# 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_Zn2Mn _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H44 Mn N2 O14 Zn2' _chemical_formula_sum 'C54 H44 Mn N2 O14 Zn2' _chemical_formula_weight 1130.59 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'R -3' _symmetry_space_group_name_Hall '-R 3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 16.1173(16) _cell_length_b 16.1173(16) _cell_length_c 16.617(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3738.3(12) _cell_formula_units_Z 3 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4202 _cell_measurement_theta_min 2.53 _cell_measurement_theta_max 25.20 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.507 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1737 _exptl_absorpt_coefficient_mu 1.275 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.785 _exptl_absorpt_correction_T_max 0.883 _exptl_absorpt_process_details 'SADABS (Bruker, 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 19140 _diffrn_reflns_av_R_equivalents 0.0486 _diffrn_reflns_av_sigmaI/netI 0.0446 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.91 _diffrn_reflns_theta_max 29.98 _reflns_number_total 2406 _reflns_number_gt 1714 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 (Bruker, 2005)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXTL (Sheldrick, 2008)' _computing_structure_refinement 'SHELXTL (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 2008)' _computing_publication_material 'SHELXTL (Sheldrick, 2008)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0569P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2406 _refine_ls_number_parameters 117 _refine_ls_number_restraints 8 _refine_ls_R_factor_all 0.0609 _refine_ls_R_factor_gt 0.0382 _refine_ls_wR_factor_ref 0.0965 _refine_ls_wR_factor_gt 0.0899 _refine_ls_goodness_of_fit_ref 0.937 _refine_ls_restrained_S_all 0.937 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.6667 0.3333 0.3333 0.01304(15) Uani 1 6 d S . . Zn1 Zn 0.6667 0.3333 0.54761(2) 0.02574(14) Uani 1 3 d S . . O1 O 0.72356(10) 0.45692(10) 0.40826(9) 0.0258(3) Uani 1 1 d . . . O2 O 0.78732(11) 0.45045(10) 0.52537(9) 0.0296(3) Uani 1 1 d . . . C1 C 0.79211(14) 0.48720(14) 0.45674(12) 0.0255(4) Uani 1 1 d . . . C2 C 0.88578(16) 0.57080(16) 0.43349(14) 0.0340(5) Uani 1 1 d . . . C3 C 0.96912(18) 0.58837(19) 0.47199(17) 0.0447(6) Uani 1 1 d . . . H3 H 0.9661 0.5484 0.5153 0.054 Uiso 1 1 calc R . . C4 C 1.05670(19) 0.6635(2) 0.44808(18) 0.0549(8) Uani 1 1 d . . . H4 H 1.1135 0.6735 0.4740 0.066 Uiso 1 1 calc R . . C5 C 1.06256(19) 0.7240(2) 0.38707(18) 0.0550(8) Uani 1 1 d . . . C6 C 0.9785(2) 0.7081(2) 0.3503(2) 0.0723(12) Uani 1 1 d . . . H6 H 0.9814 0.7503 0.3090 0.087 Uiso 1 1 calc R . . C7 C 0.89022(19) 0.6316(2) 0.37272(17) 0.0540(8) Uani 1 1 d . . . H7 H 0.8334 0.6210 0.3465 0.065 Uiso 1 1 calc R . . C8 C 1.1578(2) 0.8024(2) 0.3627(2) 0.0635(9) Uani 1 1 d . . . H8 H 1.2114 0.8090 0.3921 0.076 Uiso 1 1 calc R . . O3 O 0.6739(14) 0.3261(9) 0.6673(2) 0.117(2) Uani 0.333333 1 d PD . . N1 N 0.6780(7) 0.2450(6) 0.7800(4) 0.117(2) Uani 0.333333 1 d PD . . C9 C 0.6392(8) 0.2544(8) 0.7119(4) 0.117(2) Uani 0.333333 1 d PD . . H9 H 0.5795 0.2014 0.6961 0.140 Uiso 0.333333 1 calc PR . . C10 C 0.6234(8) 0.1658(7) 0.8349(5) 0.117(2) Uani 0.333333 1 d PD . . H10A H 0.6558 0.1300 0.8482 0.175 Uiso 0.333333 1 d PR . . H10B H 0.5593 0.1218 0.8138 0.175 Uiso 0.333333 1 d PR . . H10C H 0.6178 0.1973 0.8834 0.175 Uiso 0.333333 1 d PR . . C11 C 0.7789(7) 0.3080(8) 0.7982(5) 0.117(2) Uani 0.333333 1 d PD . . H11A H 0.8107 0.3546 0.7548 0.175 Uiso 0.333333 1 d PR . . H11B H 0.7885 0.3420 0.8493 0.175 Uiso 0.333333 1 d PR . . H11C H 0.8061 0.2658 0.8019 0.175 Uiso 0.333333 1 d PR . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.01185(19) 0.01185(19) 0.0154(3) 0.000 0.000 0.00593(10) Zn1 0.02636(16) 0.02636(16) 0.0245(2) 0.000 0.000 0.01318(8) O1 0.0208(7) 0.0206(7) 0.0349(8) -0.0067(6) -0.0041(6) 0.0095(6) O2 0.0281(8) 0.0268(7) 0.0291(8) -0.0035(6) -0.0043(6) 0.0102(6) C1 0.0246(10) 0.0208(9) 0.0299(11) -0.0064(8) -0.0026(8) 0.0104(8) C2 0.0264(11) 0.0282(11) 0.0372(12) -0.0026(9) -0.0062(9) 0.0059(9) C3 0.0331(13) 0.0400(13) 0.0505(15) 0.0097(12) -0.0109(11) 0.0105(11) C4 0.0275(13) 0.0527(17) 0.0637(18) 0.0180(14) -0.0124(12) 0.0044(12) C5 0.0302(13) 0.0478(16) 0.0580(17) 0.0168(13) -0.0119(12) -0.0023(11) C6 0.0389(15) 0.067(2) 0.069(2) 0.0366(17) -0.0194(14) -0.0049(14) C7 0.0315(13) 0.0483(16) 0.0568(17) 0.0143(13) -0.0169(12) 0.0009(11) C8 0.0309(14) 0.0596(19) 0.069(2) 0.0218(15) -0.0190(13) -0.0009(13) O3 0.245(8) 0.111(5) 0.0303(18) 0.000(3) 0.003(4) 0.116(5) N1 0.245(8) 0.111(5) 0.0303(18) 0.000(3) 0.003(4) 0.116(5) C9 0.245(8) 0.111(5) 0.0303(18) 0.000(3) 0.003(4) 0.116(5) C10 0.245(8) 0.111(5) 0.0303(18) 0.000(3) 0.003(4) 0.116(5) C11 0.245(8) 0.111(5) 0.0303(18) 0.000(3) 0.003(4) 0.116(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn1 O1 2.1288(14) . ? Zn1 O2 1.9520(15) . ? Zn1 O3 1.999(4) . ? O1 C1 1.252(2) . ? O2 C1 1.270(3) . ? C1 C2 1.487(3) . ? C2 C3 1.383(3) . ? C2 C7 1.383(3) . ? C3 C4 1.381(4) . ? C3 H3 0.9500 . ? C4 C5 1.377(4) . ? C4 H4 0.9500 . ? C5 C6 1.389(4) . ? C5 C8 1.475(4) . ? C6 C7 1.389(4) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C8 1.321(6) 16_765 ? C8 H8 0.9500 . ? O3 C9 1.245(3) . ? N1 C9 1.338(3) . ? N1 C10 1.453(3) . ? N1 C11 1.455(3) . ? C9 H9 0.9500 . ? C10 H10A 0.9797 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9799 . ? C11 H11C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Mn1 O1 89.25(6) 2_655 . ? O2 Zn1 O2 116.50(3) . 2_655 ? O2 Zn1 O3 100.7(5) . . ? O2 Zn1 O3 106.0(5) 2_655 . ? O2 Zn1 O3 95.9(3) . 