# 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_ng-main-1 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Li-salt of Co(III)-dibromide complex with amidate ligand, CH3CN solvate ; _chemical_name_common 'A-Ghosh sample 1' _chemical_melting_point 'decomposes upon heating' _chemical_formula_moiety ? _chemical_formula_sum 'C9.45 H10 Br Co0.50 Li0.50 N3.24 O' _chemical_formula_weight 297.71 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'C 2 2 21' _symmetry_space_group_name_Hall 'c 2c2' _symmetry_Int_Tables_number 20 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-x, y, -z+1/2' 'x, -y, -z' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 9.0155(12) _cell_length_b 17.429(2) _cell_length_c 15.794(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2481.8(6) _cell_formula_units_Z 8 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 133 _cell_measurement_theta_min 2.19 _cell_measurement_theta_max 54.17 _exptl_crystal_description prism _exptl_crystal_colour dark-brown-black _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.594 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1179 _exptl_absorpt_coefficient_mu 3.938 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5770 _exptl_absorpt_correction_T_max 0.7455 _exptl_absorpt_process_details 'SADABS (Bruker AXS, 2005)' _exptl_special_details ; Well-shaped with nicely difined faces dark black-brown crystal of prismatic habitus was selected for studies, placed in the MitiGen plastic loop, centered and examined at 120 K with the help of Kryoflex cryogenic device. Data were corrected for decay and absorption using the program SADABS (Sheldrick, G.M. (2003). SADABS. Version 2.10. University of Gottingen, Germany) ; _diffrn_ambient_temperature 120(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 APEX2 CCD area detector' _diffrn_measurement_method '4 omega scans - full sphere' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 14362 _diffrn_reflns_av_R_equivalents 0.0664 _diffrn_reflns_av_sigmaI/netI 0.0594 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.54 _diffrn_reflns_theta_max 27.16 _reflns_number_total 2756 _reflns_number_gt 2136 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1998)' _computing_cell_refinement 'SAINT (Bruker, 1998)' _computing_data_reduction 'SAINT (Bruker, 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-III (Burnett & Johnson, 1996)' _computing_publication_material 'CIFTAB (Sheldrick, 1997)' _refine_special_details ; The main residue in this structure appeared to be without any signs of disorder. However, there are two groups of (3 and 4) acetonitrile solvent molecules in the structure. Three of them in the vicinity of Li+ counter-cation and other two are badly disordered and face NH2-groups of the diimide ligand perhaps due to electrostatic interactions, and occupying the channels running along c-direction. Nevertheless, acetonitrile molecules were