# Electronic Supplementary Material (ESI) for Catalysis Science & Technology # 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_7b_ab1_s _audit_creation_date 2012-11-04T16:41:50-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.4 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C18 H22 Br2 N4 Ni, C H2 Cl2' _chemical_formula_sum 'C19 H24 Br2 Cl2 N4 Ni' _chemical_formula_weight 597.85 _chemical_absolute_configuration unk #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M C2221 _symmetry_space_group_name_Hall 'C 2c 2' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x, -y, -z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z+1/2' 'x+1/2, -y+1/2, -z' '-x+1/2, y+1/2, -z+1/2' _cell_length_a 14.2034(7) _cell_length_b 11.5066(7) _cell_length_c 14.6836(11) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 2399.8(3) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 8205 _cell_measurement_theta_min 2.28 _cell_measurement_theta_max 28.29 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description plate _exptl_crystal_colour blue _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.4 _exptl_crystal_size_min 0.17 _exptl_crystal_density_diffrn 1.655 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1192 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 4.373 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_absorpt_correction_T_min 0.2382 _exptl_absorpt_correction_T_max 0.5235 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1K CCD area detector' _diffrn_measurement_method '\w scans' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0434 _diffrn_reflns_av_unetI/netI 0.0339 _diffrn_reflns_number 8205 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.28 _diffrn_reflns_theta_max 28.29 _diffrn_reflns_theta_full 28.29 _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _reflns_number_total 2981 _reflns_number_gt 2795 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker SMART, Bruker (1998)' _computing_cell_refinement 'Bruker SAINT+, Bruker (1999)' _computing_data_reduction 'Bruker SAINT+' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; Ortep-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999) ; _computing_publication_material ; WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003) ; #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0818P)^2^+1.6021P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_extinction_coef 0.0060(6) _refine_ls_number_reflns 2981 _refine_ls_number_parameters 131 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0473 _refine_ls_R_factor_gt 0.0445 _refine_ls_wR_factor_ref 0.1225 _refine_ls_wR_factor_gt 0.1204 _refine_ls_goodness_of_fit_ref 1.06 _refine_ls_restrained_S_all 1.06 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.025(16) _refine_diff_density_max 0.951 _refine_diff_density_min -0.784 _refine_diff_density_rms 0.102 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 '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' Cl Cl 0.1484 0.1585 '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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 C1 C 0.1819(4) 0.6929(4) 0.0488(3) 0.0492(10) Uani 1 1 d . . . H1A H 0.133 0.6895 0.0019 0.074 Uiso 1 1 calc R . . H1B H 0.2441 0.6928 0.0199 0.074 Uiso 1 1 calc R . . H1C H 0.1744 0.7641 0.0847 0.074 Uiso 1 1 calc R . . C2 C 0.1734(3) 0.5904(4) 0.1095(3) 0.0403(8) Uani 1 1 d . . . C3 C 0.2409(3) 0.5091(4) 0.1338(3) 0.0463(10) Uani 1 1 d . . . H3 H 0.3052 0.508 0.1161 0.056 Uiso 1 1 calc R . . C4 C 0.1945(3) 0.4286(4) 0.1903(3) 0.0428(9) Uani 1 1 d . . . C5 C 0.2349(4) 0.3208(5) 0.2311(4) 0.0605(13) Uani 1 1 d . . . H5A H 0.2529 0.336 0.2944 0.091 Uiso 1 1 calc R . . H5B H 0.2905 0.297 0.1963 0.091 Uiso 1 1 calc R . . H5C H 0.1877 0.2587 0.2294 0.091 Uiso 1 1 calc R . . C6 C 0.0018(3) 0.6185(3) 0.1451(3) 0.0372(7) Uani 1 1 d . . . H6A H -0.0485 0.5654 0.1664 0.045 Uiso 1 1 calc R . . H6B H -0.0116 0.6384 0.0808 0.045 Uiso 1 1 calc R . . C7 C -0.0009(3) 0.7289(3) 0.2018(3) 0.0399(8) Uani 1 1 d . . . C8 C -0.0017(4) 0.8353(4) 0.1560(4) 0.0556(12) Uani 1 1 d . . . H8 H -0.003 0.8363 0.0913 0.067 Uiso 1 1 calc R . . C9 C -0.0008(5) 0.9401(4) 0.2038(5) 0.0715(17) Uani 1 1 d . . . H9 H -0.0012 1.0117 0.1716 0.086 Uiso 1 1 calc R . . C10 C 0.2906(8) 0 0 0.088(3) Uani 1 2 d S . . H10A H 0.3318 0.0645 -0.02 0.106 Uiso 0.5 1 calc PR . . H10B H 0.3318 -0.0645 0.02 0.106 Uiso 0.5 1 calc PR . . Br1 Br 0.04456(4) 0.26826(5) 0.38962(3) 0.05250(18) Uani 1 1 d . . . Cl1 Cl 0.2272(3) 0.0458(3) 0.0907(2) 0.1464(14) Uani 1 1 d . . . N1 N 0.1041(2) 0.4585(3) 0.1996(2) 0.0360(6) Uani 1 1 d . . . N2 N 0.0921(2) 0.5583(3) 0.1500(2) 0.0348(6) Uani 1 1 d . . . Ni1 Ni 0 0.35810(5) 0.25 0.03441(18) Uani 1 2 d S . . 