2_655 ? C1 O1 Mn1 128.62(13) . . ? C1 O2 Zn1 114.84(13) . . ? O1 C1 O2 124.06(19) . . ? O1 C1 C2 118.96(19) . . ? O2 C1 C2 116.98(18) . . ? C3 C2 C7 119.4(2) . . ? C3 C2 C1 120.5(2) . . ? C7 C2 C1 120.1(2) . . ? C4 C3 C2 120.6(2) . . ? C4 C3 H3 119.7 . . ? C2 C3 H3 119.7 . . ? C5 C4 C3 120.7(2) . . ? C5 C4 H4 119.6 . . ? C3 C4 H4 119.6 . . ? C4 C5 C6 118.6(2) . . ? C4 C5 C8 118.8(2) . . ? C6 C5 C8 122.6(3) . . ? C5 C6 C7 121.1(3) . . ? C5 C6 H6 119.4 . . ? C7 C6 H6 119.4 . . ? C2 C7 C6 119.5(2) . . ? C2 C7 H7 120.3 . . ? C6 C7 H7 120.3 . . ? C8 C8 C5 126.1(3) 16_765 . ? C8 C8 H8 117.0 16_765 . ? C5 C8 H8 117.0 . . ? C9 O3 Zn1 129.4(7) . . ? C9 N1 C10 121.2(3) . . ? C9 N1 C11 121.2(3) . . ? C10 N1 C11 117.3(3) . . ? O3 C9 N1 126.2(4) . . ? O3 C9 H9 116.9 . . ? N1 C9 H9 116.9 . . ? N1 C10 H10A 113.1 . . ? N1 C10 H10B 111.6 . . ? H10A C10 H10B 109.5 . . ? N1 C10 H10C 103.6 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 H11A 110.9 . . ? N1 C11 H11B 112.3 . . ? H11A C11 H11B 109.5 . . ? N1 C11 H11C 105.1 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? 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 O1 Mn1 O1 C1 19.33(18) 3_665 . . . ? O1 Mn1 O1 C1 -71.41(15) 17 . . . ? O1 Mn1 O1 C1 -160.67(18) 18_545 . . . ? O1 Mn1 O1 C1 108.59(15) 2_655 . . . ? O2 Zn1 O2 C1 95.08(13) 3_665 . . . ? O2 Zn1 O2 C1 -48.61(17) 2_655 . . . ? O3 Zn1 O2 C1 -162.7(4) . . . . ? O3 Zn1 O2 C1 -153.7(6) 2_655 . . . ? O3 Zn1 O2 C1 -153.9(4) 3_665 . . . ? Mn1 O1 C1 O2 -75.9(2) . . . . ? Mn1 O1 C1 C2 103.6(2) . . . . ? Zn1 O2 C1 O1 5.5(3) . . . . ? Zn1 O2 C1 C2 -174.03(15) . . . . ? O1 C1 C2 C3 -160.0(2) . . . . ? O2 C1 C2 C3 19.5(3) . . . . ? O1 C1 C2 C7 19.7(3) . . . . ? O2 C1 C2 C7 -160.8(2) . . . . ? C7 C2 C3 C4 -2.6(4) . . . . ? C1 C2 C3 C4 177.1(3) . . . . ? C2 C3 C4 C5 1.9(5) . . . . ? C3 C4 C5 C6 0.2(6) . . . . ? C3 C4 C5 C8 -179.1(3) . . . . ? C4 C5 C6 C7 -1.6(6) . . . . ? C8 C5 C6 C7 177.7(4) . . . . ? C3 C2 C7 C6 1.2(5) . . . . ? C1 C2 C7 C6 -178.5(3) . . . . ? C5 C6 C7 C2 0.9(6) . . . . ? C4 C5 C8 C8 177.8(5) . . . 16_765 ? C6 C5 C8 C8 -1.5(8) . . . 16_765 ? Zn1 O3 C9 N1 146.2(11) . . . . ? C10 N1 C9 O3 168.4(13) . . . . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 29.98 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.751 _refine_diff_density_min -0.459 _refine_diff_density_rms 0.071 _database_code_depnum_ccdc_archive 'CCDC 964384' ####################################################################### # # 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_Cd3 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H44 Cd3 N2 O14' _chemical_formula_sum 'C54 H44 Cd3 N2 O14' _chemical_formula_weight 1282.11 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cd Cd -0.8075 1.2024 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'R -3' _symmetry_space_group_name_Hall '-R 3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 16.488(3) _cell_length_b 16.488(3) _cell_length_c 16.704(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3933(3) _cell_formula_units_Z 3 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2340 _cell_measurement_theta_min 2.47 _cell_measurement_theta_max 21.93 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.47 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.624 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1914 _exptl_absorpt_coefficient_mu 1.273 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.586 _exptl_absorpt_correction_T_max 0.905 _exptl_absorpt_process_details 'SADABS (Bruker, 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 14415 _diffrn_reflns_av_R_equivalents 0.0449 _diffrn_reflns_av_sigmaI/netI 0.0742 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 3.75 _diffrn_reflns_theta_max 29.98 _reflns_number_total 2503 _reflns_number_gt 1585 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 (Bruker, 2005)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXTL (Sheldrick, 2008)' _computing_structure_refinement 'SHELXTL (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 2008)' _computing_publication_material 'SHELXTL (Sheldrick, 2008)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.01P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2503 _refine_ls_number_parameters 123 _refine_ls_number_restraints 26 _refine_ls_R_factor_all 0.0547 _refine_ls_R_factor_gt 0.0335 _refine_ls_wR_factor_ref 0.0543 _refine_ls_wR_factor_gt 0.0525 _refine_ls_goodness_of_fit_ref 0.924 _refine_ls_restrained_S_all 0.983 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cd1 Cd 0.3333 0.6667 0.87516(2) 0.03170(12) Uani 1 3 d S . . Cd2 Cd 0.3333 0.6667 0.6667 0.02162(13) Uani 1 6 d S . . O1 O 0.31443(16) 0.78866(14) 0.86045(12) 0.0472(6) Uani 1 1 d D . . O2 O 0.39013(13) 0.79141(13) 0.75059(13) 0.0384(5) Uani 1 1 d D . . C1 C 0.3497(2) 0.8233(2) 0.79352(18) 0.0358(7) Uani 1 1 d D . . C2 C 0.34469(16) 0.90535(14) 0.76534(13) 0.0460(9) Uani 1 1 d D . . C3 C 0.4009(2) 0.9631(2) 0.70453(17) 0.0814(14) Uani 1 1 d D . . H3 H 0.4451 0.9509 0.6788 0.098 Uiso 1 1 calc R . . C4 C 0.3916(3) 1.0396(2) 0.6814(2) 0.115(2) Uani 1 1 d D . . H4 H 0.4297 1.0799 0.6398 0.138 Uiso 1 1 calc R . . C5 C 0.3267(2) 1.0565(2) 0.71931(19) 0.113(2) Uani 1 1 d D . . C6 C 0.2697(3) 0.9992(2) 0.7807(2) 0.0858(15) Uani 1 1 d D . . H6 H 0.2254 1.0109 0.8068 0.103 Uiso 1 1 calc R . . C7 C 0.2810(2) 0.9255(2) 0.80151(19) 0.0632(11) Uani 1 1 d D . . H7 H 0.2429 0.8854 0.8433 0.076 Uiso 1 1 calc R . . C8 C 0.3145(3) 1.1378(2) 0.69642(16) 0.144(2) Uani 1 1 d D . . H8 H 0.2740 1.1483 0.7297 0.173 Uiso 1 1 calc R . . O3 O 0.357(2) 0.6926(14) 1.0057(4) 0.184(12) Uani 0.333333 1 d PD . . N1 N 0.3604(12) 0.7786(7) 1.1153(5) 0.303(11) Uani 0.333333 1 d PD . . C9 C 0.3208(14) 0.7268(11) 1.0499(7) 0.303(11) Uani 0.333333 1 d PD . . H9 H 0.2600 0.7150 1.0359 0.363 Uiso 0.333333 1 calc PR . . C10 C 0.3090(16) 0.8073(15) 1.1678(8) 0.303(11) Uani 0.333333 1 d PD . . H10A H 0.2456 0.7820 1.1499 0.454 Uiso 0.333333 1 d PR . . H10B H 0.3093 0.7819 1.2195 0.454 Uiso 0.333333 1 d PR . . H10C H 0.3384 0.8742 1.1716 0.454 Uiso 0.333333 1 d PR . . C11 C 0.4569(12) 0.8088(13) 1.1368(8) 0.303(11) Uani 0.333333 1 d PD . . H11A H 0.4722 0.8369 1.1890 0.454 Uiso 0.333333 1 d PR . . H11B H 0.4710 0.7589 1.1345 0.454 Uiso 0.333333 1 d PR . . H11C H 0.4929 0.8551 1.0971 0.454 Uiso 0.333333 1 d PR . . 