Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _publ_section_title ;Tetrahedral Nickel Nitrosyl Complexes with Tripodal [N3] and [Se3] Donor Ancillary Ligands: Structural and Computational Evidence that a Linear Nitrosyl is a Trivalent Ligand ; _publ_contact_author_name 'Prof. G.Parkin' _publ_contact_author_email PARKIN@COLUMBIA.EDU loop_ _publ_author_name 'G. Parkin' 'Victoria K. Landry' 'Keliang Pang.' 'Stephanie M. Quan' # Attachment 'TPNIS10_1.CIF' data_tpnis10 _database_code_depnum_ccdc_archive 'CCDC 627371' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C15 H22 B N7 Ni O' _chemical_formula_weight 385.92 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' B B 0.0013 0.0007 '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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pmc2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x, -y, z+1/2' '-x, y, z' _cell_length_a 13.1151(8) _cell_length_b 8.0075(5) _cell_length_c 17.4989(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1837.7(2) _cell_formula_units_Z 4 _cell_measurement_temperature 243(2) _cell_measurement_reflns_used 3977 _cell_measurement_theta_min 2.54 _cell_measurement_theta_max 25.69 _exptl_crystal_description Block _exptl_crystal_colour Blue _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.395 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 808 _exptl_absorpt_coefficient_mu 1.074 _exptl_absorpt_correction_type EMPIRICAL _exptl_absorpt_correction_T_min 0.9002 _exptl_absorpt_correction_T_max 0.9002 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 243(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12505 _diffrn_reflns_av_R_equivalents 0.0422 _diffrn_reflns_av_sigmaI/netI 0.0506 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.55 _diffrn_reflns_theta_max 28.30 _reflns_number_total 3957 _reflns_number_gt 2946 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0413P)^2^+1.2391P] 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 0.48(2) _refine_ls_number_reflns 3957 _refine_ls_number_parameters 266 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0703 _refine_ls_R_factor_gt 0.0371 _refine_ls_wR_factor_ref 0.0959 _refine_ls_wR_factor_gt 0.0821 _refine_ls_goodness_of_fit_ref 1.005 _refine_ls_restrained_S_all 1.005 _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 Ni1 Ni 0.5000 0.34336(9) 0.18993(3) 0.0286(2) Uani 1 2 d S . . Ni2 Ni 0.0000 0.85349(9) 0.21710(4) 0.0298(2) Uani 1 2 d S . . N1 N 0.5000 0.2740(7) 0.1030(3) 0.0378(12) Uani 1 2 d S . . N2 N 0.0000 0.8967(7) 0.3074(3) 0.0431(14) Uani 1 2 d S . . O1 O 0.5000 0.2202(8) 0.0409(3) 0.0795(19) Uani 1 2 d S . . O2 O 0.0000 0.9159(10) 0.3730(4) 0.110(3) Uani 1 2 d S . . B1 B 0.5000 0.4603(9) 0.3563(4) 0.0330(16) Uani 1 2 d S . . H1 H 0.5000 0.501(6) 0.411(3) 