modeled rather successfully, but without H-atoms that could not be found on the difference map. Atrificial placement of H-atoms on terminal carbon atoms with the possibility for their refinement in a riding mode has led to unstable refinement. Therefore, all shown CH3CN molecules do not contain hydrogen atoms. We did not want to apply the SQUEEZE routine to remove electron density that belongs to the disordered solvent in order to prevent originality of data as much as possible. Moreover, we could not "remove" the disordered solvent because of chemical reasons: Li cations have to have surrounding in the structure and could not be "naked". Therefore, a series of DFIX, SIMU, DELU, FLAT and two EADP restrains were applied to model this rather complicated disorder rather satisfactory. 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^)+(0.0458P)^2^+3.7115P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.000(17) _refine_ls_number_reflns 2756 _refine_ls_number_parameters 190 _refine_ls_number_restraints 150 _refine_ls_R_factor_all 0.0654 _refine_ls_R_factor_gt 0.0394 _refine_ls_wR_factor_ref 0.0911 _refine_ls_wR_factor_gt 0.0815 _refine_ls_goodness_of_fit_ref 0.989 _refine_ls_restrained_S_all 0.977 _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 Co1 Co 0.0000 1.15315(5) -0.2500 0.01709(19) Uani 1 2 d S . . N1 N 0.1123(5) 1.2226(2) -0.1766(2) 0.0264(10) Uani 1 1 d U . . H1A H 0.1721 1.2533 -0.2094 0.032 Uiso 1 1 calc R . . H1B H 0.0473 1.2539 -0.1478 0.032 Uiso 1 1 calc R . . C1 C 0.2071(4) 1.1794(3) -0.1135(2) 0.0248(10) Uani 1 1 d DU . . C2 C 0.1500(7) 1.1983(4) -0.0229(3) 0.0429(16) Uani 1 1 d . . . H2A H 0.1735 1.2518 -0.0092 0.064 Uiso 1 1 calc R . . H2B H 0.1982 1.1643 0.0182 0.064 Uiso 1 1 calc R . . H2C H 0.0424 1.1908 -0.0206 0.064 Uiso 1 1 calc R . . C3 C 0.3669(6) 1.1996(3) -0.1241(4) 0.0385(15) Uani 1 1 d . . . H3A H 0.4004 1.1838 -0.1805 0.058 Uiso 1 1 calc R . . H3B H 0.4257 1.1731 -0.0809 0.058 Uiso 1 1 calc R . . H3C H 0.3794 1.2552 -0.1178 0.058 Uiso 1 1 calc R . . C4 C 0.1857(4) 1.0932(3) -0.1282(2) 0.0204(9) Uani 1 1 d DU . . O1 O 0.2566(3) 1.04728(19) -0.08248(19) 0.0299(9) Uani 1 1 d DU A . N2 N 0.0924(3) 1.0751(2) -0.1891(2) 0.0193(8) Uani 1 1 d DU . . C5 C 0.0516(3) 1.0005(3) -0.2166(2) 0.0274(11) Uani 1 1 d DU . . C6 C 0.1030(4) 0.9318(3) -0.1834(3) 0.0405(14) Uani 1 1 d DU . . H6 H 0.1728 0.9316 -0.1384 0.049 Uiso 1 1 calc R . . C7 C 0.0509(5) 0.8630(3) -0.2172(3) 0.055(2) Uani 1 1 d DU . . H7 H 0.0855 0.8157 -0.1949 0.065 Uiso 1 1 calc R . . Br1 Br 0.20440(6) 1.15751(4) -0.34998(3) 0.03421(16) Uani 1 1 d . . . Li1 Li 0.3618(14) 1.0000 0.0000 0.038(3) Uani 1 2 d SU . . N3 N 0.5846(11) 1.0000 0.0000 0.052(4) Uani 0.2635(18) 1 d PDU A 1 C8 C 0.7122(11) 1.0000 0.0000 0.044(4) Uani 0.2635(18) 1 d PDU A 1 C9 C 0.8732(11) 1.0000 0.0000 0.060(6) Uani 0.2635(18) 1 d PDU A 1 N3A N 0.5113(14) 0.9250(10) -0.0584(10) 0.090(5) Uani 0.473(4) 1 d PDU A 2 C8A C 0.6359(13) 0.9282(9) -0.0746(9) 0.060(4) Uani 0.473(4) 1 d PDU A 2 C9A C 0.7963(15) 0.9310(7) -0.0896(8) 0.048(3) Uani 0.473(4) 1 d PDU A 2 N4 N 0.498(13) 0.900(6) -0.128(9) 0.076(4) Uani 0.055(4) 1 d PDU B 1 C10 C 0.483(18) 0.942(7) -0.185(8) 0.050(4) Uani 0.055(4) 1 d PDU B 1 C11 C 0.5000 1.001(9) -0.2500 0.048(5) Uani 0.055(4) 2 d SPDU . 