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 Cd1 0.03068(16) 0.03068(16) 0.0337(2) 0.000 0.000 0.01534(8) Cd2 0.02107(18) 0.02107(18) 0.0227(3) 0.000 0.000 0.01054(9) O1 0.0702(17) 0.0366(13) 0.0391(14) -0.0006(11) 0.0013(12) 0.0300(13) O2 0.0336(12) 0.0297(12) 0.0534(14) -0.0159(10) -0.0091(10) 0.0170(10) C1 0.0424(19) 0.0262(17) 0.0378(19) -0.0085(14) -0.0083(15) 0.0164(15) C2 0.071(3) 0.041(2) 0.042(2) -0.0053(16) 0.0006(18) 0.039(2) C3 0.144(4) 0.073(3) 0.054(3) 0.019(2) 0.036(3) 0.074(3) C4 0.217(7) 0.096(4) 0.067(3) 0.040(3) 0.050(4) 0.104(5) C5 0.201(7) 0.106(4) 0.109(4) -0.019(4) -0.018(4) 0.133(5) C6 0.114(4) 0.076(3) 0.091(4) 0.023(3) 0.027(3) 0.066(3) C7 0.071(3) 0.057(3) 0.081(3) 0.007(2) 0.017(2) 0.046(2) C8 0.219(7) 0.145(7) 0.105(5) 0.022(4) 0.058(5) 0.119(6) O3 0.39(4) 0.29(3) 0.016(3) -0.030(10) 0.009(12) 0.28(3) N1 0.73(3) 0.174(10) 0.032(6) -0.004(6) -0.038(11) 0.248(17) C9 0.73(3) 0.174(10) 0.032(6) -0.004(6) -0.038(11) 0.248(17) C10 0.73(3) 0.174(10) 0.032(6) -0.004(6) -0.038(11) 0.248(17) C11 0.73(3) 0.174(10) 0.032(6) -0.004(6) -0.038(11) 0.248(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 Cd1 O1 2.198(2) . ? Cd1 O3 2.219(7) . ? Cd2 O2 2.2686(19) . ? O1 C1 1.258(3) . ? O2 C1 1.259(3) . ? C1 C2 1.474(3) . ? C2 C3 1.384(3) . ? C2 C7 1.388(3) . ? C3 C4 1.399(3) . ? C3 H3 0.9500 . ? C4 C5 1.387(3) . ? C4 H4 0.9500 . ? C5 C6 1.393(3) . ? C5 C8 1.500(3) . ? C6 C7 1.364(3) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C8 1.300(3) 13_576 ? C8 H8 0.9500 . ? O3 C9 1.250(3) . ? N1 C9 1.338(3) . ? N1 C10 1.454(3) . ? N1 C11 1.454(3) . ? C9 H9 0.9500 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Cd1 O1 118.77(2) . 2_665 ? O1 Cd1 O3 90.5(7) . 2_665 ? O1 Cd1 O3 91.5(4) . . ? O1 Cd1 O3 107.1(7) 2_665 . ? O2 Cd2 O2 85.82(8) . 2_665 ? O2 Cd2 O2 94.17(8) . 14_456 ? C1 O1 Cd1 105.65(19) . . ? C1 O2 Cd2 131.75(18) . . ? O2 C1 O1 122.6(3) . . ? O2 C1 C2 119.1(3) . . ? O1 C1 C2 118.4(3) . . ? C3 C2 C7 118.8(3) . . ? C3 C2 C1 122.7(3) . . ? C7 C2 C1 118.5(3) . . ? C2 C3 C4 119.0(3) . . ? C2 C3 H3 120.5 . . ? C4 C3 H3 120.5 . . ? C5 C4 C3 120.0(4) . . ? C5 C4 H4 120.0 . . ? C3 C4 H4 120.0 . . ? C4 C5 C6 121.7(3) . . ? C4 C5 C8 121.7(3) . . ? C6 C5 C8 116.6(2) . . ? C7 C6 C5 116.5(4) . . ? C7 C6 H6 121.8 . . ? C5 C6 H6 121.8 . . ? C6 C7 C2 124.0(3) . . ? C6 C7 H7 118.0 . . ? C2 C7 H7 118.0 . . ? C8 C8 C5 128.4(4) 13_576 . ? C8 C8 H8 115.8 13_576 . ? C5 C8 H8 115.8 . . ? C9 O3 Cd1 126.0(10) . . ? C9 N1 C10 121.5(3) . . ? C9 N1 C11 121.4(3) . . ? C10 N1 C11 117.1(3) . . ? O3 C9 N1 125.4(5) . . ? O3 C9 H9 117.3 . . ? N1 C9 H9 117.3 . . ? N1 C10 H10A 110.8 . . ? N1 C10 H10B 105.7 . . ? N1 C10 H10C 111.9 . . ? H10A C10 H10B 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 H11A 111.6 . . ? N1 C11 H11B 112.9 . . ? N1 C11 H11C 103.7 . . ? H11A C11 H11B 109.4 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? 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 O1 Cd1 O1 C1 -105.23(17) 2_665 . . . ? O1 Cd1 O1 C1 52.8(2) 3_565 . . . ? O3 Cd1 O1 C1 162.8(5) 2_665 . . . ? O3 Cd1 O1 C1 144.2(7) . . . . ? O3 Cd1 O1 C1 154.4(6) 3_565 . . . ? O2 Cd2 O2 C1 -31.3(3) 2_665 . . . ? O2 Cd2 O2 C1 62.6(2) 15_556 . . . ? O2 Cd2 O2 C1 148.7(3) 14_456 . . . ? O2 Cd2 O2 C1 -117.4(2) 3_565 . . . ? Cd2 O2 C1 O1 80.1(3) . . . . ? Cd2 O2 C1 C2 -101.0(2) . . . . ? Cd1 O1 C1 O2 -3.2(3) . . . . ? Cd1 O1 C1 C2 177.92(11) . . . . ? O2 C1 C2 C3 -16.3(2) . . . . ? O1 C1 C2 C3 162.7(2) . . . . ? O2 C1 C2 C7 163.8(2) . . . . ? O1 C1 C2 C7 -17.2(2) . . . . ? C7 C2 C3 C4 -0.08(12) . . . . ? C1 C2 C3 C4 -179.99(9) . . . . ? C2 C3 C4 C5 -0.11(19) . . . . ? C3 C4 C5 C6 0.3(3) . . . . ? C3 C4 C5 C8 179.98(15) . . . . ? C4 C5 C6 C7 -0.2(3) . . . . ? C8 C5 C6 C7 -179.93(16) . . . . ? C5 C6 C7 C2 0.0(3) . . . . ? C3 C2 C7 C6 0.1(2) . . . . ? C1 C2 C7 C6 -179.94(13) . . . . ? C4 C5 C8 C8 7.3(6) . . . 13_576 ? C6 C5 C8 C8 -172.9(5) . . . 13_576 ? O1 Cd1 O3 C9 32.5(17) . . . . ? Cd1 O3 C9 N1 -149.4(12) . . . . ? C10 N1 C9 O3 -173.5(17) . . . . ? C11 N1 C9 O3 6.5(17) . . . . ? _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 29.98 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 0.907 _refine_diff_density_min -0.867 _refine_diff_density_rms 0.084 _database_code_depnum_ccdc_archive 'CCDC 964385' ####################################################################### # # 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_Co2Mn _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H44 Co2 Mn N2 O14' _chemical_formula_sum 'C54 H44 Co2 Mn N2 O14' _chemical_formula_weight 1117.71 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 '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' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'R -3' _symmetry_space_group_name_Hall '-R 3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 16.147(2) _cell_length_b 16.147(2) _cell_length_c 16.617(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3752.0(15) _cell_formula_units_Z 3 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4994 _cell_measurement_theta_min 2.52 _cell_measurement_theta_max 27.78 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.484 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1719 _exptl_absorpt_coefficient_mu 0.974 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.814 _exptl_absorpt_correction_T_max 0.926 _exptl_absorpt_process_details 'SADABS (Bruker, 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 19174 _diffrn_reflns_av_R_equivalents 0.0418 _diffrn_reflns_av_sigmaI/netI 0.0343 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.90 _diffrn_reflns_theta_max 30.00 _reflns_number_total 2419 _reflns_number_gt 1812 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 (Bruker, 2005)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXTL (Sheldrick, 2008)' _computing_structure_refinement 'SHELXTL (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 2008)' _computing_publication_material 'SHELXTL (Sheldrick, 2008)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0643P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2419 _refine_ls_number_parameters 123 _refine_ls_number_restraints 10 _refine_ls_R_factor_all 0.0543 _refine_ls_R_factor_gt 0.0372 _refine_ls_wR_factor_ref 0.0991 _refine_ls_wR_factor_gt 0.0941 _refine_ls_goodness_of_fit_ref 