0.013(13) Uiso 1 2 d S . . B2 B 0.0000 0.7493(9) 0.0485(5) 0.0311(18) Uani 1 2 d S . . H2 H 0.0000 0.710(6) -0.015(3) 0.015(14) Uiso 1 2 d S . . N11 N 0.5000 0.1947(6) 0.2821(3) 0.0328(12) Uani 1 2 d S . . N12 N 0.5000 0.2682(7) 0.3516(3) 0.0333(13) Uani 1 2 d S . . N21 N 0.3941(2) 0.4856(4) 0.23748(18) 0.0291(7) Uani 1 1 d . . . N22 N 0.4036(2) 0.5239(4) 0.31359(18) 0.0294(7) Uani 1 1 d . . . N31 N 0.0000 0.6168(5) 0.1797(3) 0.0316(10) Uani 1 2 d S . . N32 N 0.0000 0.5922(6) 0.1028(3) 0.0291(11) Uani 1 2 d S . . N41 N 0.1069(2) 0.9158(4) 0.1405(2) 0.0317(7) Uani 1 1 d . . . N42 N 0.0958(2) 0.8536(4) 0.06812(19) 0.0337(7) Uani 1 1 d . . . C14 C 0.5000 -0.0920(8) 0.2294(5) 0.052(2) Uani 1 2 d S . . H14A H 0.5000 -0.0320 0.1812 0.078 Uiso 1 2 calc SR . . H14B H 0.4396 -0.1616 0.2325 0.078 Uiso 0.50 1 calc PR . . H14C H 0.5604 -0.1616 0.2325 0.078 Uiso 0.50 1 calc PR . . C11 C 0.5000 0.0279(8) 0.2929(4) 0.0404(17) Uani 1 2 d S . . C12 C 0.5000 0.0003(8) 0.3721(4) 0.0463(17) Uani 1 2 d S . . H12A H 0.5000 -0.1043 0.3964 0.056 Uiso 1 2 calc SR . . C13 C 0.5000 0.1488(8) 0.4067(4) 0.0394(16) Uani 1 2 d S . . C15 C 0.5000 0.1947(10) 0.4908(4) 0.055(2) Uani 1 2 d S . . H15A H 0.5000 0.0937 0.5214 0.083 Uiso 1 2 calc SR . . H15B H 0.4396 0.2599 0.5024 0.083 Uiso 0.50 1 calc PR . . H15C H 0.5604 0.2599 0.5024 0.083 Uiso 0.50 1 calc PR . . C24 C 0.2716(3) 0.5330(6) 0.1328(3) 0.0465(12) Uani 1 1 d . . . H24A H 0.3231 0.4724 0.1044 0.070 Uiso 1 1 calc R . . H24B H 0.2624 0.6428 0.1105 0.070 Uiso 1 1 calc R . . H24C H 0.2076 0.4722 0.1308 0.070 Uiso 1 1 calc R . . C21 C 0.3047(3) 0.5507(4) 0.2140(3) 0.0326(9) Uani 1 1 d . . . C22 C 0.2570(3) 0.6269(5) 0.2756(3) 0.0408(11) Uani 1 1 d . . . H22A H 0.1936 0.6814 0.2750 0.049 Uiso 1 1 calc R . . C23 C 0.3197(3) 0.6076(5) 0.3373(3) 0.0343(9) Uani 1 1 d . . . C25 C 0.3043(4) 0.6618(7) 0.4185(3) 0.0549(13) Uani 1 1 d . . . H25A H 0.3631 0.6296 0.4488 0.082 Uiso 1 1 calc R . . H25B H 0.2437 0.6087 0.4390 0.082 Uiso 1 1 calc R . . H25C H 0.2962 0.7821 0.4203 0.082 Uiso 1 1 calc R . . C34 C 0.0000 0.4461(9) 0.2970(4) 0.0495(18) Uani 1 2 d S . . H34A H 0.0000 0.5554 0.3209 0.074 Uiso 1 2 calc SR . . H34B H 0.0604 0.3851 0.3127 0.074 Uiso 0.50 1 calc PR . . H34C H -0.0604 0.3851 0.3127 0.074 Uiso 0.50 1 calc PR . . C31 C 0.0000 0.4657(7) 0.2115(4) 0.0392(15) Uani 1 2 d S . . C32 C 0.0000 0.3446(8) 0.1560(4) 0.0422(18) Uani 1 2 d S . . H32A H 0.0000 0.2285 0.1638 0.051 Uiso 1 2 calc SR . . C33 C 0.0000 0.4260(8) 0.0864(4) 0.0351(14) Uani 1 2 d S . . C35 C 0.0000 0.3570(9) 0.0092(4) 0.0545(19) Uani 1 2 d S . . H35A H 0.0000 0.4475 -0.0277 0.082 Uiso 1 2 calc SR . . H35B H -0.0604 0.2889 0.0020 0.082 Uiso 0.50 1 calc PR . . H35C H 0.0604 0.2889 0.0020 0.082 Uiso 0.50 1 calc PR . . C44 C 0.2283(3) 1.0853(6) 0.2154(3) 