1 N4A N 0.4644(15) 0.8720(6) -0.2062(11) 0.076(4) Uani 0.445(4) 1 d PDU . 2 C10A C 0.488(2) 0.9370(7) -0.2172(10) 0.050(4) Uani 0.445(4) 1 d PDU . 2 C11A C 0.524(3) 1.0154(6) -0.245(3) 0.048(5) Uani 0.445(4) 1 d PDU . 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 Co1 0.0228(4) 0.0152(4) 0.0133(4) 0.000 -0.0005(3) 0.000 N1 0.030(2) 0.023(2) 0.026(2) 0.0006(16) -0.0050(19) -0.0005(18) C1 0.034(3) 0.025(2) 0.016(2) -0.0020(17) -0.005(2) 0.002(2) C2 0.054(4) 0.047(4) 0.028(3) -0.010(3) -0.007(3) 0.012(3) C3 0.041(3) 0.025(3) 0.049(4) 0.005(3) -0.013(3) -0.006(3) C4 0.022(2) 0.022(2) 0.018(2) 0.0035(17) 0.0040(17) -0.004(2) O1 0.035(2) 0.0279(18) 0.0270(18) 0.0070(15) -0.0083(14) 0.0025(15) N2 0.020(2) 0.0158(17) 0.022(2) 0.0021(15) -0.0002(16) -0.0022(16) C5 0.029(3) 0.016(2) 0.037(3) -0.001(2) -0.007(2) 0.000(2) C6 0.036(3) 0.022(2) 0.063(4) 0.009(2) -0.019(3) -0.001(2) C7 0.044(4) 0.016(2) 0.103(6) 0.004(3) -0.030(4) 0.002(2) Br1 0.0289(3) 0.0538(3) 0.0199(2) 0.0043(3) 0.0034(2) -0.0111(3) Li1 0.026(4) 0.062(8) 0.026(6) 0.022(6) 0.000 0.000 N3 0.027(4) 0.078(10) 0.050(8) 0.031(8) 0.000 0.000 C8 0.027(4) 0.071(10) 0.032(7) 0.029(7) 0.000 0.000 C9 0.028(5) 0.104(15) 0.048(10) 0.053(10) 0.000 0.000 N3A 0.062(6) 0.135(11) 0.073(8) 0.061(8) 0.038(7) 0.063(8) C8A 0.059(6) 0.077(9) 0.043(7) 0.044(7) 0.020(6) 0.041(6) C9A 0.058(6) 0.040(7) 0.045(7) 0.000(6) 0.017(8) 0.002(7) N4 0.051(8) 0.036(5) 0.140(11) 0.029(6) -0.008(8) 0.002(6) C10 0.028(6) 0.028(4) 0.094(11) 0.001(5) 0.005(9) -0.002(6) C11 0.032(13) 0.030(5) 0.080(9) 0.000 0.033(11) 0.000 N4A 0.051(8) 0.036(5) 0.140(11) 0.029(6) -0.008(8) 0.002(6) C10A 0.028(6) 0.028(4) 0.094(11) 0.001(5) 0.005(9) -0.002(6) C11A 0.032(13) 0.030(5) 0.080(9) 0.000 0.033(11) 0.000 _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 Co1 N2 1.862(4) 3_554 ? Co1 N2 1.862(4) . ? Co1 N1 1.958(4) . ? Co1 N1 1.958(4) 3_554 ? Co1 Br1 2.4279(5) 3_554 ? Co1 Br1 2.4279(5) . ? N1 C1 1.514(6) . ? N1 H1A 0.9200 . ? N1 H1B 0.9200 . ? C1 C3 1.492(6) . ? C1 C4 1.533(7) . ? C1 C2 1.556(6) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? C3 H3A 0.9800 . ? C3 H3B 0.9800 . ? C3 H3C 0.9800 . ? C4 O1 1.253(5) . ? C4 N2 1.316(6) . ? O1 Li1 1.810(8) . ? N2 C5 1.419(6) . ? C5 C6 1.387(7) . ? C5 C5 1.407(9) 3_554 ? C6 C7 1.393(8) . ? C6 H6 0.9500 . ? C7 C7 1.385(12) 3_554 ? C7 H7 0.9500 . ? Li1 O1 1.810(7) 4_575 ? Li1 N3 2.009(17) . ? Li1 N3A 2.092(16) 4_575 ? Li1 N3A 2.092(16) . ? N3 C8 1.150(4) . ? C8 C9 1.451(4) . ? N3A C8A 1.154(13) . ? C8A C9A 1.466(13) . ? N4 C10 1.160(18) . ? C10 C11 1.468(18) . ? C11 C10 1.468(18) 3_654 ? N4A C10A 1.167(13) . ? N4A N4A 1.52(3) 3_654 ? N4A C10A 1.711(19) 3_654 ? C10A C10A 1.06(3) 3_654 ? C10A C11A 1.469(14) . ? C10A C11A 1.50(3) 3_654 ? C10A N4A 1.711(19) 3_654 ? C11A C11A 0.47(6) 3_654 ? C11A C10A 1.50(3) 3_654 ? 