0.946 _refine_ls_restrained_S_all 0.946 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.6667 0.3333 0.3333 0.01437(13) Uani 1 6 d S . . Co1 Co 0.6667 0.3333 0.54926(2) 0.02439(13) Uani 1 3 d S . . O1 O 0.73296(8) 0.45706(8) 0.40837(7) 0.0264(3) Uani 1 1 d D . . O2 O 0.66380(9) 0.45126(9) 0.52594(7) 0.0289(3) Uani 1 1 d D . . C1 C 0.69483(12) 0.48759(12) 0.45649(11) 0.0255(4) Uani 1 1 d . . . C2 C 0.68534(14) 0.57110(12) 0.43356(11) 0.0313(4) Uani 1 1 d D . . C3 C 0.74146(18) 0.63219(17) 0.37250(14) 0.0476(6) Uani 1 1 d . . . H3 H 0.7871 0.6212 0.3457 0.057 Uiso 1 1 calc R . . C4 C 0.7308(2) 0.7090(2) 0.35080(16) 0.0631(9) Uani 1 1 d . . . H4 H 0.7713 0.7520 0.3106 0.076 Uiso 1 1 calc R . . C5 C 0.6615(2) 0.72465(17) 0.38700(15) 0.0505(6) Uani 1 1 d . . . C6 C 0.60641(18) 0.66322(17) 0.44834(14) 0.0467(6) Uani 1 1 d . . . H6 H 0.5594 0.6729 0.4742 0.056 Uiso 1 1 calc R . . C7 C 0.61883(16) 0.58902(15) 0.47210(13) 0.0395(5) Uani 1 1 d . . . H7 H 0.5818 0.5492 0.5153 0.047 Uiso 1 1 calc R . . C8 C 0.6446(2) 0.80232(19) 0.36309(16) 0.0588(8) Uani 1 1 d . . . H8 H 0.5981 0.8091 0.3927 0.071 Uiso 1 1 calc R . . O3 O 0.6923(4) 0.3612(4) 0.6684(2) 0.0429(15) Uani 0.333333 1 d PD . . N1 N 0.6862(6) 0.4393(6) 0.7818(3) 0.124(3) Uani 0.333333 1 d PD . . C9 C 0.6499(7) 0.3898(7) 0.7138(4) 0.124(3) Uani 0.333333 1 d PD . . H9 H 0.5873 0.3752 0.6988 0.148 Uiso 0.333333 1 calc PR . . C10 C 0.7858(6) 0.4753(8) 0.8035(5) 0.124(3) Uani 0.333333 1 d PD . . H10A H 0.8206 0.5350 0.7730 0.185 Uiso 0.333333 1 d PR . . H10B H 0.8077 0.4311 0.7870 0.185 Uiso 0.333333 1 d PR . . H10C H 0.7977 0.4888 0.8611 0.185 Uiso 0.333333 1 d PR . . C11 C 0.6297(8) 0.4633(8) 0.8346(5) 0.124(3) Uani 0.333333 1 d PD . . H11A H 0.5620 0.4322 0.8198 0.185 Uiso 0.333333 1 d PR . . H11B H 0.6365 0.4361 0.8853 0.185 Uiso 0.333333 1 d PR . . H11C H 0.6549 0.5321 0.8414 0.185 Uiso 0.333333 1 d PR . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.01303(17) 0.01303(17) 0.0171(3) 0.000 0.000 0.00652(9) Co1 0.02425(16) 0.02425(16) 0.0247(2) 0.000 0.000 0.01213(8) O1 0.0233(6) 0.0205(6) 0.0362(7) -0.0084(5) -0.0037(5) 0.0115(5) O2 0.0331(7) 0.0251(6) 0.0291(6) -0.0046(5) -0.0016(5) 0.0150(5) C1 0.0240(8) 0.0191(8) 0.0318(9) -0.0074(6) -0.0061(7) 0.0097(7) C2 0.0400(10) 0.0273(9) 0.0324(9) -0.0026(7) 0.0032(8) 0.0212(8) C3 0.0677(16) 0.0453(13) 0.0480(13) 0.0120(10) 0.0264(12) 0.0420(13) C4 0.097(2) 0.0622(16) 0.0623(16) 0.0334(13) 0.0477(16) 0.0636(17) C5 0.0734(17) 0.0461(13) 0.0533(13) 0.0148(10) 0.0268(12) 0.0458(13) C6 0.0573(14) 0.0468(13) 0.0538(13) 0.0123(10) 0.0235(11) 0.0392(12) C7 0.0446(12) 0.0351(10) 0.0459(12) 0.0056(9) 0.0142(9) 0.0252(10) C8 0.0860(19) 0.0581(15) 0.0620(16) 0.0227(12) 0.0403(14) 0.0582(15) O3 0.041(4) 0.052(4) 0.0217(15) -0.003(2) -0.004(2) 0.013(2) N1 0.266(9) 0.099(4) 0.043(3) 0.010(3) 0.004(4) 0.119(6) C9 0.266(9) 0.099(4) 0.043(3) 0.010(3) 0.004(4) 0.119(6) C10 0.266(9) 0.099(4) 0.043(3) 0.010(3) 0.004(4) 0.119(6) C11 0.266(9) 0.099(4) 0.043(3) 0.010(3) 0.004(4) 0.119(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 Mn1 O1 2.1338(12) . ? Co1 O2 1.9662(12) . ? Co1 O3 2.027(3) . ? O1 C1 1.251(2) . ? O2 C1 1.278(2) . ? C1 C2 1.481(2) . ? C2 C3 1.389(3) . ? C2 C7 1.399(3) . ? C3 C4 1.383(3) . ? C3 H3 0.9500 . ? C4 C5 1.400(3) . ? C4 H4 0.9500 . ? C5 C6 1.390(3) . ? C5 C8 1.465(3) . ? C6 C7 1.368(3) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C8 1.332(5) 16_665 ? C8 H8 0.9500 . ? O3 C9 1.251(3) . ? N1 C9 1.339(3) . ? N1 C11 1.450(3) . ? N1 C10 1.456(3) . ? C9 H9 0.9500 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Mn1 O1 89.30(5) . 2_655 ? O2 Co1 O2 116.21(2) 2_655 . ? O2 Co1 O3 113.69(11) 2_655 . ? O2 Co1 O3 94.5(3) . . ? O2 Co1 O3 95.6(3) . 2_655 ? C1 O1 Mn1 128.84(11) . . ? C1 O2 Co1 115.40(11) . . ? O1 C1 O2 123.61(16) . . ? O1 C1 C2 119.32(16) . . ? O2 C1 C2 117.06(15) . . ? C3 C2 C7 118.88(16) . . ? C3 C2 C1 120.44(16) . . ? C7 C2 C1 120.67(17) . . ? C4 C3 C2 119.86(19) . . ? C4 C3 H3 120.1 . . ? C2 C3 H3 120.1 . . ? C3 C4 C5 121.3(2) . . ? C3 C4 H4 119.4 . . ? C5 C4 H4 119.4 . . ? C6 C5 C4 118.1(2) . . ? C6 C5 C8 118.91(19) . . ? C4 C5 C8 123.0(2) . . ? C7 C6 C5 121.0(2) . . ? C7 C6 H6 119.5 . . ? C5 C6 H6 119.5 . . ? C6 C7 C2 120.85(19) . . ? C6 C7 H7 119.6 . . ? C2 C7 H7 119.6 . . ? C8 C8 C5 125.9(3) 16_665 . ? C8 C8 H8 117.0 16_665 . ? C5 C8 H8 117.0 . . ? C9 O3 Co1 125.6(6) . . ? C9 N1 C11 121.6(3) . . ? C9 N1 C10 120.8(3) . . ? C11 N1 C10 117.5(2) . . ? O3 C9 N1 124.9(4) . . ? O3 C9 H9 117.5 . . ? N1 C9 H9 117.5 . . ? N1 C10 H10A 103.9 . . ? N1 C10 H10B 111.8 . . ? H10A C10 H10B 109.5 . . ? N1 C10 H10C 112.6 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 H11A 113.7 . . ? N1 C11 H11B 100.0 . . ? H11A C11 H11B 109.5 . . ? N1 C11 H11C 114.3 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? 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 O1 Mn1 O1 C1 -109.09(13) 3_665 . . . ? O1 Mn1 O1 C1 160.22(16) 17 . . . ? O1 Mn1 O1 C1 70.91(13) 18_545 . . . ? O1 Mn1 O1 C1 -19.78(16) 2_655 . . . ? O2 Co1 O2 C1 48.70(14) 3_665 . . . ? O2 Co1 O2 C1 -93.60(11) 2_655 . . . ? O3 Co1 O2 C1 156.9(3) 3_665 . . . ? O3 Co1 O2 C1 147.2(2) . . . . ? O3 Co1 O2 C1 168.6(2) 2_655 . . . ? Mn1 O1 C1 O2 76.9(2) . . . . ? Mn1 O1 C1 C2 -103.91(17) . . . . ? Co1 O2 C1 O1 -6.4(2) . . . . ? Co1 O2 C1 C2 174.33(12) . . . . ? O1 C1 C2 C3 -19.2(3) . . . . ? O2 C1 C2 C3 160.1(2) . . . . ? O1 C1 C2 C7 159.86(19) . . . . ? O2 C1 C2 C7 -20.9(3) . . . . ? C7 C2 C3 C4 -0.1(4) . . . . ? C1 C2 C3 C4 179.0(2) . . . . ? C2 C3 C4 C5 -2.6(5) . . . . ? C3 C4 C5 C6 3.0(5) . . . . ? C3 C4 C5 C8 -176.9(3) . . . . ? C4 C5 C6 C7 -0.7(4) . . . . ? C8 C5 C6 C7 179.3(3) . . . . ? C5 C6 C7 C2 -2.0(4) . . . . ? C3 C2 C7 C6 2.4(3) . . . . ? C1 C2 C7 C6 -176.6(2) . . . . ? C6 C5 C8 C8 -177.2(4) . . . 16_665 ? C4 C5 C8 C8 2.8(6) . . . 16_665 ? O2 Co1 O3 C9 45.7(7) . . . . ? Co1 O3 C9 N1 -155.0(7) . . . . ? C11 N1 C9 O3 -174.9(10) . . . . ? C10 N1 C9 O3 8.1(16) . . . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 30.00 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.580 _refine_diff_density_min -0.383 _refine_diff_density_rms 0.067 _database_code_depnum_ccdc_archive 'CCDC 964386' ####################################################################### # # 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_Mn3 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H44 Mn3 N2 O14' _chemical_formula_sum 'C54 H44 Mn3 N2 O14' _chemical_formula_weight 1109.73 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'R -3' _symmetry_space_group_name_Hall '-R 3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 16.3456(19) _cell_length_b 16.3456(19) _cell_length_c 16.590(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3838.7(15) _cell_formula_units_Z 3 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4452 _cell_measurement_theta_min 2.492 _cell_measurement_theta_max 27.43 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.54 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.440 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1707 _exptl_absorpt_coefficient_mu 0.797 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.673 _exptl_absorpt_correction_T_max 0.910 _exptl_absorpt_process_details 'SADABS (Bruker, 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART APEX II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 14674 _diffrn_reflns_av_R_equivalents 0.0435 _diffrn_reflns_av_sigmaI/netI 0.0284 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.49 _diffrn_reflns_theta_max 30.00 _reflns_number_total 2480 _reflns_number_gt 1998 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 (Bruker, 2005)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXTL (Sheldrick, 2008)' _computing_structure_refinement 'SHELXTL (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 2008)' _computing_publication_material 'SHELXTL (Sheldrick, 2008)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0939P)^2^+11P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2480 _refine_ls_number_parameters 123 _refine_ls_number_restraints 16 _refine_ls_R_factor_all 0.0715 _refine_ls_R_factor_gt 0.0584 _refine_ls_wR_factor_ref 0.1661 _refine_ls_wR_factor_gt 0.1574 _refine_ls_goodness_of_fit_ref 1.033 _refine_ls_restrained_S_all 1.033 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.3333 0.6667 0.1667 0.01770(19) Uani 1 6 d S . . Mn2 Mn 0.3333 0.6667 0.37582(4) 0.0309(2) Uani 1 3 d S . . O1 O 0.21143(13) 0.60323(12) 0.24493(14) 0.0409(5) Uani 1 1 d D . . O2 O 0.21383(13) 0.53553(15) 0.35980(12) 0.0450(5) Uani 1 1 d D . . C1 C 0.17823(17) 0.53291(18) 0.29143(16) 0.0348(5) Uani 1 1 d D . . C2 C 0.09551(13) 0.44351(15) 0.26497(12) 0.0413(6) Uani 1 1 d D . . C3 C 0.0754(2) 0.3580(2) 0.3019(2) 0.0546(8) Uani 1 1 d D . . H3 H 0.1155 0.3589 0.3437 0.066 Uiso 1 1 calc R . . C4 C -0.0006(3) 0.2736(3) 0.2792(2) 0.0712(12) Uani 1 1 d D . . H4 H -0.0126 0.2169 0.3053 0.085 Uiso 1 1 calc R . . C5 C -0.0587(3) 0.2710(3) 0.2194(2) 0.0837(15) Uani 1 1 d D . . C6 C -0.0405(3) 0.3554(3) 0.1815(2) 0.102(2) Uani 1 1 d D . . H6 H -0.0812 0.3538 0.1398 0.122 Uiso 1 1 calc R . . C7 C 0.0371(3) 0.4419(3) 0.2046(2) 0.0706(13) Uani 1 1 d D . . H7 H 0.0492 0.4988 0.1789 0.085 Uiso 1 1 calc R . . C8 C -0.1390(3) 0.1762(3) 0.1992(3) 0.102(2) Uani 1 1 d D . . H8 H -0.1422 0.1223 0.2273 0.122 Uiso 1 1 d . . . N1 N 0.2246(6) 0.5795(8) 0.6148(4) 0.128(4) Uani 0.333333 1 d PD . . O3 O 0.3035(6) 0.6555(13) 0.4993(4) 0.078(5) Uani 0.333333 1 d PD . . C9 C 0.2759(10) 0.5891(11) 0.5487(6) 0.128(4) Uani 0.333333 1 d PD . . H9 H 0.2926 0.5420 0.5387 0.153 Uiso 0.333333 1 calc PR . . C10 C 0.1986(12) 0.5022(10) 0.6710(7) 0.128(4) Uani 0.333333 1 d PD . . H10A H 0.2240 0.4660 0.6474 0.191 Uiso 0.333333 1 d PR . . H10B H 0.2267 0.5250 0.7229 0.191 Uiso 0.333333 1 d PR . . H10C H 0.1314 0.4630 0.6769 0.191 Uiso 0.333333 1 d PR . . C11 C 0.1929(12) 0.6462(10) 0.6329(8) 0.128(4) Uani 0.333333 1 d PD . . H11A H 0.2154 0.6905 0.5890 0.191 Uiso 0.333333 1 d PR . . H11B H 0.1254 0.6168 0.6363 0.191 Uiso 0.333333 1 d PR . . H11C H 0.2207 0.6788 0.6823 0.191 Uiso 0.333333 1 d PR . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.0177(2) 0.0177(2) 0.0177(3) 0.000 0.000 0.00885(12) Mn2 0.0305(2) 0.0305(2) 0.0318(4) 0.000 0.000 0.01523(12) O1 0.0310(9) 0.0292(9) 0.0613(13) 0.0098(8) 0.0220(8) 0.0140(7) O2 0.0336(10) 0.0477(11) 0.0361(10) 0.0001(8) 0.0070(8) 0.0070(8) C1 0.0277(11) 0.0305(11) 0.0369(12) -0.0004(9) 0.0110(9) 0.0076(9) C2 0.0389(13) 0.0311(12) 0.0350(13) 0.0052(10) 0.0026(10) 0.0034(10) C3 0.0476(17) 0.0348(14) 0.066(2) 0.0112(14) -0.0026(15) 0.0090(13) C4 0.063(2) 0.0343(16) 0.088(3) 0.0068(17) -0.011(2) 0.0028(15) C5 0.079(3) 0.046(2) 0.069(3) 0.0043(18) -0.017(2) -0.0121(19) C6 0.092(3) 0.074(3) 0.072(3) 0.018(2) -0.044(3) -0.010(2) C7 0.071(2) 0.0497(19) 0.053(2) 0.0191(16) -0.0138(17) 0.0015(17) C8 0.107(4) 0.046(2) 0.093(3) 0.024(2) -0.048(3) -0.006(2) N1 0.124(7) 0.123(7) 0.045(4) -0.008(4) -0.001(4) -0.006(6) O3 0.083(8) 0.096(7) 0.031(3) -0.001(7) 0.010(3) 0.026(7) C9 0.124(7) 0.123(7) 0.045(4) -0.008(4) -0.001(4) -0.006(6) C10 0.124(7) 0.123(7) 0.045(4) -0.008(4) -0.001(4) -0.006(6) C11 0.124(7) 0.123(7) 0.045(4) -0.008(4) -0.001(4) -0.006(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 Mn1 O1 2.1600(17) . ? Mn2 O2 2.0722(19) . ? Mn2 O3 2.092(6) . ? O1 C1 1.260(3) . ? O2 C1 1.266(3) . ? C1 C2 1.477(3) . ? C2 C7 1.375(5) . ? C2 C3 1.406(4) . ? C3 C4 1.369(5) . ? C3 H3 0.9500 . ? C4 C5 1.360(6) . ? C4 H4 0.9500 . ? C5 C6 1.407(6) . ? C5 C8 1.485(5) . ? C6 C7 1.400(6) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C8 1.340(9) 13_455 ? C8 H8 0.9751 . ? N1 C9 1.340(3) . ? N1 C10 1.451(3) . ? N1 C11 1.454(3) . ? O3 C9 1.251(3) . ? C9 H9 0.9500 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Mn1 O1 92.41(9) . 14_455 ? O1 Mn1 O1 87.59(9) . 2_665 ? O2 Mn2 O2 118.38(2) . 2_665 ? O2 Mn2 O3 88.7(4) . . ? O2 Mn2 O3 108.6(4) 2_665 . ? O2 Mn2 O3 94.6(6) . 