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 C1 0.047(2) 0.054(2) 0.047(2) 0.0068(19) 0.0067(18) -0.0106(19) C2 0.0336(17) 0.046(2) 0.0414(19) -0.0042(18) 0.0028(17) -0.0038(15) C3 0.0304(17) 0.053(2) 0.055(3) 0.0014(19) 0.0017(16) 0.0016(17) C4 0.0337(18) 0.047(2) 0.047(2) -0.0006(18) 0.0017(16) 0.0048(16) C5 0.049(2) 0.063(3) 0.070(3) 0.016(3) 0.010(2) 0.019(2) C6 0.0312(15) 0.0391(16) 0.0413(19) 0.0044(14) -0.0050(16) -0.0017(16) C7 0.0224(12) 0.0363(15) 0.061(2) 0.0020(16) -0.0009(17) -0.0008(16) C8 0.0420(19) 0.042(2) 0.083(3) 0.016(2) 0.006(2) 0.004(2) C9 0.059(2) 0.0353(19) 0.120(5) 0.014(2) 0.014(4) 0.002(2) C10 0.084(7) 0.079(6) 0.101(9) 0.028(6) 0 0 Br1 0.0552(3) 0.0594(3) 0.0429(2) 0.00939(19) 0.00207(19) 0.0074(2) Cl1 0.243(4) 0.0971(17) 0.0994(19) 0.0034(14) 0.047(2) 0.027(2) N1 0.0342(15) 0.0344(15) 0.0393(16) 0.0019(12) 0.0022(12) 0.0011(12) N2 0.0302(14) 0.0381(15) 0.0362(16) 0.0009(12) 0.0015(12) -0.0013(13) Ni1 0.0337(3) 0.0318(3) 0.0377(4) 0 0.0047(3) 0 #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 C1 C2 1.483(6) . ? C1 H1A 0.98 . ? C1 H1B 0.98 . ? C1 H1C 0.98 . ? C2 N2 1.350(5) . ? C2 C3 1.386(6) . ? C3 C4 1.407(7) . ? C3 H3 0.95 . ? C4 N1 1.336(5) . ? C4 C5 1.492(6) . ? C5 H5A 0.98 . ? C5 H5B 0.98 . ? C5 H5C 0.98 . ? C6 N2 1.460(5) . ? C6 C7 1.519(5) . ? C6 H6A 0.99 . ? C6 H6B 0.99 . ? C7 C8 1.396(6) . ? C7 C7 1.416(9) 4 ? C8 C9 1.396(8) . ? C8 H8 0.95 . ? C9 C9 1.356(15) 4 ? C9 H9 0.95 . ? C10 Cl1 1.692(7) 3 ? C10 Cl1 1.692(7) . ? C10 H10A 0.99 . ? C10 H10B 0.99 . ? Br1 Ni1 2.3817(5) . ? N1 N2 1.371(4) . ? N1 Ni1 2.017(3) . ? Ni1 N1 2.017(3) 4 ? Ni1 Br1 2.3817(5) 4 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N2 C2 C3 107.1(4) . . ? N2 C2 C1 123.5(4) . . ? C3 C2 C1 129.4(4) . . ? C2 C3 C4 105.8(4) . . ? C2 C3 H3 127.1 . . ? C4 C3 H3 127.1 . . ? N1 C4 C3 109.9(4) . . ? N1 C4 C5 122.9(4) . . ? C3 C4 C5 127.1(4) . . ? C4 C5 H5A 109.5 . . ? C4 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C4 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? N2 C6 C7 113.1(3) . . ? N2 C6 H6A 109 . . ? C7 C6 H6A 109 . . ? N2 C6 H6B 109 . . ? C7 C6 H6B 109 . . ? H6A C6 H6B 107.8 . . ? C8 C7 C7 118.8(3) . 4 ? C8 C7 C6 117.9(4) . . ? C7 C7 C6 123.2(2) 4 . ? C7 C8 C9 120.9(5) . . ? C7 C8 H8 119.5 . . ? C9 C8 H8 119.5 . . ? C9 C9 C8 120.2(4) 4 . ? C9 C9 H9 119.9 4 . ? C8 C9 H9 119.9 . . ? Cl1 C10 Cl1 115.7(8) 3 . ? Cl1 C10 H10A 108.4 3 . ? Cl1 C10 H10A 108.4 . . ? Cl1 C10 H10B 108.4 3 . ? Cl1 C10 H10B 108.4 . . ? H10A C10 H10B 107.4 . . ? C4 N1 N2 106.4(3) . . ? C4 N1 Ni1 126.5(3) . . ? N2 N1 Ni1 125.7(2) . . ? C2 N2 N1 110.8(3) . . ? C2 N2 C6 126.9(3) . . ? N1 N2 C6 122.2(3) . . ? N1 Ni1 N1 110.14(18) . 4 ? N1 Ni1 Br1 97.32(10) . 4 ? N1 Ni1 Br1 111.69(10) 4 4 ? N1 Ni1 Br1 111.69(10) . . ? N1 Ni1 Br1 97.32(10) 4 . ? Br1 Ni1 Br1 128.55(4) 4 . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N2 C2 C3 C4 0.0(5) . . . . ? C1 C2 C3 C4 -178.1(5) . . . . ? C2 C3 C4 N1 0.3(5) . . . . ? C2 C3 C4 C5 176.9(5) . . . . ? N2 C6 C7 C8 108.9(4) . . . . ? N2 C6 C7 C7 -68.7(6) . . . 4 ? C7 C7 C8 C9 0.0(8) 4 . . . ? C6 C7 C8 C9 -177.7(5) . . . . ? C7 C8 C9 C9 -0.2(12) . . . 4 ? C3 C4 N1 N2 -0.4(5) . . . . ? C5 C4 N1 N2 -177.2(4) . . . . ? C3 C4 N1 Ni1 166.2(3) . . . . ? C5 C4 N1 Ni1 -10.7(7) . . . . ? C3 C2 N2 N1 -0.2(5) . . . . ? C1 C2 N2 N1 178.0(4) . . . . ? C3 C2 N2 C6 179.0(4) . . . . ? C1 C2 N2 C6 -2.8(7) . . . . ? C4 N1 N2 C2 0.4(4) . . . . ? Ni1 N1 N2 C2 -166.3(3) . . . . ? C4 N1 N2 C6 -178.9(4) . . . . ? Ni1 N1 N2 C6 14.4(5) . . . . ? C7 C6 N2 C2 -74.1(5) . . . . ? C7 C6 N2 N1 105.1(4) . . . . ? C4 N1 Ni1 N1 155.1(4) . . . 4 ? N2 N1 Ni1 N1 -40.8(3) . . . 4 ? C4 N1 Ni1 Br1 -88.5(4) . . . 4 ? N2 N1 Ni1 Br1 75.5(3) . . . 4 ? C4 N1 Ni1 Br1 48.1(4) . . . . ? N2 N1 Ni1 Br1 -147.8(3) . . . . ? # END of CIF _database_code_depnum_ccdc_archive 'CCDC 942278' ####################################################################### # # 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_8b_ab2_f _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C18 H22 Cl2 N4 Ni' _chemical_formula_sum 'C18 H22 Cl2 N4 Ni' _chemical_formula_weight 424.01 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.2765(5) _cell_length_b 10.7428(5) _cell_length_c 12.1287(6) _cell_angle_alpha 110.976(3) _cell_angle_beta 96.346(3) _cell_angle_gamma 113.712(3) _cell_volume 986.47(9) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 7571 _cell_measurement_theta_min 1.88 _cell_measurement_theta_max 25.00 _exptl_crystal_description block _exptl_crystal_colour purple _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.427 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 440 _exptl_absorpt_coefficient_mu 1.262 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6735 _exptl_absorpt_correction_T_max 0.7864 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1K CCD area detector' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 7571 _diffrn_reflns_av_R_equivalents 0.0303 _diffrn_reflns_av_sigmaI/netI 0.0264 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.88 _diffrn_reflns_theta_max 25.00 _reflns_number_total 3468 _reflns_number_gt 3062 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART, Bruker (1998)' _computing_cell_refinement 'Bruker SAINT+, Bruker (1999)' _computing_data_reduction 'Bruker SAINT+' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; Ortep-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999) ; _computing_publication_material ; WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003) ; _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^)+(0.0507P)^2^+0.5335P] 