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 N2 Co1 N2 86.2(2) 3_554 . ? N2 Co1 N1 171.29(18) 3_554 . ? N2 Co1 N1 85.11(17) . . ? N2 Co1 N1 85.11(17) 3_554 3_554 ? N2 Co1 N1 171.29(18) . 3_554 ? N1 Co1 N1 103.6(2) . 3_554 ? N2 Co1 Br1 91.09(5) 3_554 3_554 ? N2 Co1 Br1 91.53(5) . 3_554 ? N1 Co1 Br1 89.31(13) . 3_554 ? N1 Co1 Br1 88.47(13) 3_554 3_554 ? N2 Co1 Br1 91.53(5) 3_554 . ? N2 Co1 Br1 91.09(4) . . ? N1 Co1 Br1 88.47(13) . . ? N1 Co1 Br1 89.31(13) 3_554 . ? Br1 Co1 Br1 176.42(5) 3_554 . ? C1 N1 Co1 111.9(3) . . ? C1 N1 H1A 109.2 . . ? Co1 N1 H1A 109.2 . . ? C1 N1 H1B 109.2 . . ? Co1 N1 H1B 109.2 . . ? H1A N1 H1B 107.9 . . ? C3 C1 N1 110.7(4) . . ? C3 C1 C4 109.6(3) . . ? N1 C1 C4 108.5(4) . . ? C3 C1 C2 111.9(4) . . ? N1 C1 C2 108.2(4) . . ? C4 C1 C2 107.8(3) . . ? C1 C2 H2A 109.5 . . ? C1 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? C1 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? C1 C3 H3A 109.5 . . ? C1 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? C1 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? O1 C4 N2 126.5(4) . . ? O1 C4 C1 118.3(4) . . ? N2 C4 C1 115.2(4) . . ? C4 O1 Li1 166.6(3) . . ? C4 N2 C5 127.5(4) . . ? C4 N2 Co1 119.3(3) . . ? C5 N2 Co1 113.3(3) . . ? C6 C5 C5 120.3(3) . 3_554 ? C6 C5 N2 126.1(4) . . ? C5 C5 N2 113.6(3) 3_554 . ? C5 C6 C7 119.1(5) . . ? C5 C6 H6 120.5 . . ? C7 C6 H6 120.5 . . ? C7 C7 C6 120.7(3) 3_554 . ? C7 C7 H7 119.7 3_554 . ? C6 C7 H7 119.7 . . ? O1 Li1 O1 116.8(7) 4_575 . ? O1 Li1 N3 121.6(4) 4_575 . ? O1 Li1 N3 121.6(4) . . ? O1 Li1 N3A 107.8(4) 4_575 4_575 ? O1 Li1 N3A 111.7(4) . 4_575 ? N3 Li1 N3A 49.9(6) . 4_575 ? O1 Li1 N3A 111.7(4) 4_575 . ? O1 Li1 N3A 107.8(4) . . ? N3 Li1 N3A 49.9(6) . . ? N3A Li1 N3A 99.8(12) 4_575 . ? C8 N3 Li1 180.0 . . ? N3 C8 C9 180.0 . . ? C8A N3A Li1 134.0(17) . . ? N3A C8A C9A 176.3(15) . . ? N4 C10 C11 166(10) . . ? C10 C11 C10 90(10) . 3_654 ? C10A N4A N4A 77.7(11) . 3_654 ? C10A N4A C10A 37.4(12) . 3_654 ? N4A N4A C10A 41.8(6) 3_654 3_654 ? C10A C10A N4A 100.5(12) 3_654 . ? C10A C10A C11A 70.6(18) 3_654 . ? N4A C10A C11A 171(2) . . ? C10A C10A C11A 67.7(16) 3_654 3_654 ? N4A C10A C11A 159(2) . 3_654 ? C11A C10A C11A 18(2) . 3_654 ? C10A C10A N4A 42.1(6) 3_654 3_654 ? N4A C10A N4A 60.5(14) . 3_654 ? C11A C10A N4A 110.7(19) . 3_654 ? C11A C10A N4A 109.9(18) 3_654 3_654 ? C11A C11A C10A 84(3) 3_654 . ? C11A C11A C10A 77(4) 3_654 3_654 ? C10A C11A C10A 41.7(13) . 3_654 ? 