2_665 ? C1 O1 Mn1 132.79(16) . . ? C1 O2 Mn2 109.24(17) . . ? O1 C1 O2 122.5(2) . . ? O1 C1 C2 119.0(2) . . ? O2 C1 C2 118.5(2) . . ? C7 C2 C3 118.9(3) . . ? C7 C2 C1 121.3(3) . . ? C3 C2 C1 119.8(3) . . ? C4 C3 C2 121.7(3) . . ? C4 C3 H3 119.1 . . ? C2 C3 H3 119.1 . . ? C5 C4 C3 120.0(4) . . ? C5 C4 H4 120.0 . . ? C3 C4 H4 120.0 . . ? C4 C5 C6 119.6(3) . . ? C4 C5 C8 115.9(4) . . ? C6 C5 C8 124.5(4) . . ? C7 C6 C5 120.5(4) . . ? C7 C6 H6 119.7 . . ? C5 C6 H6 119.7 . . ? C2 C7 C6 119.3(3) . . ? C2 C7 H7 120.4 . . ? C6 C7 H7 120.4 . . ? C8 C8 C5 124.5(5) 13_455 . ? C8 C8 H8 116.8 13_455 . ? C5 C8 H8 117.1 . . ? C9 N1 C10 121.5(3) . . ? C9 N1 C11 121.2(3) . . ? C10 N1 C11 117.4(3) . . ? C9 O3 Mn2 133.2(11) . . ? O3 C9 N1 124.8(4) . . ? O3 C9 H9 117.6 . . ? N1 C9 H9 117.6 . . ? N1 C10 H10A 104.2 . . ? N1 C10 H10B 111.3 . . ? H10A C10 H10B 109.5 . . ? N1 C10 H10C 112.8 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 H11A 105.3 . . ? N1 C11 H11B 112.8 . . ? H11A C11 H11B 109.5 . . ? N1 C11 H11C 110.2 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? 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 O1 Mn1 O1 C1 -113.5(2) 3_565 . . . ? O1 Mn1 O1 C1 154.2(3) 14_455 . . . ? O1 Mn1 O1 C1 66.5(2) 15 . . . ? O1 Mn1 O1 C1 -25.8(3) 2_665 . . . ? O2 Mn2 O2 C1 53.2(2) 3_565 . . . ? O2 Mn2 O2 C1 -101.70(17) 2_665 . . . ? O3 Mn2 O2 C1 147.8(6) . . . . ? O3 Mn2 O2 C1 152.1(6) 3_565 . . . ? O3 Mn2 O2 C1 167.3(3) 2_665 . . . ? Mn1 O1 C1 O2 76.9(3) . . . . ? Mn1 O1 C1 C2 -102.2(2) . . . . ? Mn2 O2 C1 O1 -3.0(3) . . . . ? Mn2 O2 C1 C2 176.13(11) . . . . ? O1 C1 C2 C7 -20.2(2) . . . . ? O2 C1 C2 C7 160.7(2) . . . . ? O1 C1 C2 C3 159.9(2) . . . . ? O2 C1 C2 C3 -19.2(2) . . . . ? C7 C2 C3 C4 0.12(11) . . . . ? C1 C2 C3 C4 180.00(8) . . . . ? C2 C3 C4 C5 0.10(18) . . . . ? C3 C4 C5 C6 -0.3(2) . . . . ? C3 C4 C5 C8 179.95(13) . . . . ? C4 C5 C6 C7 0.2(2) . . . . ? C8 C5 C6 C7 179.98(16) . . . . ? C3 C2 C7 C6 -0.17(17) . . . . ? C1 C2 C7 C6 179.96(11) . . . . ? C5 C6 C7 C2 0.0(2) . . . . ? C4 C5 C8 C8 -168.7(5) . . . 13_455 ? C6 C5 C8 C8 11.6(6) . . . 13_455 ? O2 Mn2 O3 C9 41.9(12) . . . . ? Mn2 O3 C9 N1 -151.3(9) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 30.00 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.171 _refine_diff_density_min -0.640 _refine_diff_density_rms 0.090 _database_code_depnum_ccdc_archive 'CCDC 964387' ####################################################################### # # 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_Zn2Cd _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H44 Cd N2 O14 Zn2' _chemical_formula_sum 'C54 H44 Cd N2 O14 Zn2' _chemical_formula_weight 1188.05 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cd Cd -0.8075 1.2024 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'R -3' _symmetry_space_group_name_Hall '-R 3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 16.1672(10) _cell_length_b 16.1672(10) _cell_length_c 16.6171(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3761.4(4) _cell_formula_units_Z 3 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4452 _cell_measurement_theta_min 2.52 _cell_measurement_theta_max 24.79 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.573 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1806 _exptl_absorpt_coefficient_mu 1.439 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.597 _exptl_absorpt_correction_T_max 0.870 _exptl_absorpt_process_details 'SADABS (Bruker, 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 16570 _diffrn_reflns_av_R_equivalents 0.0454 _diffrn_reflns_av_sigmaI/netI 0.0246 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 1.90 _diffrn_reflns_theta_max 27.99 _reflns_number_total 1973 _reflns_number_gt 1639 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 (Bruker, 2005)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXTL (Sheldrick, 2008)' _computing_structure_refinement 'SHELXTL (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 2008)' _computing_publication_material 'SHELXTL (Sheldrick, 2008)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.066P)^2^+112P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1973 _refine_ls_number_parameters 81 _refine_ls_number_restraints 20 _refine_ls_R_factor_all 0.0789 _refine_ls_R_factor_gt 0.0661 _refine_ls_wR_factor_ref 0.1708 _refine_ls_wR_factor_gt 0.1618 _refine_ls_goodness_of_fit_ref 1.001 _refine_ls_restrained_S_all 0.996 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cd1 Cd 0.6667 0.3333 0.3333 0.0228(3) Uani 1 6 d S . . Zn1 Zn 0.6667 0.3333 0.54749(6) 0.0179(3) Uani 1 3 d S . . O1 O 0.5498(3) 0.3377(3) 0.5253(3) 0.0340(9) Uani 1 1 d . . . O2 O 0.5406(3) 0.2655(3) 0.4090(2) 0.0272(8) Uani 1 1 d . . . C1 C 0.5116(4) 0.3048(4) 0.4569(4) 0.0297(12) Uani 1 1 d . . . C2 C 0.4279(4) 0.3135(4) 0.4350(3) 0.0523(8) Uani 1 1 d D . . C3 C 0.3669(4) 0.2581(5) 0.3737(4) 0.0523(8) Uani 1 1 d D . . H3 H 0.3768 0.2113 0.3480 0.063 Uiso 1 1 calc R . . C4 C 0.2915(4) 0.2706(4) 0.3495(4) 0.0523(8) Uani 1 1 d D . . H4 H 0.2504 0.2322 0.3075 0.063 Uiso 1 1 calc R . . C5 C 0.2758(4) 0.3388(4) 0.3864(3) 0.0523(8) Uani 1 1 d D . . C6 C 0.3367(4) 0.3943(4) 0.4478(3) 0.0523(8) Uani 1 1 d D . . H6 H 0.3268 0.4411 0.4735 0.063 Uiso 1 1 calc R . . C7 C 0.4120(4) 0.3816(5) 0.4718(4) 0.0523(8) Uani 1 1 d D . . H7 H 0.4531 0.4200 0.5138 0.063 Uiso 1 1 calc R . . C8 C 0.1971(5) 0.3548(5) 0.3630(4) 0.0523(8) Uani 1 1 d D . . H8 H 0.1894 0.4002 0.3935 0.063 Uiso 1 1 calc R . . O3 O 0.6513(16) 0.333(3) 0.6659(7) 0.103(6) Uani 0.333333 1 d PD . . N1 N 0.5635(11) 0.3132(16) 0.7804(6) 0.103(6) Uani 0.333333 1 d PD . . C9 C 0.6178(13) 0.3635(19) 0.7180(8) 0.103(6) Uani 0.333333 1 d PD . . H9 H 0.6326 0.4288 0.7149 0.124 Uiso 0.333333 1 d PR . . C10 C 0.538(2) 0.2143(17) 0.7932(14) 0.103(6) Uani 0.333333 1 d PD . . H10A H 0.5661 0.1943 0.7504 0.155 Uiso 0.333333 1 calc PR . . H10B H 0.4684 0.1737 0.7922 0.155 Uiso 0.333333 1 calc PR . . H10C H 0.5625 0.2082 0.8455 0.155 Uiso 0.333333 1 calc PR . . C11 C 0.5276(19) 0.355(2) 0.8382(11) 0.103(6) Uani 0.333333 1 d PD . . H11A H 0.5533 0.4228 0.8254 0.155 Uiso 0.333333 1 calc PR . . H11B H 0.5477 0.3491 0.8925 0.155 Uiso 0.333333 1 calc PR . . H11C H 0.4577 0.3217 0.8356 0.155 Uiso 0.333333 1 calc PR . . 