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 3468 _refine_ls_number_parameters 229 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0398 _refine_ls_R_factor_gt 0.0329 _refine_ls_wR_factor_ref 0.0928 _refine_ls_wR_factor_gt 0.0893 _refine_ls_goodness_of_fit_ref 1.047 _refine_ls_restrained_S_all 1.047 _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 C1 C -0.6260(4) 0.0676(4) 0.1720(4) 0.0690(10) Uani 1 1 d . . . H1A H -0.6563 -0.0382 0.1353 0.103 Uiso 1 1 calc R . . H1B H -0.7078 0.0827 0.1311 0.103 Uiso 1 1 calc R . . H1C H -0.6190 0.1015 0.2582 0.103 Uiso 1 1 calc R . . C2 C -0.4631(3) 0.1557(3) 0.1588(3) 0.0460(7) Uani 1 1 d . . . C3 C -0.4230(4) 0.2328(4) 0.0886(3) 0.0538(8) Uani 1 1 d . . . H3 H -0.4961 0.2390 0.0344 0.065 Uiso 1 1 calc R . . C4 C -0.2533(4) 0.2998(3) 0.1133(3) 0.0478(7) Uani 1 1 d . . . C5 C -0.1478(4) 0.3993(4) 0.0622(4) 0.0721(10) Uani 1 1 d . . . H5A H -0.0702 0.4962 0.1289 0.108 Uiso 1 1 calc R . . H5B H -0.2164 0.4128 0.0071 0.108 Uiso 1 1 calc R . . H5C H -0.0894 0.3528 0.0180 0.108 Uiso 1 1 calc R . . C6 C -0.2956(3) 0.1238(3) 0.3166(2) 0.0378(6) Uani 1 1 d . . . H6A H -0.3595 0.1448 0.3719 0.045 Uiso 1 1 calc R . . H6B H -0.1803 0.1818 0.3652 0.045 Uiso 1 1 calc R . . C7 C -0.3451(3) -0.0439(3) 0.2641(2) 0.0362(6) Uani 1 1 d . . . C8 C -0.4887(3) -0.1413(3) 0.2770(3) 0.0486(7) Uani 1 1 d . . . H8 H -0.5500 -0.1019 0.3189 0.058 Uiso 1 1 calc R . . C9 C -0.5430(4) -0.2972(4) 0.2285(3) 0.0560(8) Uani 1 1 d . . . H9 H -0.6397 -0.3604 0.2377 0.067 Uiso 1 1 calc R . . C10 C -0.4537(4) -0.3557(3) 0.1677(3) 0.0558(8) Uani 1 1 d . . . H10 H -0.4904 -0.4595 0.1342 0.067 Uiso 1 1 calc R . . C11 C -0.3077(4) -0.2609(3) 0.1555(3) 0.0471(7) Uani 1 1 d . . . H11 H -0.2471 -0.3022 0.1144 0.056 Uiso 1 1 calc R . . C12 C -0.2508(3) -0.1044(3) 0.2042(2) 0.0364(6) Uani 1 1 d . . . C13 C -0.0891(3) -0.0073(3) 0.1902(2) 0.0377(6) Uani 1 1 d . . . H13A H -0.0545 -0.0727 0.1347 0.045 Uiso 1 1 calc R . . H13B H -0.1061 0.0537 0.1527 0.045 Uiso 1 1 calc R . . C14 C 0.0881(4) -0.1054(4) 0.3438(4) 0.0703(10) Uani 1 1 d . . . H14A H 0.0046 -0.1710 0.2653 0.105 Uiso 1 1 calc R . . H14B H 0.0513 -0.1364 0.4051 0.105 Uiso 1 1 calc R . . H14C H 0.1877 -0.1112 0.3376 0.105 Uiso 1 1 calc R . . C15 C 0.1205(3) 0.0540(3) 0.3804(3) 0.0464(7) Uani 1 1 d . . . C16 C 0.2292(4) 0.1852(4) 0.4833(3) 0.0553(8) Uani 1 1 d . . . H16 H 0.3004 0.1936 0.5490 0.066 Uiso 1 1 calc R . . C17 C 0.2133(3) 0.3028(3) 0.4712(2) 0.0447(6) Uani 1 1 d . . . C18 C 0.3032(4) 0.4671(4) 0.5592(3) 0.0658(9) Uani 1 1 d . . . H18A H 0.3492 0.5254 0.5159 0.099 Uiso 1 1 calc R . . H18B H 0.3902 0.4853 0.6235 0.099 Uiso 1 1 calc R . . H18C H 0.2280 0.4966 0.5952 0.099 Uiso 1 1 calc R . . N1 N -0.1882(3) 0.2650(2) 0.1955(2) 0.0388(5) Uani 1 1 d . . . N2 N -0.3190(2) 0.1760(2) 0.22286(19) 0.0357(5) Uani 1 1 d . . . N3 N 0.0431(2) 0.0936(2) 0.30862(19) 0.0352(5) Uani 1 1 d . . . N4 N 0.0989(2) 0.2472(2) 0.36317(19) 0.0361(5) Uani 1 1 d . . . Cl1 Cl 0.12355(11) 0.60112(8) 0.38366(7) 0.0610(2) Uani 1 1 d U . . Cl2 Cl 0.16152(10) 0.28819(8) 0.11807(7) 0.0523(2) Uani 1 1 d U . . Ni1 Ni 0.05680(4) 0.36016(3) 0.27429(3) 0.03530(12) Uani 1 1 d U . . 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 C1 0.0388(16) 0.076(2) 0.099(3) 0.044(2) 0.0181(17) 0.0298(17) C2 0.0387(14) 0.0410(15) 0.0540(17) 0.0152(13) 0.0064(12) 0.0220(12) C3 0.0515(17) 0.0526(18) 0.0580(18) 0.0256(15) 0.0001(14) 0.0285(15) C4 0.0508(16) 0.0436(16) 0.0493(16) 0.0257(14) 0.0057(13) 0.0207(13) C5 0.071(2) 0.076(2) 0.075(2) 0.056(2) 0.0087(18) 0.0239(19) C6 0.0373(13) 0.0427(15) 0.0337(13) 0.0166(12) 0.0127(11) 0.0190(12) C7 0.0343(13) 0.0370(14) 0.0314(13) 0.0180(11) 0.0047(10) 0.0107(11) C8 0.0382(14) 0.0587(19) 0.0510(17) 0.0333(15) 0.0116(12) 0.0174(13) C9 0.0413(16) 0.0532(19) 0.0605(19) 0.0382(16) 0.0040(14) 0.0022(14) C10 0.0570(18) 0.0339(15) 0.0532(18) 0.0226(14) -0.0031(15) 0.0029(14) C11 0.0558(17) 0.0327(14) 0.0434(15) 0.0176(12) 0.0071(13) 0.0141(13) C12 0.0413(14) 0.0293(13) 0.0313(13) 0.0150(10) 0.0052(10) 0.0102(11) C13 0.0454(15) 0.0313(13) 0.0371(14) 0.0153(11) 0.0149(11) 0.0179(11) C14 0.062(2) 0.064(2) 0.117(3) 0.062(2) 0.029(2) 0.0385(18) C15 0.0444(15) 0.0562(18) 0.0625(19) 0.0402(16) 0.0232(14) 0.0312(14) C16 0.0491(17) 0.075(2) 0.0540(18) 0.0388(17) 0.0086(14) 0.0334(16) C17 0.0383(14) 0.0546(17) 0.0370(14) 0.0176(13) 0.0073(11) 0.0219(13) C18 0.060(2) 0.061(2) 0.0480(18) 0.0067(16) -0.0054(15) 0.0248(17) N1 0.0384(12) 0.0367(12) 0.0419(12) 0.0205(10) 0.0086(9) 0.0165(10) N2 0.0331(11) 0.0332(11) 0.0399(12) 0.0149(9) 0.0090(9) 0.0165(9) N3 0.0342(11) 0.0318(11) 0.0407(12) 0.0171(9) 0.0119(9) 0.0157(9) N4 0.0365(11) 0.0331(11) 0.0347(11) 0.0129(9) 0.0071(9) 0.0158(9) Cl1 0.0851(6) 0.0311(4) 0.0536(4) 0.0069(3) 0.0137(4) 0.0279(4) Cl2 0.0682(5) 0.0428(4) 0.0547(4) 0.0240(3) 0.0371(4) 0.0273(4) Ni1 0.03511(19) 0.02634(18) 0.0405(2) 0.01423(15) 0.00911(14) 0.01208(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 C1 C2 1.489(4) . ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 N2 1.362(3) . ? C2 C3 1.370(4) . ? C3 C4 1.384(4) . ? C3 H3 0.9300 . ? C4 N1 1.347(3) . ? C4 C5 1.501(4) . ? C5 H5A 0.9600 . ? C5 H5B 0.9600 . ? C5 H5C 0.9600 . ? C6 N2 1.467(3) . ? C6 C7 1.520(4) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C8 1.391(4) . ? C7 C12 1.406(4) . ? C8 C9 1.398(5) . ? C8 H8 0.9300 . ? C9 C10 1.359(5) . ? C9 H9 0.9300 . ? C10 C11 1.391(4) . ? C10 H10 0.9300 . ? C11 C12 1.400(4) . ? C11 H11 0.9300 . ? C12 C13 1.514(3) . ? C13 N3 1.473(3) . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 C15 1.494(4) . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C15 N3 1.352(3) . ? C15 C16 1.371(5) . ? C16 C17 1.385(4) . ? C16 H16 0.9300 . ? C17 N4 1.350(3) . ? C17 C18 1.491(4) . ? C18 H18A 0.9600 . ? C18 H18B 0.9600 . ? C18 H18C 0.9600 . ? N1 N2 1.371(3) . ? N1 Ni1 2.019(2) . ? N3 N4 1.372(3) . ? N4 Ni1 2.003(2) . ? Cl1 Ni1 2.2169(8) . ? Cl2 Ni1 2.2569(7) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N2 C2 C3 106.5(2) . . ? N2 C2 C1 123.0(3) . . ? C3 C2 C1 130.4(3) . . ? C2 C3 C4 107.2(3) . . ? C2 C3 H3 126.4 . . ? C4 C3 H3 126.4 . . ? N1 C4 C3 109.8(3) . . ? N1 C4 C5 122.0(3) . . ? C3 C4 C5 128.2(3) . . ? C4 C5 H5A 109.5 . . ? C4 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C4 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? N2 C6 C7 114.3(2) . . ? N2 C6 H6A 108.7 . . ? C7 C6 H6A 108.7 . . ? N2 C6 H6B 108.7 . . ? C7 C6 H6B 108.7 . . ? H6A C6 H6B 107.6 . . ? C8 C7 C12 118.6(2) . . ? C8 C7 C6 118.8(2) . . ? C12 C7 C6 122.7(2) . . ? C7 C8 C9 121.6(3) . . ? C7 C8 H8 119.2 . . ? C9 C8 H8 119.2 . . ? C10 C9 C8 119.6(3) . . ? C10 C9 H9 120.2 . . ? C8 C9 H9 120.2 . . ? C9 C10 C11 120.3(3) . . ? C9 C10 H10 119.9 . . ? C11 C10 H10 119.9 . . ? C10 C11 C12 120.9(3) . . ? C10 C11 H11 119.5 . . ? C12 C11 H11 119.5 . . ? C11 C12 C7 119.0(2) . . ? C11 C12 C13 118.3(2) . . ? C7 C12 C13 122.7(2) . . ? N3 C13 C12 113.0(2) . . ? N3 C13 H13A 109.0 . . ? C12 C13 H13A 109.0 . . ? N3 C13 H13B 109.0 . . ? C12 C13 H13B 109.0 . . ? H13A C13 H13B 107.8 . . ? C15 C14 H14A 109.5 . . ? C15 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C15 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? N3 C15 C16 106.7(3) . . ? N3 C15 C14 123.0(3) . . ? C16 C15 C14 130.3(3) . . ? C15 C16 C17 107.3(3) . . ? C15 C16 H16 126.3 . . ? C17 C16 H16 126.3 . . ? N4 C17 C16 109.4(3) . . ? N4 C17 C18 122.6(3) . . ? C16 C17 C18 128.1(3) . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C4 N1 N2 105.8(2) . . ? C4 N1 Ni1 123.12(18) . . ? N2 N1 Ni1 130.41(16) . . ? C2 N2 N1 110.6(2) . . ? C2 N2 C6 127.4(2) . . ? N1 N2 C6 121.80(19) . . ? C15 N3 N4 110.8(2) . . ? C15 N3 C13 127.6(2) . . ? N4 N3 C13 121.53(19) . . ? C17 N4 N3 105.8(2) . . ? C17 N4 Ni1 128.45(19) . . ? N3 N4 Ni1 123.89(15) . . ? N4 Ni1 N1 109.26(8) . . ? N4 Ni1 Cl1 118.63(6) . . ? N1 Ni1 Cl1 102.01(7) . . ? N4 Ni1 Cl2 98.76(6) . . ? N1 Ni1 Cl2 105.86(7) . . ? Cl1 Ni1 Cl2 121.60(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 N2 C2 C3 C4 -0.6(3) . . . . ? C1 C2 C3 C4 177.9(3) . . . . ? C2 C3 C4 N1 0.6(4) . . . . ? C2 C3 C4 C5 -178.5(3) . . . . ? N2 C6 C7 C8 -107.2(3) . . . . ? N2 C6 C7 C12 73.5(3) . . . . ? C12 C7 C8 C9 -2.1(4) . . . . ? C6 C7 C8 C9 178.6(2) . . . . ? C7 C8 C9 C10 0.4(4) . . . . ? C8 C9 C10 C11 1.0(5) . . . . ? C9 C10 C11 C12 -0.6(4) . . . . ? C10 C11 C12 C7 -1.2(4) . . . . ? C10 C11 C12 C13 178.7(2) . . . . ? C8 C7 C12 C11 2.5(4) . . . . ? C6 C7 C12 C11 -178.2(2) . . . . ? C8 C7 C12 C13 -177.4(2) . . . . ? C6 C7 C12 C13 1.9(4) . . . . ? C11 C12 C13 N3 -111.8(3) . . . . ? C7 C12 C13 N3 68.1(3) . . . . ? N3 C15 C16 C17 0.5(3) . . . . ? C14 C15 C16 C17 178.7(3) . . . . ? C15 C16 C17 N4 -0.5(3) . . . . ? C15 C16 C17 C18 179.3(3) . . . . ? C3 C4 N1 N2 -0.3(3) . . . . ? C5 C4 N1 N2 178.8(3) . . . . ? C3 C4 N1 Ni1 -171.9(2) . . . . ? C5 C4 N1 Ni1 7.2(4) . . . . ? C3 C2 N2 N1 0.4(3) . . . . ? C1 C2 N2 N1 -178.2(3) . . . . ? C3 C2 N2 C6 175.8(2) . . . . ? C1 C2 N2 C6 -2.8(4) . . . . ? C4 N1 N2 C2 0.0(3) . . . . ? Ni1 N1 N2 C2 170.66(19) . . . . ? C4 N1 N2 C6 -175.8(2) . . . . ? Ni1 N1 N2 C6 -5.1(3) . . . . ? C7 C6 N2 C2 77.4(3) . . . . ? C7 C6 N2 N1 -107.6(3) . . . . ? C16 C15 N3 N4 -0.3(3) . . . . ? C14 C15 N3 N4 -178.6(3) . . . . ? C16 C15 N3 C13 -177.6(2) . . . . ? C14 C15 N3 C13 4.1(4) . . . . ? C12 C13 N3 C15 69.2(3) . . . . ? C12 C13 N3 N4 -107.9(2) . . . . ? C16 C17 N4 N3 0.3(3) . . . . ? C18 C17 N4 N3 -179.5(3) . . . . ? C16 C17 N4 Ni1 -164.5(2) . . . . ? C18 C17 N4 Ni1 15.7(4) . . . . ? C15 N3 N4 C17 0.0(3) . . . . ? C13 N3 N4 C17 177.5(2) . . . . ? C15 N3 N4 Ni1 165.67(17) . . . . ? C13 N3 N4 Ni1 -16.8(3) . . . . ? C17 N4 Ni1 N1 -143.0(2) . . . . ? N3 N4 Ni1 N1 54.7(2) . . . . ? C17 N4 Ni1 Cl1 -26.8(2) . . . . ? N3 N4 Ni1 Cl1 170.88(15) . . . . ? C17 N4 Ni1 Cl2 106.7(2) . . . . ? N3 N4 Ni1 Cl2 -55.63(18) . . . . ? C4 N1 Ni1 N4 -169.0(2) . . . . ? N2 N1 Ni1 N4 21.7(2) . . . . ? C4 N1 Ni1 Cl1 64.6(2) . . . . ? N2 N1 Ni1 Cl1 -104.7(2) . . . . ? C4 N1 Ni1 Cl2 -63.5(2) . . . . ? N2 N1 Ni1 Cl2 127.2(2) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.396 _refine_diff_density_min -0.480 _refine_diff_density_rms 0.073 _database_code_depnum_ccdc_archive 'CCDC 942279' ####################################################################### # # 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_8b_ab1_a _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H22 