0.0511(13) Uani 1 1 d . . . H44A H 0.1786 1.0655 0.2554 0.077 Uiso 1 1 calc R . . H44B H 0.2344 1.2044 0.2064 0.077 Uiso 1 1 calc R . . H44C H 0.2939 1.0408 0.2309 0.077 Uiso 1 1 calc R . . C41 C 0.1941(3) 1.0004(5) 0.1432(3) 0.0383(10) Uani 1 1 d . . . C42 C 0.2395(3) 0.9938(6) 0.0722(3) 0.0471(11) Uani 1 1 d . . . H42A H 0.3013 1.0447 0.0581 0.057 Uiso 1 1 calc R . . C43 C 0.1778(3) 0.8992(5) 0.0257(3) 0.0394(10) Uani 1 1 d . . . C45 C 0.1922(4) 0.8449(7) -0.0555(3) 0.0574(13) Uani 1 1 d . . . H45C H 0.1341 0.7787 -0.0715 0.086 Uiso 1 1 calc R . . H45D H 0.2538 0.7783 -0.0595 0.086 Uiso 1 1 calc R . . H45A H 0.1982 0.9425 -0.0880 0.086 Uiso 1 1 calc R . . 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 Ni1 0.0278(4) 0.0260(4) 0.0321(5) -0.0011(4) 0.000 0.000 Ni2 0.0262(4) 0.0273(4) 0.0359(5) 0.0002(4) 0.000 0.000 N1 0.036(3) 0.033(3) 0.044(4) -0.003(3) 0.000 0.000 N2 0.052(3) 0.037(3) 0.040(4) 0.004(3) 0.000 0.000 O1 0.102(5) 0.088(5) 0.048(4) -0.024(3) 0.000 0.000 O2 0.171(8) 0.118(6) 0.042(4) -0.018(4) 0.000 0.000 B1 0.029(3) 0.036(4) 0.034(4) -0.012(3) 0.000 0.000 B2 0.027(4) 0.030(4) 0.036(5) 0.009(4) 0.000 0.000 N11 0.032(2) 0.023(3) 0.044(3) 0.004(2) 0.000 0.000 N12 0.034(3) 0.036(3) 0.030(3) 0.006(3) 0.000 0.000 N21 0.0261(16) 0.0254(16) 0.036(2) 0.0031(14) -0.0013(13) 0.0028(13) N22 0.0260(16) 0.0271(17) 0.035(2) -0.0012(14) -0.0002(13) 0.0000(13) N31 0.032(2) 0.027(2) 0.036(3) 0.003(2) 0.000 0.000 N32 0.029(3) 0.025(3) 0.033(3) 0.002(2) 0.000 0.000 N41 0.0266(17) 0.0287(17) 0.040(2) 0.0004(16) 0.0011(15) -0.0043(14) N42 0.0274(16) 0.0350(18) 0.0387(19) 0.0042(17) 0.0026(13) -0.0010(15) C14 0.069(5) 0.021(3) 0.066(6) -0.006(4) 0.000 0.000 C11 0.027(3) 0.027(3) 0.068(5) 0.008(4) 0.000 0.000 C12 0.048(4) 0.031(4) 0.060(5) 0.022(3) 0.000 0.000 C13 0.033(3) 0.039(4) 0.046(4) 0.015(3) 0.000 0.000 C15 0.062(5) 0.062(5) 0.042(4) 0.016(4) 0.000 0.000 C24 0.037(2) 0.045(3) 0.057(3) 0.003(2) -0.010(2) 0.007(2) C21 0.0264(18) 0.0254(19) 0.046(2) 0.003(2) -0.0031(19) -0.0006(15) C22 0.0241(19) 0.036(2) 0.062(3) -0.002(2) 0.0042(19) 0.0082(18) C23 0.0257(19) 0.030(2) 0.047(3) -0.0028(18) 0.0091(17) 0.0006(16) C25 0.041(3) 0.066(4) 0.057(3) -0.018(3) 0.015(2) 0.007(3) C34 0.051(4) 0.042(4) 0.056(5) 0.015(4) 0.000 0.000 C31 0.035(3) 0.031(3) 0.051(4) 0.008(3) 0.000 0.000 C32 0.028(3) 0.027(3) 0.072(5) 0.003(3) 0.000 0.000 C33 0.029(3) 0.026(3) 0.050(4) -0.007(3) 0.000 0.000 C35 0.059(4) 0.045(4) 0.060(5) -0.018(4) 0.000 0.000 C44 0.041(3) 0.042(2) 0.070(4) -0.002(3) -0.014(3) -0.008(2) C41 0.030(2) 0.028(2) 0.057(3) 0.006(2) 0.000(2) 0.0010(18) C42 0.030(2) 0.044(3) 0.067(3) 0.011(2) 0.003(2) -0.007(2) C43 0.033(2) 0.038(2) 0.047(3) 0.015(2) 0.0066(19) 0.0030(19) C45 0.051(3) 0.071(4) 0.051(3) 0.003(3) 