_max 0.423 _diffrn_measurement_device_type 'SuperNova, Single source at offset), Atlas' _diffrn_measurement_method '\w scans' _diffrn_orient_matrix_UB_11 -0.0002047000 _diffrn_orient_matrix_UB_12 0.0366927000 _diffrn_orient_matrix_UB_13 -0.0524851000 _diffrn_orient_matrix_UB_21 0.0086905000 _diffrn_orient_matrix_UB_22 -0.0424495000 _diffrn_orient_matrix_UB_23 -0.0441146000 _diffrn_orient_matrix_UB_31 -0.0519311000 _diffrn_orient_matrix_UB_32 -0.0072727000 _diffrn_orient_matrix_UB_33 -0.0071254000 _diffrn_radiation_monochromator mirror _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_source 'SuperNova (Mo) X-ray Source' _reflns_Friedel_coverage 0.532 _reflns_Friedel_fraction_full 0.345 _reflns_Friedel_fraction_max 0.250 _reflns_number_gt 958 _reflns_number_total 1489 _reflns_odcompleteness_completeness 47.42 _reflns_odcompleteness_iscentric 1 _reflns_odcompleteness_theta 26.32 _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _reflns_threshold_expression 'I > 2\s(I)' _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) ; _computing_molecular_graphics ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_publication_material ; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. ; _computing_structure_refinement ; XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122 ; _refine_diff_density_max 0.925 _refine_diff_density_min -1.239 _refine_diff_density_rms 0.140 _refine_ls_abs_structure_details ; Flack x determined using 295 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). ; _refine_ls_abs_structure_Flack 0.000(5) _refine_ls_extinction_coef . _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.131 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 153 _refine_ls_number_reflns 1489 _refine_ls_number_restraints 589 _refine_ls_R_factor_all 0.1284 _refine_ls_R_factor_gt 0.0598 _refine_ls_restrained_S_all 1.034 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.0610P)^2^+2.4474P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.1222 _refine_ls_wR_factor_ref 0.1574 _refine_special_details ; ? ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups 2. Restrained distances C21A-Cl3A = C21A-Cl2A 1.7 with sigma of 0.1 Cl2A-Cl3A 2.95 with sigma of 0.5 C21B-Cl3B = C21B-Cl2B 1.7 with sigma of 0.1 Cl2B-Cl3B 2.95 with sigma of 0.5 3. Restrained planarity N1, C1, C2, C3, C4, C5 with sigma of 0.1 N2, C6, C7, C8, C9, C10 with sigma of 0.1 N3, C11, C12, C13, C14, C15 with sigma of 0.1 N4, C16, C17, C18, C19, C20 with sigma of 0.1 4. Uiso/Uaniso restraints and constraints Cl2B \\sim C21B \\sim C21A \\sim Cl3A \\sim Cl3B \\sim Cl2A: within 5A with sigma of 0.04 and sigma for terminal atoms of 0.08 5. Same fragment restrains {N2, C6, C7, C8, C9, C10} {N3, C11, C12, C13, C14, C15} {N4, C16, C17, C18, C19, C20} {N1, C5, C4, C3, C2, C1} {C1, C2, C3, C4, C5, N1} as {N1, C1, C2, C3, C4, C5} {C21B, Cl2B, Cl3B} as {C21A, Cl2A, Cl3A} 6. Others 0.5*Sof(C21A)=0.5*Sof(H21A)=0.5*Sof(H21B)=0.5*Sof(Cl2A)=0.5*Sof(Cl3A)=1-0.5* Sof(C21B)=1-0.5*Sof(H21C)=1-0.5*Sof(H21D)=1-0.5*Sof(Cl2B)=1-0.5*Sof(Cl3B) 7.a Secondary CH2 refined with riding coordinates: C21A(H21A,H21B), C21B(H21C,H21D) 7.b Aromatic/amide H refined with riding coordinates: C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19) ; _atom_sites_solution_hydrogens geom _atom_sites_solution_primary ? _atom_sites_solution_secondary ? 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5336(8) 0.6788(11) -0.1754(15) 0.023(4) Uiso 1 1 d D . . . . C1 C 0.4530(10) 0.6234(12) -0.2228(18) 0.024(5) Uiso 1 1 d D . . . . C2 C 0.4197(11) 0.6382(13) -0.3471(17) 0.033(6) Uiso 1 1 d D . . . . H2 H 0.3654 0.5993 -0.3767 0.040 Uiso 1 1 calc R U . . . C3 C 0.4649(12) 0.7090(15) -0.4279(18) 0.045(6) Uiso 1 1 d D . . . . H3 H 0.4430 0.7181 -0.5129 0.054 Uiso 1 1 calc R U . . . C4 C 0.5435(12) 0.7665(16) -0.3809(19) 0.045(6) Uiso 1 1 d D . . . . H4 H 0.5753 0.8157 -0.4343 0.054 Uiso 1 1 calc R U . . . C5 C 0.5759(11) 0.7526(15) -0.2561(18) 0.036(5) Uiso 1 1 d D . . . . H5 H 0.6280 0.7942 -0.2254 0.043 Uiso 1 1 calc R U . . . N2 N 0.4713(8) 0.7264(12) 0.0720(14) 0.025(4) Uiso 1 1 d D . . . . C6 C 0.3993(9) 0.6646(12) 0.1310(16) 0.023(5) Uiso 1 1 d D . . . . C7 C 0.3141(10) 0.7128(13) 0.1803(19) 0.036(6) Uiso 1 1 d D . . . . H7 H 0.2650 0.6714 0.2190 0.043 Uiso 1 1 calc R U . . . C8 C 0.3027(11) 0.8211(14) 0.172(2) 0.037(6) Uiso 1 1 d D . . . . H8 H 0.2468 0.8530 0.2078 0.044 Uiso 1 1 calc R U . . . C9 C 0.3726(11) 0.8833(14) 0.111(2) 0.045(6) Uiso 1 1 d D . . . . H9 H 0.3640 0.9567 0.1019 0.054 Uiso 1 1 calc R U . . . C10 C 0.4551(11) 0.8334(14) 0.063(2) 0.037(6) Uiso 1 1 d D . . . . H10 H 0.5030 0.8749 0.0222 0.044 Uiso 1 1 calc R U . . . N3 N 0.6961(8) 0.5710(11) -0.0604(15) 0.023(4) Uiso 1 1 d D . . . . C11 C 0.7913(10) 0.5980(13) -0.027(2) 0.048(6) Uiso 1 1 d D . . . . H11 H 0.8020 0.6577 0.0252 0.057 Uiso 1 1 calc R U . . . C12 C 0.8719(11) 0.5388(15) -0.068(2) 0.042(6) Uiso 1 1 d D . . . . H12 H 0.9356 0.5562 -0.0406 0.050 Uiso 1 1 calc R U . . . C13 C 0.8571(10) 0.4540(14) -0.151(2) 0.041(6) Uiso 1 1 d D . . . . H13 H 0.9109 0.4176 -0.1861 0.049 Uiso 1 1 calc R U . . . C14 C 0.7617(9) 0.4240(12) -0.1807(19) 0.027(5) Uiso 1 1 d D . . . . H14 H 0.7504 0.3669 -0.2365 0.033 Uiso 1 1 calc R U . . . C15 C 0.6827(11) 0.4786(13) -0.128(2) 0.029(5) Uiso 1 1 d D . . . . N4 N 0.6208(9) 0.6157(11) 0.1785(14) 0.027(4) Uiso 1 1 d D . . . . C16 C 0.6490(10) 0.6911(14) 0.2667(19) 0.040(6) Uiso 1 1 d D . . . . H16 H 0.6489 0.7626 0.2421 0.048 Uiso 1 1 calc R U . . . C17 C 0.6769(12) 0.6652(17) 0.388(2) 0.065(8) Uiso 1 1 d D . . . . H17 H 