Br2 N4 Ni' _chemical_formula_weight 512.93 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' Ni Ni 0.3393 1.1124 '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 ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.3446(18) _cell_length_b 14.994(3) _cell_length_c 15.681(3) _cell_angle_alpha 75.599(10) _cell_angle_beta 78.411(10) _cell_angle_gamma 81.522(11) _cell_volume 2073.7(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.643 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1024 _exptl_absorpt_coefficient_mu 4.797 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min 0.2499 _exptl_absorpt_correction_T_max 0.7002 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 20762 _diffrn_reflns_av_R_equivalents 0.0722 _diffrn_reflns_av_sigmaI/netI 0.1281 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.36 _diffrn_reflns_theta_max 28.45 _reflns_number_total 10280 _reflns_number_gt 4617 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution ? _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0689P)^2^+0.0267P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 10280 _refine_ls_number_parameters 451 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1531 _refine_ls_R_factor_gt 0.0554 _refine_ls_wR_factor_ref 0.1563 _refine_ls_wR_factor_gt 0.1175 _refine_ls_goodness_of_fit_ref 0.913 _refine_ls_restrained_S_all 0.913 _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 C1 C 0.7442(7) 0.0803(4) 0.5879(4) 0.0452(16) Uani 1 1 d . . . H1A H 0.8124 0.0630 0.5378 0.054 Uiso 1 1 calc R . . H1B H 0.6576 0.1142 0.5655 0.054 Uiso 1 1 calc R . . C2 C 0.7002(6) -0.0074(4) 0.6562(4) 0.0400(15) Uani 1 1 d . . . C3 C 0.6186(7) -0.0674(5) 0.6353(5) 0.0597(19) Uani 1 1 d . . . H3 H 0.5903 -0.0551 0.5796 0.072 Uiso 1 1 calc R . . C4 C 0.5802(8) -0.1472(5) 0.7011(7) 0.077(3) Uani 1 1 d . . . H4 H 0.5248 -0.1871 0.6878 0.093 Uiso 1 1 calc R . . C5 C 0.6203(8) -0.1684(5) 0.7824(6) 0.066(2) Uani 1 1 d . . . H5 H 0.5935 -0.2220 0.8237 0.079 Uiso 1 1 calc R . . C6 C 0.7005(6) -0.1102(4) 0.8032(5) 0.0451(16) Uani 1 1 d . . . C7 C 0.7412(8) -0.1309(5) 0.8955(5) 0.061(2) Uani 1 1 d . . . H7A H 0.6580 -0.1101 0.9364 0.073 Uiso 1 1 calc R . . H7B H 0.7610 -0.1973 0.9160 0.073 Uiso 1 1 calc R . . C8 C 0.7408(6) -0.0300(4) 0.7400(4) 0.0399(14) Uani 1 1 d . . . H8 H 0.7961 0.0091 0.7546 0.048 Uiso 1 1 calc R . . C9 C 0.7750(7) 0.2863(4) 0.7811(5) 0.0553(18) Uani 1 1 d . . . H9A H 0.6698 0.2973 0.7915 0.083 Uiso 1 1 calc R . . H9B H 0.8161 0.3442 0.7569 0.083 Uiso 1 1 calc R . . H9C H 0.8082 0.2568 0.8364 0.083 Uiso 1 1 calc R . . C10 C 0.8239(7) 0.2241(4) 0.7153(4) 0.0416(15) Uani 1 1 d . . . C11 C 0.9678(7) 0.1925(4) 0.6831(5) 0.0472(16) Uani 1 1 d . . . H11 H 1.0537 0.2050 0.6972 0.057 Uiso 1 1 calc R . . C12 C 0.9550(6) 0.1390(4) 0.6258(4) 0.0424(15) Uani 1 1 d . . . C13 C 1.0718(7) 0.0840(5) 0.5726(5) 0.066(2) Uani 1 1 d . . . H13A H 1.0266 0.0544 0.5386 0.100 Uiso 1 1 calc R . . H13B H 1.1244 0.0378 0.6126 0.100 Uiso 1 1 calc R . . H13C H 1.1388 0.1248 0.5327 0.100 Uiso 1 1 calc R . . C14 C 0.7300(10) 0.0491(6) 0.9576(6) 0.095(3) Uani 1 1 d . . . H14A H 0.6494 0.0121 0.9710 0.142 Uiso 1 1 calc R . . H14B H 0.7068 0.1067 0.9171 0.142 Uiso 1 1 calc R . . H14C H 0.7473 0.0612 1.0118 0.142 Uiso 1 1 calc R . . C15 C 0.8663(10) -0.0022(5) 0.9149(5) 0.064(2) Uani 1 1 d . . . C16 C 1.0041(9) 0.0253(5) 0.8861(5) 0.063(2) Uani 1 1 d . . . H16 H 1.0362 0.0799 0.8897 0.076 Uiso 1 1 calc R . . C17 C 1.0871(8) -0.0467(5) 0.8496(5) 0.0583(19) Uani 1 1 d . . . C18 C 1.2468(8) -0.0516(6) 0.8069(6) 0.079(3) Uani 1 1 d . . . H18A H 1.2747 -0.1090 0.7883 0.119 Uiso 1 1 calc R . . H18B H 1.3057 -0.0480 0.8493 0.119 Uiso 1 1 calc R . . H18C H 1.2616 -0.0009 0.7559 0.119 Uiso 1 1 calc R . . C19 C 0.4871(7) 0.6131(4) 0.6653(5) 0.0531(17) Uani 1 1 d . . . H19A H 0.4145 0.6033 0.7187 0.080 Uiso 1 1 calc R . . H19B H 0.4460 0.6576 0.6187 0.080 Uiso 1 1 calc R . . H19C H 0.5704 0.6359 0.6769 0.080 Uiso 1 1 calc R . . C20 C 0.5339(6) 0.5247(4) 0.6372(4) 0.0357(13) Uani 1 1 d . . . C21 C 0.6343(6) 0.5045(4) 0.5658(4) 0.0383(14) Uani 1 1 d . . . H21 H 0.6897 0.5463 0.5225 0.046 Uiso 1 1 calc R . . C22 C 0.6384(6) 0.4118(4) 0.5698(4) 0.0331(13) Uani 1 1 d . . . C23 C 0.7315(7) 0.3568(4) 0.5082(4) 0.0436(15) Uani 1 1 d . . . H23A H 0.7103 0.2934 0.5276 0.065 Uiso 1 1 calc R . . H23B H 0.8333 0.3600 0.5085 0.065 Uiso 1 1 calc R . . H23C H 0.7110 0.3814 0.4487 0.065 Uiso 1 1 calc R . . C24 C 0.6828(8) -0.4930(5) 0.8961(5) 0.070(2) Uani 1 1 d . . . H24A H 0.6875 -0.4815 0.8326 0.105 Uiso 1 1 calc R . . H24B H 0.5832 -0.4799 0.9241 0.105 Uiso 1 1 calc R . . H24C H 0.7160 -0.5567 0.9185 0.105 Uiso 1 1 calc R . . C25 C 0.7794(7) -0.4315(4) 0.9165(5) 0.0495(17) Uani 1 1 d . . . C26 C 0.8073(8) -0.4229(5) 0.9954(5) 0.0581(19) Uani 1 1 d . . . H26 H 0.7675 -0.4551 1.0519 0.070 Uiso 1 1 calc R . . C27 C 0.9057(7) -0.3575(4) 0.9766(4) 0.0480(16) Uani 1 1 d . . . C36 C 0.8762(7) -0.3629(4) 0.7560(4) 0.0447(15) Uani 1 1 d . . . H36A H 0.9136 -0.3044 0.7247 0.054 Uiso 1 1 calc R . . H36B H 0.7807 -0.3627 0.7405 0.054 Uiso 1 1 calc R . . C28 C 0.9652(8) -0.3217(6) 1.0414(4) 0.067(2) Uani 1 1 d . . . H28A H 1.0314 -0.2766 1.0095 0.100 Uiso 1 1 calc R . . H28B H 1.0168 -0.3719 1.0782 0.100 Uiso 1 1 calc R . . H28C H 0.8858 -0.2935 1.0784 0.100 Uiso 1 1 calc R . . C29 C 1.3562(6) -0.5661(4) 0.7566(4) 0.0409(15) Uani 1 1 d . . . H29A H 1.3649 -0.5284 0.7971 0.049 Uiso 1 1 calc R . . H29B H 1.3606 -0.6302 0.7895 0.049 Uiso 1 1 calc R . . C30 C 1.2092(6) -0.5388(4) 0.7263(4) 0.0357(14) Uani 1 1 d . . . C31 C 1.1687(7) -0.5826(4) 0.6678(4) 0.0470(16) Uani 1 1 d . . . H31 H 1.2311 -0.6306 0.6484 0.056 Uiso 1 1 calc R . . C32 C 1.0353(7) -0.5548(5) 0.6381(5) 0.0570(19) Uani 1 1 d . . . H32 H 1.0086 -0.5845 0.5990 0.068 Uiso 1 1 calc R . . C33 C 0.9427(7) -0.4839(5) 0.6660(5) 0.0507(17) Uani 1 1 d . . . H33 H 0.8545 -0.4650 0.6448 0.061 Uiso 1 1 calc R . . C34 C 0.9789(6) -0.4406(4) 0.7248(4) 0.0391(14) Uani 1 1 d . . . C35 C 1.1145(6) -0.4675(4) 0.7541(4) 0.0378(14) Uani 1 1 d . . . H35 H 1.1410 -0.4371 0.7927 0.045 Uiso 1 1 calc R . . N1 N 0.7281(5) 0.1921(3) 0.6811(3) 0.0356(11) Uani 1 1 d . . . N2 N 0.8116(5) 0.1401(3) 0.6242(3) 0.0374(12) Uani 1 1 d . . . N3 N 0.8675(6) -0.0875(4) 0.8986(4) 0.0534(14) Uani 1 1 d . . . N4 N 1.0060(6) -0.1151(4) 0.8567(3) 0.0490(14) Uani 1 1 d . . . N5 N 0.4808(5) 0.4448(3) 0.6822(3) 0.0336(11) Uani 1 1 d . . . N6 N 0.5430(5) 0.3733(3) 0.6418(3) 0.0339(11) Uani 1 1 d . . . N7 N 0.9389(5) -0.3257(3) 0.8885(3) 0.0388(12) Uani 1 1 d . . . N8 N 0.8590(5) -0.3709(3) 0.8521(3) 0.0398(12) Uani 1 1 d . . . Ni1 Ni 0.51334(8) 0.23697(5) 0.68376(5) 0.0410(2) Uani 1 1 d . . . Ni2 Ni 1.08381(9) -0.23356(5) 0.81824(6) 0.0473(2) Uani 1 1 d . . . Br1 Br 0.39450(8) 0.21661(5) 0.56965(5) 0.0623(2) Uani 1 1 d . . . Br2 Br 0.40089(9) 0.18169(5) 0.83459(5) 0.0707(3) Uani 1 1 d . . . Br3 Br 1.12950(9) -0.19057(5) 0.66008(5) 0.0668(2) Uani 1 1 d . . . Br4 Br 1.29571(8) -0.31193(5) 0.88101(5) 0.0647(2) 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 C1 0.045(4) 0.048(4) 0.041(4) -0.013(3) -0.005(3) 0.000(3) C2 0.028(3) 0.037(3) 0.055(4) -0.019(3) 0.003(3) 0.002(3) C3 0.047(4) 0.063(5) 0.077(5) -0.028(4) -0.012(4) -0.006(4) C4 0.047(5) 0.042(4) 0.145(9) -0.024(5) -0.010(5) -0.016(3) C5 0.044(4) 0.043(4) 0.100(7) 0.004(4) -0.009(4) -0.006(3) C6 0.031(3) 0.032(3) 0.062(5) -0.006(3) 0.004(3) 0.003(3) C7 0.049(4) 0.051(4) 0.060(5) 0.008(4) 0.008(4) 0.007(3) C8 0.034(3) 0.037(3) 0.044(4) -0.006(3) 0.000(3) -0.006(3) C9 0.058(4) 0.055(4) 0.060(5) -0.027(4) -0.015(4) 0.000(3) C10 0.039(4) 0.036(3) 0.049(4) -0.005(3) -0.009(3) -0.006(3) C11 0.035(4) 0.043(4) 0.067(5) -0.018(3) -0.010(3) -0.005(3) C12 0.036(4) 0.026(3) 0.056(4) -0.003(3) 0.000(3) 0.001(3) C13 0.049(4) 0.059(4) 0.085(6) -0.026(4) 0.007(4) 0.004(4) C14 0.110(7) 0.100(7) 0.067(6) -0.038(5) -0.022(5) 0.052(6) C15 0.098(6) 0.054(5) 0.032(4) -0.007(4) -0.018(4) 0.023(4) C16 0.085(6) 0.057(5) 0.056(5) -0.013(4) -0.034(4) 0.001(4) C17 0.073(5) 0.055(4) 0.046(4) -0.010(4) -0.016(4) 0.004(4) C18 0.068(5) 0.084(6) 0.097(7) -0.035(5) -0.004(5) -0.030(5) C19 0.062(4) 0.041(4) 0.058(5) -0.011(3) -0.010(4) -0.011(3) C20 0.034(3) 0.036(3) 0.037(4) -0.002(3) -0.012(3) -0.002(3) C21 0.031(3) 0.044(4) 0.040(4) -0.004(3) -0.007(3) -0.009(3) C22 0.033(3) 0.039(3) 0.030(3) -0.009(3) -0.009(3) -0.002(3) C23 0.043(4) 0.046(3) 0.034(4) -0.002(3) 0.002(3) -0.003(3) C24 0.055(5) 0.077(5) 0.072(6) -0.008(4) 0.000(4) -0.017(4) C25 0.038(4) 0.048(4) 0.049(4) 0.003(3) 0.005(3) -0.003(3) C26 0.062(5) 0.063(4) 0.037(4) 0.002(4) 0.001(3) -0.002(4) C27 0.050(4) 0.053(4) 0.034(4) -0.004(3) -0.005(3) 0.004(3) C36 0.036(3) 0.051(4) 0.042(4) -0.004(3) -0.010(3) 0.003(3) C28 0.070(5) 0.089(6) 0.036(4) -0.009(4) 0.000(4) -0.013(4) C29 0.041(4) 0.046(3) 0.032(3) -0.010(3) -0.001(3) 0.001(3) C30 0.032(3) 0.039(3) 0.029(3) -0.001(3) 0.004(3) -0.008(3) C31 0.037(4) 0.043(4) 0.058(4) -0.016(3) 0.003(3) -0.004(3) C32 0.045(4) 0.057(4) 0.083(6) -0.034(4) -0.010(4) -0.019(3) C33 0.028(3) 0.070(5) 0.059(5) -0.018(4) -0.015(3) -0.005(3) C34 0.030(3) 0.045(3) 0.038(4) -0.007(3) 0.001(3) -0.002(3) C35 0.038(3) 0.038(3) 0.035(3) -0.009(3) -0.003(3) -0.002(3) N1 0.037(3) 0.027(2) 0.036(3) 0.000(2) -0.003(2) 0.004(2) N2 0.044(3) 0.030(2) 0.034(3) -0.006(2) 0.001(2) -0.002(2) N3 0.057(4) 0.052(3) 0.039(3) 0.000(3) -0.002(3) 0.008(3) N4 0.046(3) 0.050(3) 0.045(3) -0.007(3) -0.005(3) 0.002(3) N5 0.031(3) 0.036(3) 0.031(3) -0.008(2) -0.002(2) 0.001(2) N6 0.030(3) 0.033(3) 0.034(3) -0.006(2) -0.003(2) 0.001(2) N7 0.038(3) 0.036(3) 0.035(3) 0.000(2) -0.005(2) 0.001(2) N8 0.031(3) 0.042(3) 0.038(3) -0.005(2) 0.002(2) 0.005(2) Ni1 0.0335(4) 0.0372(4) 0.0469(5) -0.0042(4) 0.0005(4) -0.0053(3) Ni2 0.0479(5) 0.0426(4) 0.0423(5) -0.0036(4) 0.0039(4) -0.0019(4) Br1 0.0480(4) 0.0689(5) 0.0791(6) -0.0277(4) -0.0162(4) -0.0087(3) Br2 0.0745(5) 0.0579(4) 0.0563(5) 0.0063(4) 0.0171(4) -0.0042(4) Br3 0.0906(6) 0.0582(4) 0.0404(4) -0.0019(3) 0.0046(4) -0.0095(4) Br4 0.0515(4) 0.0683(5) 0.0647(5) 0.0014(4) -0.0091(4) -0.0052(4) _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 C1 N2 1.446(7) . ? C1 C2 1.526(8) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C2 C8 1.389(9) . ? C2 C3 1.395(8) . ? C3 C4 1.410(11) . ? C3 H3 0.9300 . ? C4 C5 1.350(11) . ? C4 H4 0.9300 . ? C5 C6 1.365(9) . ? C5 H5 0.9300 . ? C6 C8 1.400(8) . ? C6 C7 1.516(10) . ? C7 N3 1.443(9) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 H8 0.9300 . ? C9 C10 1.519(8) . ? C9 H9A 0.9600 . ? C9 H9B 0.9600 . ? C9 H9C 0.9600 . ? C10 N1 1.328(7) . ? C10 C11 1.395(8) . ? C11 C12 1.377(8) . ? C11 H11 0.9300 . ? C12 N2 1.342(7) . ? C12 C13 1.510(8) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C14 C15 1.512(10) . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C15 N3 1.363(9) . ? C15 C16 1.365(11) . ? C16 C17 1.406(9) . ? C16 H16 0.9300 . ? C17 N4 1.334(8) . ? C17 C18 1.507(10) . ? C18 H18A 0.9600 . ? C18 H18B 0.9600 . ? C18 H18C 0.9600 . ? C19 C20 1.479(8) . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 0.9600 . ? C20 N5 1.339(7) . ? C20 C21 1.374(8) . ? C21 C22 1.371(8) . ? C21 H21 0.9300 . ? C22 N6 1.351(7) . ? C22 C23 1.490(8) . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? C24 C25 1.508(9) . ? C24 H24A 0.9600 . ? C24 H24B 0.9600 . ? C24 H24C 0.9600 . ? C25 C26 1.355(9) . ? C25 N8 1.357(7) . ? C26 C27 1.380(9) . ? C26 H26 0.9300 . ? C27 N7 1.332(7) . ? C27 C28 1.490(9) . ? C36 N8 1.459(7) . ? C36 C34 1.509(8) . ? C36 H36A 0.9700 . ? C36 H36B 0.9700 . ? C28 H28A 0.9600 . ? C28 H28B 0.9600 . ? C28 H28C 0.9600 . ? C29 N5 1.469(7) 1_645 ? C29 C30 1.511(8) . ? C29 H29A 0.9700 . ? C29 H29B 0.9700 . ? C30 C35 1.384(8) . ? C30 C31 1.388(8) . ? C31 C32 1.389(9) . ? C31 H31 0.9300 . ? C32 C33 1.371(9) . ? C32 H32 0.9300 . ? C33 C34 1.370(8) . ? C33 H33 0.9300 . ? C34 C35 1.404(8) . ? C35 H35 0.9300 . ? N1 N2 1.379(6) . ? N1 Ni1 2.016(5) . ? N3 N4 1.383(7) . ? N4 Ni2 2.005(5) . ? N5 N6 1.376(6) . ? N5 C29 1.469(7) 1_465 ? N6 Ni1 2.029(4) . ? N7 N8 1.362(7) . ? N7 Ni2 2.037(5) . ? Ni1 Br2 2.3809(11) . ? Ni1 Br1 2.3872(12) . ? Ni2 Br3 2.3685(12) . ? Ni2 Br4 2.4067(12) . ? 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 C1 C2 113.1(5) . . ? N2 C1 H1A 109.0 . . ? C2 C1 H1A 109.0 . . ? N2 C1 H1B 109.0 . . ? C2 C1 H1B 109.0 . . ? H1A C1 H1B 107.8 . . ? C8 C2 C3 118.4(6) . . ? C8 C2 C1 121.2(5) . . ? C3 C2 C1 120.4(6) . . ? C2 C3 C4 118.1(7) . . ? C2 C3 H3 121.0 . . ? C4 C3 H3 121.0 . . ? C5 C4 C3 123.0(7) . . ? C5 C4 H4 118.5 . . ? C3 C4 H4 118.5 . . ? C4 C5 C6 119.3(7) . . ? C4 C5 H5 120.4 . . ? C6 C5 H5 120.4 . . ? C5 C6 C8 119.7(7) . . ? C5 C6 C7 120.0(6) . . ? C8 C6 C7 120.2(6) . . ? N3 C7 C6 113.7(5) . . ? N3 C7 H7A 108.8 . . ? C6 C7 H7A 108.8 . . ? N3 C7 H7B 108.8 . . ? C6 C7 H7B 108.8 . . ? H7A C7 H7B 107.7 . . ? C2 C8 C6 121.5(6) . . ? C2 C8 H8 119.2 . . ? C6 C8 H8 119.2 . . ? C10 C9 H9A 109.5 . . ? C10 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C10 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? N1 C10 C11 111.2(5) . . ? N1 C10 C9 121.9(5) . . ? C11 C10 C9 126.9(6) . . ? C12 C11 C10 105.0(6) . . ? C12 C11 H11 127.5 . . ? C10 C11 H11 127.5 . . ? N2 C12 C11 108.0(5) . . ? N2 C12 C13 121.8(6) . . ? C11 C12 C13 130.1(6) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C15 C14 H14A 109.5 . . ? C15 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C15 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? N3 C15 C16 108.4(7) . . ? N3 C15 C14 123.0(8) . . ? C16 C15 C14 128.5(8) . . ? C15 C16 C17 105.1(7) . . ? C15 C16 H16 127.5 . . ? C17 C16 H16 127.5 . . ? N4 C17 C16 111.3(7) . . ? N4 C17 C18 121.3(6) . . ? C16 C17 C18 127.4(7) . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C20 C19 H19A 109.5 . . ? C20 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C20 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? N5 C20 C21 106.2(5) . . ? N5 C20 C19 123.2(5) . . ? C21 C20 C19 130.6(6) . . ? C22 C21 C20 107.9(5) . . ? C22 C21 H21 126.1 . . ? C20 C21 H21 126.1 . . ? N6 C22 C21 109.4(5) . . ? N6 C22 C23 122.4(5) . . ? C21 C22 C23 128.2(5) . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C25 C24 H24A 109.5 . . ? C25 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C25 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C26 C25 N8 106.1(6) . . ? C26 C25 C24 130.9(6) . . ? N8 C25 C24 123.0(6) . . ? C25 C26 C27 107.5(6) . . ? C25 C26 H26 126.3 . . ? C27 C26 H26 126.3 . . ? N7 C27 C26 109.9(6) . . ? N7 C27 C28 122.5(6) . . ? C26 C27 C28 127.6(6) . . ? N8 C36 C34 112.9(5) . . ? N8 C36 H36A 109.0 . . ? C34 C36 H36A 109.0 . . ? N8 C36 H36B 109.0 . . ? C34 C36 H36B 109.0 . . ? H36A C36 H36B 107.8 . . ? C27 C28 H28A 109.5 . . ? C27 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C27 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? N5 C29 C30 113.0(5) 1_645 . ? N5 C29 H29A 109.0 1_645 . ? C30 C29 H29A 109.0 . . ? N5 C29 H29B 109.0 1_645 . ? C30 C29 H29B 109.0 . . ? H29A C29 H29B 107.8 . . ? C35 C30 C31 118.9(6) . . ? C35 C30 C29 120.4(5) . . ? C31 C30 C29 120.7(5) . . ? C32 C31 C30 120.2(6) . . ? C32 C31 H31 119.9 . . ? C30 C31 H31 119.9 . . ? C33 C32 C31 120.4(6) . . ? C33 C32 H32 119.8 . . ? C31 C32 H32 119.8 . . ? C34 C33 C32 120.6(6) . . ? C34 C33 H33 119.7 . . ? C32 C33 H33 119.7 . . ? C33 C34 C35 119.2(5) . . ? C33 C34 C36 120.5(5) . . ? C35 C34 C36 120.2(5) . . ? C30 C35 C34 120.7(5) . . ? C30 C35 H35 119.7 . . ? C34 C35 H35 119.7 . . ? C10 N1 N2 105.5(4) . . ? C10 N1 Ni1 127.2(4) . . ? N2 N1 Ni1 125.4(4) . . ? C12 N2 N1 110.3(5) . . ? C12 N2 C1 127.4(5) . . ? N1 N2 C1 120.7(5) . . ? C15 N3 N4 109.7(6) . . ? C15 N3 C7 126.4(6) . . ? N4 N3 C7 120.8(5) . . ? C17 N4 N3 105.5(5) . . ? C17 N4 Ni2 124.2(4) . . ? N3 N4 Ni2 130.2(4) . . ? C20 N5 N6 111.3(4) . . ? C20 N5 C29 126.0(5) . 