0.015(2) -0.005(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 Ni1 N1 1.619(6) . ? Ni1 N21 1.980(3) 4_655 ? Ni1 N21 1.980(3) . ? Ni1 N11 2.004(5) . ? Ni2 N2 1.617(6) . ? Ni2 N41 2.003(3) 4 ? Ni2 N41 2.003(3) . ? Ni2 N31 2.006(4) . ? N1 O1 1.170(7) . ? N2 O2 1.158(7) . ? B1 N12 1.541(9) . ? B1 N22 1.555(5) . ? B1 N22 1.555(5) 4_655 ? B2 N42 1.547(6) . ? B2 N42 1.547(6) 4 ? B2 N32 1.576(9) . ? N11 C11 1.349(7) . ? N11 N12 1.351(7) . ? N12 C13 1.359(8) . ? N21 C21 1.348(5) . ? N21 N22 1.372(4) . ? N22 C23 1.353(5) . ? N31 C31 1.331(7) . ? N31 N32 1.360(7) . ? N32 C33 1.362(7) . ? N41 C41 1.330(5) . ? N41 N42 1.370(5) . ? N42 C43 1.356(5) . ? C14 C11 1.469(10) . ? C11 C12 1.403(9) . ? C12 C13 1.335(10) . ? C13 C15 1.517(10) . ? C24 C21 1.491(6) . ? C21 C22 1.388(6) . ? C22 C23 1.366(6) . ? C23 C25 1.500(6) . ? C34 C31 1.505(9) . ? C31 C32 1.373(9) . ? C32 C33 1.381(9) . ? C33 C35 1.460(9) . ? C44 C41 1.502(6) . ? C41 C42 1.379(6) . ? C42 C43 1.374(6) . ? C43 C45 1.498(6) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Ni1 N21 126.32(14) . 4_655 ? N1 Ni1 N21 126.32(14) . . ? N21 Ni1 N21 89.11(18) 4_655 . ? N1 Ni1 N11 123.5(2) . . ? N21 Ni1 N11 90.21(14) 4_655 . ? N21 Ni1 N11 90.21(14) . . ? N2 Ni2 N41 126.88(14) . 4 ? N2 Ni2 N41 126.88(14) . . ? N41 Ni2 N41 88.90(19) 4 . ? N2 Ni2 N31 121.4(3) . . ? N41 Ni2 N31 90.99(14) 4 . ? N41 Ni2 N31 90.99(14) . . ? O1 N1 Ni1 178.5(6) . . ? O2 N2 Ni2 175.3(7) . . ? N12 B1 N22 107.5(3) . . ? N12 B1 N22 107.5(3) . 4_655 ? N22 B1 N22 108.8(5) . 4_655 ? N42 B2 N42 108.6(5) . 4 ? N42 B2 N32 107.3(4) . . ? N42 B2 N32 107.3(4) 4 . ? C11 N11 N12 107.7(5) . . ? C11 N11 Ni1 134.5(5) . . ? N12 N11 Ni1 117.8(4) . . ? N11 N12 C13 109.5(6) . . ? N11 N12 B1 118.9(5) . . ? C13 N12 B1 131.6(6) . . ? C21 N21 N22 106.8(3) . . ? C21 N21 Ni1 134.8(3) . . ? N22 N21 Ni1 118.2(2) . . ? C23 N22 N21 109.5(3) . . ? C23 N22 B1 132.5(4) . . ? N21 N22 B1 117.9(3) . . ? C31 N31 N32 106.4(5) . . ? C31 N31 Ni2 136.2(5) . . ? N32 N31 Ni2 117.4(4) . . ? N31 N32 C33 110.4(5) . . ? N31 N32 B2 118.7(5) . . ? C33 N32 B2 130.8(6) . . ? C41 N41 N42 108.0(3) . . ? C41 N41 Ni2 134.9(3) . . ? N42 N41 Ni2 117.0(2) . . ? C43 N42 N41 108.9(3) . . ? C43 N42 B2 131.9(4) . . ? N41 N42 B2 119.2(4) . . ? N11 C11 C12 107.1(6) . . ? N11 C11 C14 122.7(7) . . ? C12 C11 C14 130.1(6) . . ? C13 C12 C11 108.0(6) . . ? C12 C13 N12 107.7(6) . . ? C12 C13 C15 131.1(6) . . ? N12 C13 C15 121.2(6) . . ? N21 C21 C22 108.9(4) . . ? N21 C21 C24 120.5(4) . . ? C22 C21 C24 130.6(4) . . ? C23 C22 C21 107.1(3) . . ? N22 C23 C22 107.6(4) . . ? N22 C23 C25 122.9(4) . . ? C22 C23 C25 129.4(4) . . ? N31 C31 C32 110.2(6) . . ? N31 C31 C34 120.7(6) . . ? C32 C31 C34 129.1(6) . . ? C31 C32 C33 106.9(6) . . ? N32 C33 C32 106.0(6) . . ? N32 C33 C35 124.4(6) . . ? C32 C33 C35 129.6(6) . . ? N41 C41 C42 