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 N2 Co1 N1 C1 -1.3(11) 3 . . . ? N2 Co1 N1 C1 -0.3(2) . . . . ? N1 Co1 N1 C1 179.6(3) 3 . . . ? Br1 Co1 N1 C1 91.3(2) 3 . . . ? Br1 Co1 N1 C1 -91.5(2) . . . . ? Co1 N1 C1 C3 120.9(4) . . . . ? Co1 N1 C1 C4 0.6(3) . . . . ? Co1 N1 C1 C2 -116.1(4) . . . . ? C3 C1 C4 O1 58.2(3) . . . . ? N1 C1 C4 O1 179.3(2) . . . . ? C2 C1 C4 O1 -63.8(3) . . . . ? C3 C1 C4 N2 -121.8(3) . . . . ? N1 C1 C4 N2 -0.7(2) . . . . ? C2 C1 C4 N2 116.2(3) . . . . ? N2 C4 O1 Li1 -158.5(17) . . . . ? C1 C4 O1 Li1 21.5(17) . . . . ? O1 C4 N2 C5 -0.10(7) . . . . ? C1 C4 N2 C5 179.89(5) . . . . ? O1 C4 N2 Co1 -179.47(9) . . . . ? C1 C4 N2 Co1 0.51(10) . . . . ? N2 Co1 N2 C4 179.73(8) 3 . . . ? N1 Co1 N2 C4 -0.13(13) . . . . ? N1 Co1 N2 C4 -179.3(9) 3 . . . ? Br1 Co1 N2 C4 -89.29(6) 3 . . . ? Br1 Co1 N2 C4 88.26(6) . . . . ? N2 Co1 N2 C5 0.27(5) 3 . . . ? N1 Co1 N2 C5 -179.58(15) . . . . ? N1 Co1 N2 C5 1.2(9) 3 . . . ? Br1 Co1 N2 C5 91.25(8) 3 . . . ? Br1 Co1 N2 C5 -91.19(8) . . . . ? C4 N2 C5 C6 0.30(9) . . . . ? Co1 N2 C5 C6 179.71(5) . . . . ? C4 N2 C5 C5 179.84(5) . . . 3 ? Co1 N2 C5 C5 -0.76(13) . . . 3 ? C5 C5 C6 C7 -0.06(3) 3 . . . ? N2 C5 C6 C7 179.45(9) . . . . ? C5 C6 C7 C7 -0.04(3) . . . 3 ? C4 O1 Li1 O1 89.4(16) . . . 4_575 ? C4 O1 Li1 N3 -90.6(16) . . . . ? C4 O1 Li1 N3A -35(2) . . . 4_575 ? C4 O1 Li1 N3A -143.8(14) . . . . ? O1 Li1 N3 C8 0.0 4_575 . . . ? O1 Li1 N3 C8 0.0 . . . . ? N3A Li1 N3 C8 0.0 4_575 . . . ? N3A Li1 N3 C8 0.0 . . . . ? Li1 N3 C8 C9 0.0 . . . . ? O1 Li1 N3A C8A -130.6(15) 4_575 . . . ? O1 Li1 N3A C8A 99.6(17) . . . . ? N3 Li1 N3A C8A -17.0(14) . . . . ? N3A Li1 N3A C8A -17.0(14) 4_575 . . . ? Li1 N3A C8A C9A 85(31) . . . . ? N4 C10 C11 C10 113(67) . . . 3_655 ? N4A N4A C10A C10A 14(3) 3_655 . . 3_655 ? N4A N4A C10A C11A 10(15) 3_655 . . . ? C10A N4A C10A C11A -4(13) 3_655 . . . ? N4A N4A C10A C11A 68(6) 3_655 . . 3_655 ? C10A N4A C10A C11A 54(5) 3_655 . . 3_655 ? C10A N4A C10A N4A -14(3) 3_655 . . 3_655 ? C10A C10A C11A C11A 77(10) 3_655 . . 3_655 ? N4A C10A C11A C11A 81(16) . . . 3_655 ? N4A C10A C11A C11A 90(10) 3_655 . . 3_655 ? N4A C10A C11A C10A 4(13) . . . 3_655 ? C11A C10A C11A C10A -77(10) 3_655 . . 3_655 ? N4A C10A C11A C10A 13.3(14) 3_655 . . 3_655 ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.16 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.469 _refine_diff_density_min -0.548 _refine_diff_density_rms 0.099 _database_code_depnum_ccdc_archive 'CCDC 936734' ####################################################################### # # 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_try-1 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Co(III) Schiff-base dianion, bromide; CH3CN solvate ; _chemical_name_common AGhosh-3 _chemical_melting_point ? _chemical_formula_moiety 'C16 H21 Br Cl2 Co N5 O2' _chemical_formula_sum 'C16 H21 Br Cl2 Co N5 O2' _chemical_formula_weight 525.12 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pnma _symmetry_space_group_name_Hall '-P 2ac 2n' _symmetry_Int_Tables_number 62 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z+1/2' '-x, y+1/2, -z' '-x+1/2, -y, z+1/2' '-x, -y, -z' '-x-1/2, y-1/2, z-1/2' 