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 Cd1 0.0210(3) 0.0210(3) 0.0266(5) 0.000 0.000 0.01048(16) Zn1 0.0173(3) 0.0173(3) 0.0190(5) 0.000 0.000 0.00866(16) O1 0.031(2) 0.039(2) 0.032(2) 0.0022(18) 0.0042(17) 0.0176(19) O2 0.0193(18) 0.0243(19) 0.040(2) -0.0007(16) 0.0024(15) 0.0122(15) C1 0.025(3) 0.028(3) 0.035(3) 0.003(2) 0.004(2) 0.012(2) C2 0.0499(16) 0.070(2) 0.0551(17) -0.0261(15) -0.0132(13) 0.0440(16) C3 0.0499(16) 0.070(2) 0.0551(17) -0.0261(15) -0.0132(13) 0.0440(16) C4 0.0499(16) 0.070(2) 0.0551(17) -0.0261(15) -0.0132(13) 0.0440(16) C5 0.0499(16) 0.070(2) 0.0551(17) -0.0261(15) -0.0132(13) 0.0440(16) C6 0.0499(16) 0.070(2) 0.0551(17) -0.0261(15) -0.0132(13) 0.0440(16) C7 0.0499(16) 0.070(2) 0.0551(17) -0.0261(15) -0.0132(13) 0.0440(16) C8 0.0499(16) 0.070(2) 0.0551(17) -0.0261(15) -0.0132(13) 0.0440(16) O3 0.120(12) 0.218(19) 0.031(4) -0.003(9) -0.002(7) 0.129(14) N1 0.120(12) 0.218(19) 0.031(4) -0.003(9) -0.002(7) 0.129(14) C9 0.120(12) 0.218(19) 0.031(4) -0.003(9) -0.002(7) 0.129(14) C10 0.120(12) 0.218(19) 0.031(4) -0.003(9) -0.002(7) 0.129(14) C11 0.120(12) 0.218(19) 0.031(4) -0.003(9) -0.002(7) 0.129(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 Cd1 O2 2.169(4) . ? Zn1 O1 1.960(4) . ? Zn1 O3 1.982(6) . ? O1 C1 1.277(7) . ? O2 C1 1.247(7) . ? C1 C2 1.474(8) . ? C2 C3 1.389(9) . ? C2 C7 1.391(9) . ? C3 C4 1.391(10) . ? C3 H3 0.9500 . ? C4 C5 1.391(9) . ? C4 H4 0.9500 . ? C5 C6 1.390(8) . ? C5 C8 1.472(11) . ? C6 C7 1.390(10) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C8 1.319(8) 16 ? C8 H8 0.9500 . ? O3 C9 1.250(11) . ? N1 C9 1.339(12) . ? N1 C11 1.453(12) . ? N1 C10 1.454(12) . ? C9 H9 0.9600 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Cd1 O2 89.75(15) . 3_665 ? O1 Zn1 O1 116.56(8) 2_655 . ? O1 Zn1 O3 104.7(10) . 2_655 ? O1 Zn1 O3 103.8(11) . 3_665 ? O1 Zn1 O3 93.8(6) . . ? C1 O1 Zn1 115.3(4) . . ? C1 O2 Cd1 127.6(4) . . ? O2 C1 O1 123.6(5) . . ? O2 C1 C2 119.3(5) . . ? O1 C1 C2 117.1(5) . . ? C3 C2 C7 118.6(6) . . ? C3 C2 C1 120.6(5) . . ? C7 C2 C1 120.7(5) . . ? C4 C3 C2 120.7(6) . . ? C4 C3 H3 119.7 . . ? C2 C3 H3 119.7 . . ? C3 C4 C5 120.5(6) . . ? C3 C4 H4 119.7 . . ? C5 C4 H4 119.7 . . ? C6 C5 C4 118.9(6) . . ? C6 C5 C8 118.4(5) . . ? C4 C5 C8 122.6(5) . . ? C7 C6 C5 120.4(6) . . ? C7 C6 H6 119.8 . . ? C5 C6 H6 119.8 . . ? C6 C7 C2 120.9(6) . . ? C6 C7 H7 119.6 . . ? C2 C7 H7 119.6 . . ? C8 C8 C5 126.1(8) 16 . ? C8 C8 H8 117.0 16 . ? C5 C8 H8 117.0 . . ? C9 O3 Zn1 139.8(15) . . ? C9 N1 C11 121.4(3) . . ? C9 N1 C10 121.4(3) . . ? C11 N1 C10 117.2(3) . . ? O3 C9 N1 125.3(4) . . ? O3 C9 H9 118.8 . . ? N1 C9 H9 115.9 . . ? N1 C10 H10A 109.5 . . ? N1 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? N1 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 H11A 109.5 . . ? N1 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? N1 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? 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 O1 Zn1 O1 C1 -47.9(5) 2_655 . . . ? O1 Zn1 O1 C1 96.1(4) 3_665 . . . ? O3 Zn1 O1 C1 -149.9(9) 2_655 . . . ? O3 Zn1 O1 C1 -162.4(8) 3_665 . . . ? O3 Zn1 O1 C1 -155.4(12) . . . . ? O2 Cd1 O2 C1 108.7(4) 2_655 . . . ? O2 Cd1 O2 C1 -161.0(5) 18_545 . . . ? O2 Cd1 O2 C1 -71.3(4) 17 . . . ? O2 Cd1 O2 C1 19.0(5) 3_665 . . . ? Cd1 O2 C1 O1 -75.2(7) . . . . ? Cd1 O2 C1 C2 105.6(5) . . . . ? Zn1 O1 C1 O2 5.4(7) . . . . ? Zn1 O1 C1 C2 -175.4(4) . . . . ? O2 C1 C2 C3 16.9(7) . . . . ? O1 C1 C2 C3 -162.3(4) . . . . ? O2 C1 C2 C7 -158.9(5) . . . . ? O1 C1 C2 C7 21.9(7) . . . . ? C7 C2 C3 C4 0.1(9) . . . . ? C1 C2 C3 C4 -175.8(5) . . . . ? C2 C3 C4 C5 -0.1(10) . . . . ? C3 C4 C5 C6 0.1(9) . . . . ? C3 C4 C5 C8 179.97(12) . . . . ? C4 C5 C6 C7 0.0(3) . . . . ? C8 C5 C6 C7 -179.99(17) . . . . ? C5 C6 C7 C2 0.0(3) . . . . ? C3 C2 C7 C6 -0.1(9) . . . . ? C1 C2 C7 C6 175.8(5) . . . . ? C6 C5 C8 C8 176.4(9) . . . 16 ? C4 C5 C8 C8 -3.6(10) . . . 16 ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 27.99 _diffrn_measured_fraction_theta_full 0.976 _refine_diff_density_max 1.103 _refine_diff_density_min -1.195 _refine_diff_density_rms 0.156 _database_code_depnum_ccdc_archive 'CCDC 964388' ####################################################################### # # 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_Zn2Co _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H44 Co N2 O14 Zn2' _chemical_formula_sum 'C54 H44 Co N2 O14 Zn2' _chemical_formula_weight 1134.58 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'R -3' _symmetry_space_group_name_Hall '-R 3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 16.1476(19) _cell_length_b 16.1476(19) _cell_length_c 16.476(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3720.5(15) _cell_formula_units_Z 3 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 7771 _cell_measurement_theta_min 2.52 _cell_measurement_theta_max 29.92 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.519 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1743 _exptl_absorpt_coefficient_mu 1.361 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.686 _exptl_absorpt_correction_T_max 0.763 _exptl_absorpt_process_details 'SADABS (Bruker, 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 18962 _diffrn_reflns_av_R_equivalents 0.0276 _diffrn_reflns_av_sigmaI/netI 0.0190 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.91 _diffrn_reflns_theta_max 30.00 _reflns_number_total 2396 _reflns_number_gt 1980 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 (Bruker, 2005)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXTL (Sheldrick, 2008)' _computing_structure_refinement 'SHELXTL (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 2008)' _computing_publication_material 'SHELXTL (Sheldrick, 2008)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0786P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2396 _refine_ls_number_parameters 117 _refine_ls_number_restraints 8 _refine_ls_R_factor_all 0.0455 _refine_ls_R_factor_gt 0.0375 _refine_ls_wR_factor_ref 0.1120 _refine_ls_wR_factor_gt 0.1077 _refine_ls_goodness_of_fit_ref 1.062 _refine_ls_restrained_S_all 1.062 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zn1 Zn 0.6667 0.3333 0.54604(2) 0.02760(13) Uani 