0.6977 0.7189 0.4446 0.078 Uiso 1 1 calc R U . . . C18 C 0.6755(14) 0.5616(16) 0.431(2) 0.059(8) Uiso 1 1 d D . . . . H18 H 0.6944 0.5438 0.5154 0.071 Uiso 1 1 calc R U . . . C19 C 0.6446(12) 0.4846(15) 0.3439(19) 0.044(6) Uiso 1 1 d D . . . . H19 H 0.6416 0.4136 0.3699 0.053 Uiso 1 1 calc R U . . . C20 C 0.6184(12) 0.5117(13) 0.2189(18) 0.028(5) Uiso 1 1 d D . . . . N6 N 0.5847(10) 0.4412(13) 0.127(2) 0.027(5) Uiso 1 1 d . . . . . N5 N 0.5852(11) 0.4467(13) -0.1325(19) 0.025(5) Uiso 1 1 d . . . . . Cl1 Cl 0.6868(3) 0.8228(3) 0.0044(9) 0.0330(14) Uani 1 1 d . . . . . Co1 Co 0.58724(13) 0.65809(18) 0.0032(5) 0.0261(8) Uani 1 1 d . . . . . Co2 Co 0.5000 0.5000 -0.0041(7) 0.0259(10) Uani 1 2 d S T P . . C21A C 0.023(5) 0.495(12) 0.308(9) 0.05(3) Uiso 0.300(16) 1 d D U P A -1 H21A H 0.0157 0.4256 0.3490 0.054 Uiso 0.300(16) 1 calc R U P A -1 H21B H 0.0486 0.5426 0.3736 0.054 Uiso 0.300(16) 1 calc R U P A -1 Cl2A Cl 0.1153(19) 0.481(2) 0.196(4) 0.079(11) Uiso 0.300(16) 1 d D U P A -1 Cl3A Cl -0.092(2) 0.537(2) 0.277(4) 0.059(9) Uiso 0.300(16) 1 d D U P A -1 C21B C 0.068(9) 0.485(10) 0.313(19) 0.05(3) Uiso 0.200(16) 1 d D U P A -2 H21C H 0.0727 0.4924 0.4070 0.055 Uiso 0.200(16) 1 calc R U P A -2 H21D H 0.1050 0.5438 0.2765 0.055 Uiso 0.200(16) 1 calc R U P A -2 Cl2B Cl 0.1321(18) 0.372(3) 0.275(4) 0.051(12) Uiso 0.200(16) 1 d D U P A -2 Cl3B Cl -0.051(4) 0.508(4) 0.276(6) 0.046(12) Uiso 0.200(16) 1 d D U P A -2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.040(2) 0.018(4) 0.041(5) 0.001(3) 0.001(5) -0.0071(18) Co1 0.0284(11) 0.0162(18) 0.034(3) -0.0028(16) 0.004(2) -0.0009(9) Co2 0.0272(14) 0.019(3) 0.032(4) 0.000 0.000 0.0021(14) _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 N1 C1 1.378(14) . ? N1 C5 1.367(14) . ? N1 Co1 1.993(15) . ? C1 C2 1.369(15) . ? C1 N5 1.38(2) 2_665 ? C2 C3 1.360(15) . ? C3 C4 1.370(15) . ? C4 C5 1.369(16) . ? N2 C6 1.381(14) . ? N2 C10 1.362(14) . ? N2 Co1 1.917(13) . ? C6 C7 1.392(14) . ? C6 N6 1.34(2) 2_665 ? C7 C8 1.368(15) . ? C8 C9 1.375(15) . ? C9 C10 1.365(15) . ? N3 C11 1.371(14) . ? N3 C15 1.360(15) . ? N3 Co1 1.942(12) . ? C11 C12 1.382(15) . ? C12 C13 1.376(15) . ? C13 C14 1.374(14) . ? C14 C15 1.378(14) . ? C15 N5 1.37(2) . ? N4 C16 1.365(15) . ? N4 C20 1.368(15) . ? N4 Co1 1.936(15) . ? C16 C17 1.348(16) . ? C17 C18 1.372(16) . ? C18 C19 1.383(16) . ? C19 C20 1.377(16) . ? C20 N6 1.37(2) . ? N6 C6 1.34(2) 2_665 ? N6 Co2 1.913(19) . ? N5 C1 1.38(2) 2_665 ? N5 Co2 1.874(18) . ? Cl1 Co1 2.461(4) . ? Co1 Co2 2.304(2) . ? Co2 N6 1.913(19) 2_665 ? Co2 N5 1.874(18) 2_665 ? Co2 Co1 2.304(2) 2_665 ? C21A Cl2A 1.71(6) . ? C21A Cl3A 1.67(6) . ? C21B Cl2B 1.71(6) . ? C21B Cl3B 1.67(6) . ? 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 C1 N1 Co1 123.2(11) . . ? C5 N1 C1 117.0(14) . . ? C5 N1 Co1 119.9(10) . . ? N1 C1 N5 112.1(15) . 