'x, -y-1/2, z' 'x-1/2, y, -z-1/2' _cell_length_a 10.2678(6) _cell_length_b 13.4525(8) _cell_length_c 14.9665(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2067.3(2) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 167 _cell_measurement_theta_min 2.173 _cell_measurement_theta_max 27.056 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.49 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.687 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1056 _exptl_absorpt_coefficient_mu 3.043 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.5285 _exptl_absorpt_correction_T_max 0.7620 _exptl_absorpt_process_details 'SADABS (Bruker AXS, 2005)' _exptl_special_details ; A very bright diffractor! Large dark block was selected under the microscope in dimmed top light, mounted on the MitiGen 150 uM, centered on a goniometer head of APEX 2 diffractometer, and studied at 120 K. Data were corrected for decay and absorption using the program SADABS (Sheldrick, G.M. (2003). SADABS. Version 2.10. University of Gottingen, Germany) ; _diffrn_ambient_temperature 120(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 APEX2 CCD area detector' _diffrn_measurement_method '4 omega scans; full sphere' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 26557 _diffrn_reflns_av_R_equivalents 0.0301 _diffrn_reflns_av_sigmaI/netI 0.0162 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.04 _diffrn_reflns_theta_max 29.13 _reflns_number_total 2880 _reflns_number_gt 2528 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1998)' _computing_cell_refinement 'SAINT (Bruker, 1998)' _computing_data_reduction 'SAINT (Bruker, 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-III (Burnett & Johnson, 1996)' _computing_publication_material 'CIFTAB (Sheldrick, 1997)' _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^)+(0.0434P)^2^+5.1956P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens rafall _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2880 _refine_ls_number_parameters 173 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0466 _refine_ls_R_factor_gt 0.0383 _refine_ls_wR_factor_ref 0.0987 _refine_ls_wR_factor_gt 0.0941 _refine_ls_goodness_of_fit_ref 1.091 _refine_ls_restrained_S_all 1.091 _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 Br1 Br 0.39997(4) 0.2500 0.29922(3) 0.02437(12) Uani 1 2 d S . . C1 C 0.5421(3) 0.03803(19) 0.17698(18) 0.0182(5) Uani 1 1 d . . . C2 C 0.6244(3) -0.0179(3) 0.1091(2) 0.0276(6) Uani 1 1 d . . . C3 C 0.5249(3) -0.0215(2) 0.2625(2) 0.0262(6) Uani 1 1 d . . . C4 C 0.4066(3) 0.05835(19) 0.13503(17) 0.0169(5) Uani 1 1 d . . . C5 C 0.2731(2) 0.19714(17) 0.08025(15) 0.0137(5) Uani 1 1 d . . . C6 C 0.1668(3) 0.14581(18) 0.04555(16) 0.0150(5) Uani 1 1 d . . . C7 C 0.0614(3) 0.19855(19) 0.01139(16) 0.0156(5) Uani 1 1 d . . . C8 C 0.6174(4) 0.2500 -0.0306(3) 0.0224(8) Uani 1 2 d S . . C9 C 0.6548(5) 0.2500 -0.1241(3) 0.0231(8) Uani 1 2 d S . . Cl1 Cl -0.07224(7) 0.13206(5) -0.02683(5) 0.02282(15) Uani 1 1 d . . . Co1 Co 0.50409(5) 0.2500 0.15797(3) 0.01555(12) Uani 1 2 d S . . H6 H 0.163(4) 0.085(3) 0.048(2) 0.026(9) Uiso 1 1 d . . . H1A H 0.481(4) -0.078(3) 0.254(3) 0.032(10) Uiso 1 1 d . . . H2A H 0.640(4) 0.019(3) 0.060(3) 0.028(9) Uiso 1 1 d . . . H9A H 0.688(5) 0.306(4) -0.136(3) 0.060(14) Uiso 1 1 d . . . H1B H 0.479(4) 0.015(3) 0.307(3) 0.031(10) Uiso 1 1 d . . . H2B H 0.708(4) -0.032(3) 0.131(2) 0.026(9) Uiso 1 1 d . . . H9B H 0.577(10) 0.2500 -0.156(6) 0.09(3) Uiso 1 2 d S . . H1C H 0.605(4) -0.024(3) 0.288(3) 0.040(11) Uiso 1 1 d . . . H2C H 0.581(4) -0.086(4) 0.094(3) 0.051(13) Uiso 1 1 d . . . H1N1 H 0.685(4) 0.138(3) 0.177(2) 0.021(8) Uiso 1 1 d . . . H2N1 H 0.616(4) 0.138(3) 0.251(3) 0.035(11) Uiso 1 1 d . . . N1 N 0.6081(2) 0.13547(18) 0.19823(18) 0.0202(5) Uani 1 1 d . . . N2 N 0.3861(2) 0.15476(16) 0.11671(15) 0.0159(4) Uani 1 1 d . . . N3 N 0.5886(3) 0.2500 0.0422(2) 0.0219(7) Uani 1 2 d S . . O1 O 0.3316(2) -0.01140(14) 0.12064(14) 0.0236(4) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Br1 0.0229(2) 0.0278(2) 0.0224(2) 0.000 -0.00197(15) 0.000 C1 0.0182(12) 0.0149(11) 0.0217(12) 0.0015(10) -0.0026(10) 0.0018(10) C2 0.0216(14) 0.0298(15) 0.0315(15) -0.0038(13) -0.0006(12) 0.0063(12) C3 0.0270(15) 0.0264(15) 0.0252(14) 0.0068(12) -0.0078(12) -0.0015(12) C4 0.0190(12) 0.0156(11) 0.0162(11) 0.0006(9) -0.0010(9) 0.0024(9) C5 0.0159(11) 0.0124(11) 0.0129(10) -0.0003(8) -0.0006(8) 0.0014(9) C6 0.0200(12) 0.0105(11) 0.0146(11) -0.0021(9) -0.0019(9) -0.0006(9) C7 0.0179(12) 0.0162(12) 0.0127(11) -0.0022(9) -0.0034(9) -0.0016(9) C8 0.0211(19) 0.0146(16) 0.032(2) 0.000 -0.0019(16) 0.000 C9 0.030(2) 0.0161(18) 0.0233(19) 0.000 -0.0014(16) 0.000 Cl1 0.0228(3) 0.0156(3) 0.0301(3) -0.0040(2) -0.0120(3) -0.0010(2) Co1 0.0142(2) 0.0140(2) 0.0185(2) 0.000 -0.00339(18) 0.000 N1 0.0154(11) 0.0180(11) 0.0273(13) 0.0007(9) -0.0063(9) 0.0012(9) N2 0.0144(10) 0.0135(9) 0.0198(10) 0.0001(8) -0.0036(8) -0.0007(8) N3 0.0201(16) 0.0192(15) 0.0265(17) 0.000 -0.0019(13) 0.000 O1 0.0221(10) 0.0148(9) 0.0341(11) 0.0015(8) -0.0070(8) -0.0007(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 Br1 Co1 2.3690(7) . ? C1 N1 1.509(4) . ? C1 C3 1.520(4) . ? C1 C2 1.520(4) . ? C1 C4 1.551(4) . ? C2 H2A 0.90(4) . ? C2 H2B 0.94(4) . ? C2 H2C 1.04(5) . ? C3 H1A 0.89(4) . ? C3 H1B 0.95(4) . ? C3 H1C 0.91(4) . ? C4 O1 1.233(3) . ? C4 N2 1.342(3) . ? C5 C6 1.392(3) . ? C5 N2 1.403(3) . ? C5 C5 1.422(5) 7_565 ? C6 C7 1.391(4) . ? C6 H6 0.82(4) . ? C7 C7 1.384(5) 7_565 ? C7 Cl1 1.735(3) . ? C8 N3 1.129(6) . ? C8 C9 1.452(6) . ? C9 H9A 0.84(5) . ? C9 H9B 0.93(10) . ? Co1 N2 1.868(2) . ? Co1 N2 1.868(2) 7_565 ? Co1 N3 1.937(4) . ? Co1 N1 1.969(2) 7_565 ? Co1 N1 1.969(2) . ? N1 H1N1 0.85(4) . ? N1 H2N1 0.80(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 C3 109.4(2) . . ? N1 C1 C2 108.8(2) . . ? C3 C1 C2 111.5(3) . . ? N1 C1 C4 