1_465 ? N6 N5 C29 122.0(4) . 1_465 ? C22 N6 N5 105.2(4) . . ? C22 N6 Ni1 126.0(4) . . ? N5 N6 Ni1 128.6(3) . . ? C27 N7 N8 105.6(5) . . ? C27 N7 Ni2 129.0(4) . . ? N8 N7 Ni2 125.4(4) . . ? C25 N8 N7 111.0(5) . . ? C25 N8 C36 125.7(6) . . ? N7 N8 C36 122.8(5) . . ? N1 Ni1 N6 95.52(18) . . ? N1 Ni1 Br2 104.66(14) . . ? N6 Ni1 Br2 118.22(13) . . ? N1 Ni1 Br1 119.09(14) . . ? N6 Ni1 Br1 100.89(14) . . ? Br2 Ni1 Br1 117.11(4) . . ? N4 Ni2 N7 105.0(2) . . ? N4 Ni2 Br3 104.66(16) . . ? N7 Ni2 Br3 122.85(15) . . ? N4 Ni2 Br4 113.64(16) . . ? N7 Ni2 Br4 97.42(14) . . ? Br3 Ni2 Br4 113.34(4) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N2 C1 C2 C8 -7.9(7) . . . . ? N2 C1 C2 C3 172.5(5) . . . . ? C8 C2 C3 C4 0.8(9) . . . . ? C1 C2 C3 C4 -179.7(6) . . . . ? C2 C3 C4 C5 -0.8(11) . . . . ? C3 C4 C5 C6 0.6(11) . . . . ? C4 C5 C6 C8 -0.4(10) . . . . ? C4 C5 C6 C7 177.5(6) . . . . ? C5 C6 C7 N3 157.6(6) . . . . ? C8 C6 C7 N3 -24.5(8) . . . . ? C3 C2 C8 C6 -0.7(8) . . . . ? C1 C2 C8 C6 179.8(5) . . . . ? C5 C6 C8 C2 0.4(9) . . . . ? C7 C6 C8 C2 -177.5(5) . . . . ? N1 C10 C11 C12 0.4(7) . . . . ? C9 C10 C11 C12 -180.0(6) . . . . ? C10 C11 C12 N2 0.6(7) . . . . ? C10 C11 C12 C13 -178.1(6) . . . . ? N3 C15 C16 C17 1.5(8) . . . . ? C14 C15 C16 C17 -178.1(7) . . . . ? C15 C16 C17 N4 -0.9(8) . . . . ? C15 C16 C17 C18 179.1(8) . . . . ? N5 C20 C21 C22 0.2(6) . . . . ? C19 C20 C21 C22 179.5(6) . . . . ? C20 C21 C22 N6 0.1(7) . . . . ? C20 C21 C22 C23 -179.1(6) . . . . ? N8 C25 C26 C27 -0.9(7) . . . . ? C24 C25 C26 C27 179.2(7) . . . . ? C25 C26 C27 N7 0.1(8) . . . . ? C25 C26 C27 C28 177.6(7) . . . . ? N5 C29 C30 C35 -119.1(6) 1_645 . . . ? N5 C29 C30 C31 58.8(7) 1_645 . . . ? C35 C30 C31 C32 0.0(9) . . . . ? C29 C30 C31 C32 -177.9(6) . . . . ? C30 C31 C32 C33 0.2(10) . . . . ? C31 C32 C33 C34 -1.3(10) . . . . ? C32 C33 C34 C35 2.1(10) . . . . ? C32 C33 C34 C36 -179.6(6) . . . . ? N8 C36 C34 C33 135.5(6) . . . . ? N8 C36 C34 C35 -46.2(8) . . . . ? C31 C30 C35 C34 0.9(8) . . . . ? C29 C30 C35 C34 178.8(5) . . . . ? C33 C34 C35 C30 -1.9(9) . . . . ? C36 C34 C35 C30 179.8(5) . . . . ? C11 C10 N1 N2 -1.2(6) . . . . ? C9 C10 N1 N2 179.2(5) . . . . ? C11 C10 N1 Ni1 -165.8(4) . . . . ? C9 C10 N1 Ni1 14.6(8) . . . . ? C11 C12 N2 N1 -1.3(7) . . . . ? C13 C12 N2 N1 177.5(5) . . . . ? C11 C12 N2 C1 -166.9(5) . . . . ? C13 C12 N2 C1 11.9(9) . . . . ? C10 N1 N2 C12 1.6(6) . . . . ? Ni1 N1 N2 C12 166.5(4) . . . . ? C10 N1 N2 C1 168.2(5) . . . . ? Ni1 N1 N2 C1 -26.8(7) . . . . ? C2 C1 N2 C12 90.0(7) . . . . ? C2 C1 N2 N1 -74.2(6) . . . . ? C16 C15 N3 N4 -1.6(8) . . . . ? C14 C15 N3 N4 178.0(6) . . . . ? C16 C15 N3 C7 -161.8(6) . . . . ? C14 C15 N3 C7 17.8(10) . . . . ? C6 C7 N3 C15 90.2(8) . . . . ? C6 C7 N3 N4 -68.0(7) . . . . ? C16 C17 N4 N3 -0.1(7) . . . . ? C18 C17 N4 N3 179.9(7) . . . . ? C16 C17 N4 Ni2 -177.0(4) . . . . ? C18 C17 N4 Ni2 3.0(10) . . . . ? C15 N3 N4 C17 1.0(7) . . . . ? C7 N3 N4 C17 162.5(6) . . . . ? C15 N3 N4 Ni2 177.7(4) . . . . ? C7 N3 N4 Ni2 -20.8(8) . . . . ? C21 C20 N5 N6 -0.4(6) . . . . ? C19 C20 N5 N6 -179.8(5) . . . . ? C21 C20 N5 C29 -171.3(5) . . . 1_465 ? C19 C20 N5 C29 9.4(9) . . . 1_465 ? C21 C22 N6 N5 -0.3(6) . . . . ? C23 C22 N6 N5 178.9(5) . . . . ? C21 C22 N6 Ni1 -176.2(4) . . . . ? C23 C22 N6 Ni1 3.0(8) . . . . ? C20 N5 N6 C22 0.5(6) . . . . ? C29 N5 N6 C22 171.7(5) 1_465 . . . ? C20 N5 N6 Ni1 176.2(4) . . . . ? C29 N5 N6 Ni1 -12.6(7) 1_465 . . . ? C26 C27 N7 N8 0.7(7) . . . . ? C28 C27 N7 N8 -176.9(6) . . . . ? C26 C27 N7 Ni2 -176.8(4) . . . . ? C28 C27 N7 Ni2 5.6(9) . . . . ? C26 C25 N8 N7 1.3(7) . . . . ? C24 C25 N8 N7 -178.7(6) . . . . ? C26 C25 N8 C36 172.9(5) . . . . ? C24 C25 N8 C36 -7.1(9) . . . . ? C27 N7 N8 C25 -1.3(6) . . . . ? Ni2 N7 N8 C25 176.3(4) . . . . ? C27 N7 N8 C36 -173.2(5) . . . . ? Ni2 N7 N8 C36 4.4(7) . . . . ? C34 C36 N8 C25 -74.8(7) . . . . ? C34 C36 N8 N7 95.9(6) . . . . ? C10 N1 Ni1 N6 48.1(5) . . . . ? N2 N1 Ni1 N6 -113.6(4) . . . . ? C10 N1 Ni1 Br2 -73.0(5) . . . . ? N2 N1 Ni1 Br2 125.3(4) . . . . ? C10 N1 Ni1 Br1 153.8(4) . . . . ? N2 N1 Ni1 Br1 -7.9(4) . . . . ? C22 N6 Ni1 N1 50.1(5) . . . . ? N5 N6 Ni1 N1 -124.7(4) . . . . ? C22 N6 Ni1 Br2 160.0(4) . . . . ? N5 N6 Ni1 Br2 -14.8(5) . . . . ? C22 N6 Ni1 Br1 -70.9(5) . . . . ? N5 N6 Ni1 Br1 114.2(4) . . . . ? C17 N4 Ni2 N7 158.1(5) . . . . ? N3 N4 Ni2 N7 -18.0(6) . . . . ? C17 N4 Ni2 Br3 -71.3(5) . . . . ? N3 N4 Ni2 Br3 112.5(5) . . . . ? C17 N4 Ni2 Br4 52.9(6) . . . . ? N3 N4 Ni2 Br4 -123.3(5) . . . . ? C27 N7 Ni2 N4 -62.9(5) . . . . ? N8 N7 Ni2 N4 120.1(4) . . . . ? C27 N7 Ni2 Br3 178.1(4) . . . . ? N8 N7 Ni2 Br3 1.1(5) . . . . ? C27 N7 Ni2 Br4 54.1(5) . . . . ? N8 N7 Ni2 Br4 -122.9(4) . . . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 28.45 _diffrn_measured_fraction_theta_full 0.983 _refine_diff_density_max 0.848 _refine_diff_density_min -0.671 _refine_diff_density_rms 0.115 _database_code_depnum_ccdc_archive 'CCDC 942280'