1 3 d S . . Co1 Co 0.6667 0.3333 0.3333 0.01593(13) Uani 1 6 d S . . O1 O 0.72467(9) 0.45567(9) 0.40513(7) 0.0279(3) Uani 1 1 d . . . O2 O 0.78777(9) 0.44883(9) 0.52386(8) 0.0319(3) Uani 1 1 d . . . C1 C 0.79261(12) 0.48547(12) 0.45411(11) 0.0272(3) Uani 1 1 d . . . C2 C 0.88585(14) 0.56972(14) 0.43158(12) 0.0353(4) Uani 1 1 d . . . C3 C 0.89065(17) 0.63087(19) 0.37104(17) 0.0597(8) Uani 1 1 d . . . H3 H 0.8340 0.6200 0.3442 0.072 Uiso 1 1 calc R . . C4 C 0.97883(19) 0.7087(2) 0.3492(2) 0.0778(11) Uani 1 1 d . . . H4 H 0.9818 0.7521 0.3088 0.093 Uiso 1 1 calc R . . C5 C 1.06325(16) 0.72340(19) 0.38675(16) 0.0575(7) Uani 1 1 d . . . C6 C 1.05742(16) 0.66271(19) 0.44762(17) 0.0560(7) Uani 1 1 d . . . H6 H 1.1140 0.6723 0.4736 0.067 Uiso 1 1 calc R . . C7 C 0.96934(15) 0.58752(17) 0.47138(15) 0.0455(5) Uani 1 1 d . . . H7 H 0.9659 0.5477 0.5152 0.055 Uiso 1 1 calc R . . C8 C 1.15805(16) 0.8016(2) 0.36261(19) 0.0674(9) Uani 1 1 d . . . H8 H 1.2117 0.8074 0.3913 0.081 Uiso 1 1 calc R . . O3 O 0.6744(8) 0.3497(9) 0.6669(2) 0.113(2) Uani 0.333333 1 d PD . . N1 N 0.7562(6) 0.4335(6) 0.7808(3) 0.113(2) Uani 0.333333 1 d PD . . C9 C 0.7470(8) 0.3883(7) 0.7104(4) 0.113(2) Uani 0.333333 1 d PD . . H9 H 0.8013 0.3855 0.6919 0.135 Uiso 0.333333 1 calc PR . . C10 C 0.6945(7) 0.4724(8) 0.8008(5) 0.113(2) Uani 0.333333 1 d PD . . H10A H 0.6846 0.4703 0.8596 0.169 Uiso 0.333333 1 d PR . . H10B H 0.6325 0.4394 0.7732 0.169 Uiso 0.333333 1 d PR . . H10C H 0.7300 0.5391 0.7828 0.169 Uiso 0.333333 1 d PR . . C11 C 0.8383(6) 0.4605(8) 0.8333(5) 0.113(2) Uani 0.333333 1 d PD . . H11A H 0.8706 0.4274 0.8158 0.169 Uiso 0.333333 1 d PR . . H11B H 0.8836 0.5275 0.8383 0.169 Uiso 0.333333 1 d PR . . H11C H 0.8084 0.4357 0.8848 0.169 Uiso 0.333333 1 d PR . . 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 Zn1 0.02784(15) 0.02784(15) 0.0271(2) 0.000 0.000 0.01392(8) Co1 0.01388(16) 0.01388(16) 0.0200(2) 0.000 0.000 0.00694(8) O1 0.0230(6) 0.0225(6) 0.0373(7) -0.0074(5) -0.0048(5) 0.0108(5) O2 0.0293(6) 0.0280(6) 0.0329(6) -0.0049(5) -0.0045(5) 0.0100(5) C1 0.0260(8) 0.0223(7) 0.0328(8) -0.0070(6) -0.0026(6) 0.0117(6) C2 0.0274(8) 0.0295(9) 0.0380(10) -0.0018(7) -0.0068(7) 0.0060(7) C3 0.0317(11) 0.0546(15) 0.0617(15) 0.0198(12) -0.0179(10) -0.0018(10) C4 0.0369(12) 0.0712(19) 0.0780(19) 0.0424(16) -0.0217(13) -0.0083(12) C5 0.0302(11) 0.0541(14) 0.0578(14) 0.0161(11) -0.0137(10) -0.0018(10) C6 0.0271(10) 0.0532(14) 0.0681(16) 0.0178(12) -0.0133(10) 0.0054(10) C7 0.0303(10) 0.0407(11) 0.0538(13) 0.0097(9) -0.0102(9) 0.0089(8) C8 0.0290(11) 0.0664(17) 0.0711(18) 0.0263(14) -0.0181(11) -0.0029(11) O3 0.111(4) 0.105(4) 0.0368(16) 0.000(2) 0.007(2) -0.010(3) N1 0.111(4) 0.105(4) 0.0368(16) 0.000(2) 0.007(2) -0.010(3) C9 0.111(4) 0.105(4) 0.0368(16) 0.000(2) 0.007(2) -0.010(3) C10 0.111(4) 0.105(4) 0.0368(16) 0.000(2) 0.007(2) -0.010(3) C11 0.111(4) 0.105(4) 0.0368(16) 0.000(2) 0.007(2) -0.010(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zn1 O2 1.9464(13) . ? Zn1 O3 2.005(4) . ? Co1 O1 2.0806(12) . ? O1 C1 1.248(2) . ? O2 C1 1.277(2) . ? C1 C2 1.486(3) . ? C2 C3 1.378(3) . ? C2 C7 1.394(3) . ? C3 C4 1.395(3) . ? C3 H3 0.9500 . ? C4 C5 1.405(4) . ? C4 H4 0.9500 . ? C5 C6 1.372(3) . ? C5 C8 1.471(3) . ? C6 C7 1.387(3) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C8 1.332(5) 16_765 ? C8 H8 0.9500 . ? O3 C9 1.244(3) . ? N1 C9 1.338(3) . ? N1 C11 1.455(3) . ? N1 C10 1.456(3) . ? C9 H9 0.9500 . ? C10 H10A 0.9799 . ? C10 H10B 0.9800 . ? C10 H10C 0.9801 . ? C11 H11A 0.9602 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Zn1 O2 116.56(2) . 2_655 ? O2 Zn1 O3 100.3(5) . 3_665 ? O2 Zn1 O3 106.7(5) . 2_655 ? O2 Zn1 O3 95.4(2) . . ? O1 Co1 O1 90.87(5) 2_655 . ? C1 O1 Co1 128.69(11) . . ? C1 O2 Zn1 114.36(11) . . ? O1 C1 O2 124.38(16) . . ? O1 C1 C2 118.97(16) . . ? O2 C1 C2 116.65(15) . . ? C3 C2 C7 119.38(19) . . ? C3 C2 C1 120.34(18) . . ? C7 C2 C1 120.27(18) . . ? C2 C3 C4 119.9(2) . . ? C2 C3 H3 120.1 . . ? C4 C3 H3 120.1 . . ? C3 C4 C5 120.4(2) . . ? C3 C4 H4 119.8 . . ? C5 C4 H4 119.8 . . ? C6 C5 C4 119.1(2) . . ? C6 C5 C8 118.8(2) . . ? C4 C5 C8 122.1(2) . . ? C5 C6 C7 120.4(2) . . ? C5 C6 H6 119.8 . . ? C7 C6 H6 119.8 . . ? C6 C7 C2 120.7(2) . . ? C6 C7 H7 119.7 . . ? C2 C7 H7 119.7 . . ? C8 C8 C5 125.7(3) 16_765 . ? C8 C8 H8 117.1 16_765 . ? C5 C8 H8 117.1 . . ? C9 O3 Zn1 128.3(6) . . ? C9 N1 C11 120.9(3) . . ? C9 N1 C10 121.2(3) . . ? C11 N1 C10 116.9(3) . . ? O3 C9 N1 126.3(4) . . ? O3 C9 H9 116.9 . . ? N1 C9 H9 116.9 . . ? N1 C10 H10A 110.2 . . ? N1 C10 H10B 113.2 . . ? H10A C10 H10B 109.5 . . ? N1 C10 H10C 104.9 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 H11A 108.8 . . ? N1 C11 H11B 117.2 . . ? H11A C11 H11B 109.5 . . ? N1 C11 H11C 102.0 . . ? H11A C11 H11C 109.4 . . ? H11B C11 H11C 109.5 . . ? 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 O1 Co1 O1 C1 17.61(16) 3_665 . . . ? O1 Co1 O1 C1 -71.51(13) 17 . . . ? O1 Co1 O1 C1 -162.39(16) 18_545 . . . ? O1 Co1 O1 C1 108.49(13) 2_655 . . . ? O2 Zn1 O2 C1 95.17(11) 3_665 . . . ? O2 Zn1 O2 C1 -48.80(14) 2_655 . . . ? O3 Zn1 O2 C1 -163.5(3) 3_665 . . . ? O3 Zn1 O2 C1 -153.8(4) 2_655 . . . ? O3 Zn1 O2 C1 -153.1(6) . . . . ? Co1 O1 C1 O2 -74.2(2) . . . . ? Co1 O1 C1 C2 106.47(18) . . . . ? Zn1 O2 C1 O1 4.9(2) . . . . ? Zn1 O2 C1 C2 -175.73(13) . . . . ? O1 C1 C2 C3 19.3(3) . . . . ? O2 C1 C2 C3 -160.1(2) . . . . ? O1 C1 C2 C7 -160.5(2) . . . . ? O2 C1 C2 C7 20.1(3) . . . . ? C7 C2 C3 C4 1.1(5) . . . . ? C1 C2 C3 C4 -178.7(3) . . . . ? C2 C3 C4 C5 2.2(6) . . . . ? C3 C4 C5 C6 -3.0(6) . . . . ? C3 C4 C5 C8 176.8(4) . . . . ? C4 C5 C6 C7 0.4(5) . . . . ? C8 C5 C6 C7 -179.3(3) . . . . ? C5 C6 C7 C2 2.9(5) . . . . ? C3 C2 C7 C6 -3.6(4) . . . . ? C1 C2 C7 C6 176.2(2) . . . . ? C6 C5 C8 C8 178.9(5) . . . 16_765 ? C4 C5 C8 C8 -0.8(7) . . . 16_765 ? C11 N1 C9 O3 168.7(12) . . . . ? C10 N1 C9 O3 -22.5(18) . . . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 30.00 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.916 _refine_diff_density_min -0.435 _refine_diff_density_rms 0.082 _database_code_depnum_ccdc_archive 'CCDC 964389'