109.6(2) . . ? C3 C1 C4 109.2(2) . . ? C2 C1 C4 108.4(2) . . ? C1 C2 H2A 112(2) . . ? C1 C2 H2B 112(2) . . ? H2A C2 H2B 103(3) . . ? C1 C2 H2C 110(2) . . ? H2A C2 H2C 112(3) . . ? H2B C2 H2C 107(3) . . ? C1 C3 H1A 113(3) . . ? C1 C3 H1B 112(2) . . ? H1A C3 H1B 107(3) . . ? C1 C3 H1C 106(3) . . ? H1A C3 H1C 119(4) . . ? H1B C3 H1C 100(3) . . ? O1 C4 N2 127.0(2) . . ? O1 C4 C1 119.8(2) . . ? N2 C4 C1 113.2(2) . . ? C6 C5 N2 126.3(2) . . ? C6 C5 C5 119.74(14) . 7_565 ? N2 C5 C5 113.98(13) . 7_565 ? C7 C6 C5 119.6(2) . . ? C7 C6 H6 119(3) . . ? C5 C6 H6 121(3) . . ? C7 C7 C6 120.65(15) 7_565 . ? C7 C7 Cl1 121.03(9) 7_565 . ? C6 C7 Cl1 118.26(19) . . ? N3 C8 C9 179.9(5) . . ? C8 C9 H9A 108(3) . . ? C8 C9 H9B 105(6) . . ? H9A C9 H9B 104(4) . . ? N2 Co1 N2 86.58(13) . 7_565 ? N2 Co1 N3 89.70(10) . . ? N2 Co1 N3 89.70(10) 7_565 . ? N2 Co1 N1 171.63(10) . 7_565 ? N2 Co1 N1 85.19(10) 7_565 7_565 ? N3 Co1 N1 91.77(10) . 7_565 ? N2 Co1 N1 85.19(10) . . ? N2 Co1 N1 171.63(10) 7_565 . ? N3 Co1 N1 91.77(10) . . ? N1 Co1 N1 102.99(14) 7_565 . ? N2 Co1 Br1 90.13(7) . . ? N2 Co1 Br1 90.13(7) 7_565 . ? N3 Co1 Br1 179.77(10) . . ? N1 Co1 Br1 88.37(8) 7_565 . ? N1 Co1 Br1 88.37(8) . . ? C1 N1 Co1 111.84(16) . . ? C1 N1 H1N1 112(2) . . ? Co1 N1 H1N1 111(2) . . ? C1 N1 H2N1 107(3) . . ? Co1 N1 H2N1 109(3) . . ? H1N1 N1 H2N1 106(4) . . ? C4 N2 C5 127.0(2) . . ? C4 N2 Co1 119.55(18) . . ? C5 N2 Co1 112.72(16) . . ? C8 N3 Co1 168.6(3) . . ? 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 C4 O1 -173.1(2) . . . . ? C3 C1 C4 O1 -53.2(3) . . . . ? C2 C1 C4 O1 68.4(3) . . . . ? N1 C1 C4 N2 8.1(3) . . . . ? C3 C1 C4 N2 127.9(3) . . . . ? C2 C1 C4 N2 -110.4(3) . . . . ? N2 C5 C6 C7 -179.9(2) . . . . ? C5 C5 C6 C7 -0.2(3) 7_565 . . . ? C5 C6 C7 C7 0.2(3) . . . 7_565 ? C5 C6 C7 Cl1 -177.25(19) . . . . ? C3 C1 N1 Co1 -123.5(2) . . . . ? C2 C1 N1 Co1 114.5(2) . . . . ? C4 C1 N1 Co1 -3.8(3) . . . . ? N2 Co1 N1 C1 -0.50(19) . . . . ? N3 Co1 N1 C1 -90.1(2) . . . . ? N1 Co1 N1 C1 177.72(12) 7_565 . . . ? Br1 Co1 N1 C1 89.77(18) . . . . ? O1 C4 N2 C5 2.5(5) . . . . ? C1 C4 N2 C5 -178.8(2) . . . . ? O1 C4 N2 Co1 172.0(2) . . . . ? C1 C4 N2 Co1 -9.3(3) . . . . ? C6 C5 N2 C4 -8.8(4) . . . . ? C5 C5 N2 C4 171.5(2) 7_565 . . . ? C6 C5 N2 Co1 -178.8(2) . . . . ? C5 C5 N2 Co1 1.43(17) 7_565 . . . ? N2 Co1 N2 C4 -172.69(16) 7_565 . . . ? N3 Co1 N2 C4 97.6(2) . . . . ? N1 Co1 N2 C4 5.8(2) . . . . ? Br1 Co1 N2 C4 -82.6(2) . . . . ? N2 Co1 N2 C5 -1.8(2) 7_565 . . . ? N3 Co1 N2 C5 -91.52(18) . . . . ? N1 Co1 N2 C5 176.68(19) . . . . ? Br1 Co1 N2 C5 88.33(16) . . . . ? N2 Co1 N3 C8 43.29(7) . . . . ? N2 Co1 N3 C8 -43.29(7) 7_565 . . . ? N1 Co1 N3 C8 -128.47(7) 7_565 . . . ? N1 Co1 N3 C8 128.47(7) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 29.13 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.922 _refine_diff_density_min -1.106 _refine_diff_density_rms 0.114 _database_code_depnum_ccdc_archive 'CCDC 936336'