2_665 ? C2 C1 N1 121.4(14) . . ? C2 C1 N5 126.5(14) . 2_665 ? C3 C2 C1 120.9(14) . . ? C2 C3 C4 118.2(16) . . ? C5 C4 C3 120.8(15) . . ? N1 C5 C4 121.6(15) . . ? C6 N2 Co1 119.0(11) . . ? C10 N2 C6 118.0(12) . . ? C10 N2 Co1 123.0(10) . . ? N2 C6 C7 119.7(13) . . ? N6 C6 N2 115.2(13) 2_665 . ? N6 C6 C7 124.9(14) 2_665 . ? C8 C7 C6 119.9(14) . . ? C7 C8 C9 121.0(15) . . ? C10 C9 C8 117.4(15) . . ? N2 C10 C9 123.9(15) . . ? C11 N3 Co1 118.9(11) . . ? C15 N3 C11 117.6(13) . . ? C15 N3 Co1 123.3(9) . . ? N3 C11 C12 121.6(15) . . ? C13 C12 C11 119.5(14) . . ? C14 C13 C12 119.0(14) . . ? C13 C14 C15 119.8(14) . . ? N3 C15 C14 121.5(13) . . ? N3 C15 N5 113.2(14) . . ? N5 C15 C14 125.3(14) . . ? C16 N4 C20 117.6(15) . . ? C16 N4 Co1 119.7(14) . . ? C20 N4 Co1 122.7(11) . . ? C17 C16 N4 122.0(17) . . ? C16 C17 C18 121.5(17) . . ? C17 C18 C19 117.1(17) . . ? C20 C19 C18 120.9(17) . . ? N4 C20 C19 120.9(14) . . ? N4 C20 N6 114.2(17) . . ? N6 C20 C19 124.9(16) . . ? C6 N6 C20 123.9(18) 2_665 . ? C6 N6 Co2 119.9(14) 2_665 . ? C20 N6 Co2 115.9(13) . . ? C1 N5 Co2 118.3(11) 2_665 . ? C15 N5 C1 124.5(16) . 2_665 ? C15 N5 Co2 117.1(13) . . ? N1 Co1 Cl1 95.3(4) . . ? N1 Co1 Co2 84.1(4) . . ? N2 Co1 N1 89.3(6) . . ? N2 Co1 N3 172.3(6) . . ? N2 Co1 N4 88.1(6) . . ? N2 Co1 Cl1 93.9(4) . . ? N2 Co1 Co2 88.9(4) . . ? N3 Co1 N1 92.1(6) . . ? N3 Co1 Cl1 93.5(4) . . ? N3 Co1 Co2 83.8(4) . . ? N4 Co1 N1 168.9(5) . . ? N4 Co1 N3 89.1(6) . . ? N4 Co1 Cl1 95.6(4) . . ? N4 Co1 Co2 85.0(4) . . ? Co2 Co1 Cl1 177.2(2) . . ? N6 Co2 N6 90.5(12) 2_665 . ? N6 Co2 Co1 87.1(5) 2_665 . ? N6 Co2 Co1 90.2(5) . . ? N6 Co2 Co1 87.1(5) . 2_665 ? N6 Co2 Co1 90.2(5) 2_665 2_665 ? N5 Co2 N6 89.7(6) 2_665 2_665 ? N5 Co2 N6 178.1(8) . 2_665 ? N5 Co2 N6 89.7(6) . . ? N5 Co2 N6 178.1(8) 2_665 . ? N5 Co2 N5 90.2(11) . 2_665 ? N5 Co2 Co1 91.7(5) 2_665 . ? N5 Co2 Co1 91.7(5) . 2_665 ? N5 Co2 Co1 91.0(5) 2_665 2_665 ? N5 Co2 Co1 91.0(5) . . ? Co1 Co2 Co1 176.3(4) 2_665 . ? Cl3A C21A Cl2A 125(6) . . ? Cl3B C21B Cl2B 125(7) . . ? 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 C1 C2 C3 0(2) . . . . ? C1 N1 C5 C4 -4(2) . . . . ? C1 C2 C3 C4 -1(3) . . . . ? C1 N5 Co2 N6 121.1(16) 2_665 . . . ? C1 N5 Co2 N5 -57.0(13) 2_665 . . 2_665 ? C1 N5 Co2 Co1 34.0(15) 2_665 . . 2_665 ? C1 N5 Co2 Co1 -148.7(15) 2_665 . . . ? C2 C3 C4 C5 0(3) . . . . ? C3 C4 C5 N1 2(3) . . . . ? C5 N1 C1 C2 2.8(18) . . . . ? C5 N1 C1 N5 -178.5(17) . . . 2_665 ? N2 C6 C7 C8 -1(2) . . . . ? C6 N2 C10 C9 1(2) . . . . ? C6 C7 C8 C9 2(3) . . . . ? C7 C8 C9 C10 -2(3) . . . . ? C8 C9 C10 N2 1(3) . . . . ? C10 N2 C6 C7 -0.7(17) . . . . ? C10 N2 C6 N6 174.3(16) . . . 2_665 ? N3 C11 C12 C13 4(2) . . . . ? N3 C15 N5 C1 160.0(18) . . . 2_665 ? _database_code_depnum_ccdc_archive 'CCDC 952409'