108.6(4) . . ? N41 C41 C44 121.1(4) . . ? C42 C41 C44 130.3(4) . . ? C43 C42 C41 107.5(4) . . ? N42 C43 C42 107.0(4) . . ? N42 C43 C45 122.7(4) . . ? C42 C43 C45 130.3(4) . . ? _diffrn_measured_fraction_theta_max 0.968 _diffrn_reflns_theta_full 28.30 _diffrn_measured_fraction_theta_full 0.968 _refine_diff_density_max 0.309 _refine_diff_density_min -0.331 _refine_diff_density_rms 0.065 # Attachment 'NIPS10_1.CIF' data_nips10 _database_code_depnum_ccdc_archive 'CCDC 627372' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C45 H47.50 B N7 Ni O P0.50 Se3' _chemical_formula_weight 1024.29 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' B B 0.0013 0.0007 '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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Rhombohedral _symmetry_space_group_name_H-M R-3c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, -z+1/2' 'x-y, -y, -z+1/2' '-x, -x+y, -z+1/2' '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' 'y+2/3, x+1/3, -z+5/6' 'x-y+2/3, -y+1/3, -z+5/6' '-x+2/3, -x+y+1/3, -z+5/6' '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' 'y+1/3, x+2/3, -z+7/6' 'x-y+1/3, -y+2/3, -z+7/6' '-x+1/3, -x+y+2/3, -z+7/6' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-y, -x, z-1/2' '-x+y, y, z-1/2' 'x, x-y, z-1/2' '-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' '-y+2/3, -x+1/3, z-1/6' '-x+y+2/3, y+1/3, z-1/6' 'x+2/3, x-y+1/3, z-1/6' '-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' '-y+1/3, -x+2/3, z+1/6' '-x+y+1/3, y+2/3, z+1/6' 'x+1/3, x-y+2/3, z+1/6' _cell_length_a 14.5179(5) _cell_length_b 14.5179(5) _cell_length_c 73.730(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 13458.0(12) _cell_formula_units_Z 12 _cell_measurement_temperature 243(2) _cell_measurement_reflns_used 9289 _cell_measurement_theta_min 2.74 _cell_measurement_theta_max 27.06 _exptl_crystal_description BLOCK _exptl_crystal_colour BLUE _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.517 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 6204 _exptl_absorpt_coefficient_mu 2.927 _exptl_absorpt_correction_type EMPIRICAL _exptl_absorpt_correction_T_min 0.7584 _exptl_absorpt_correction_T_max 0.7584 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 243(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 24431 _diffrn_reflns_av_R_equivalents 0.0712 _diffrn_reflns_av_sigmaI/netI 0.0523 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -96 _diffrn_reflns_limit_l_max 73 _diffrn_reflns_theta_min 1.71 _diffrn_reflns_theta_max 28.31 _reflns_number_total 3489 _reflns_number_gt 2347 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0200P)^2^+0.0000P] 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 3489 _refine_ls_number_parameters 197 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0583 _refine_ls_R_factor_gt 0.0315 _refine_ls_wR_factor_ref 0.0648 _refine_ls_wR_factor_gt 0.0609 _refine_ls_goodness_of_fit_ref 1.083 _refine_ls_restrained_S_all 1.083 _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 Ni Ni 0.3333 0.6667 0.015150(7) 0.03909(15) Uani 1 3 d S . . Se Se 0.50894(2) 0.77442(2) 0.028974(3) 0.04031(9) Uani 1 1 d . . . N1 N 0.3333 0.6667 -0.00700(5) 0.0466(10) Uani 1 3 d S . . O1 O 0.3333 0.6667 -0.02268(5) 0.1104(18) Uani 1 3 d S . . B B 0.3333 0.6667 0.06752(6) 0.0319(10) Uani 1 3 d S . . H1 H 0.3333 0.6667 0.0852(5) 0.048 Uiso 1 3 d S . . N11 N 0.42659(15) 0.64967(15) 0.06200(2) 0.0309(4) Uani 1 1 d . . . N12 N 0.56767(15) 0.65190(15) 0.05121(2) 0.0344(4) Uani 1 1 d . . . C11 C 0.49875(18) 0.68774(18) 0.04842(3) 0.0325(5) Uani 1 1 d . . . C12 C 0.4500(2) 0.58632(19) 0.07299(3) 0.0383(6) Uani 1 1 d . . . H12A H 0.4115 0.5490 0.0833 0.046 Uiso 1 1 calc R . . C13 C 0.5363(2) 0.5872(2) 0.06643(3) 0.0403(6) Uani 1 1 d . . . H13A H 0.5693 0.5509 0.0712 0.048 Uiso 1 1 calc R . . C21 C 0.66094(18) 0.67509(19) 0.04079(3) 0.0355(6) Uani 1 1 d . . . C22 C 0.6547(2) 0.5980(2) 0.02879(3) 0.0411(6) Uani 1 1 d . . . C23 C 0.7481(2) 0.6188(2) 0.02010(3) 0.0462(6) Uani 1 1 d . . . H23A H 0.7462 0.5678 0.0120 0.055 Uiso 1 1 calc R . . C24 C 0.8431(2) 0.7112(3) 0.02282(4) 0.0505(7) Uani 1 1 d . . . C25 C 0.8453(2) 0.7866(2) 0.03467(3) 0.0463(7) Uani 1 1 d . . . H25A H 0.9096 0.8504 0.0365 0.056 Uiso 1 1 calc R . . C26 C 0.7537(2) 0.7696(2) 0.04390(3) 0.0384(6) Uani 1 1 d . . . C27 C 0.5520(2) 0.4979(2) 0.02521(4) 0.0614(8) Uani 1 1 d . . . H27A H 0.4960 0.5149 0.0233 0.092 Uiso 1 1 calc R . . H27B H 0.5343 0.4505 0.0355 0.092 Uiso 1 1 calc R . . H27C H 0.5592 0.4635 0.0145 0.092 Uiso 1 1 calc R . . C28 C 0.9430(2) 0.7305(3) 0.01303(4) 0.0766(10) Uani 1 1 d . . . H28A H 0.9934 0.8062 0.0126 0.115 Uiso 1 1 calc R . . H28B H 0.9251 0.7028 0.0008 0.115 Uiso 1 1 calc R . . H28C H 0.9746 0.6947 0.0195 0.115 Uiso 1 1 calc R . . C29 C 0.7575(2) 0.8534(2) 0.05642(4) 0.0520(7) Uani 1 1 d . . . H29A H 0.7266 0.8214 0.0680 0.078 Uiso 1 1 calc R . . H29B H 0.7177 0.8839 0.0511 0.078 Uiso 1 1 calc R . . H29C H 0.8309 0.9088 0.0582 0.078 Uiso 1 1 calc R . . P1 P 0.3333 0.6667 -0.06627(3) 0.0436(6) Uani 0.50 3 d SP . . C31 C 0.2174(3) 0.5574(3) -0.07704(6) 0.0408(14) Uani 0.50 1 d PG A -1 C32 C 0.1681(4) 0.4662(4) -0.06642(7) 0.053(2) Uani 0.50 1 d PG A -1 H32A H 0.1960 0.4652 -0.0550 0.063 Uiso 0.50 1 calc PR A -1 C33 C 0.0773(6) 0.3765(4) -0.07271(12) 0.064(3) Uani 0.50 1 d PG A -1 H33A H 0.0439 0.3148 -0.0655 0.077 Uiso 0.50 1 calc PR A -1 C34 C 0.0359(6) 0.3779(5) -0.08964(12) 0.083(6) Uani 0.50 1 d PG A -1 H34A H -0.0255 0.3172 -0.0939 0.099 Uiso 0.50 1 calc PR A -1 C35 C 0.0853(4) 0.4691(5) -0.10027(8) 0.059(3) Uani 0.50 1 d PG A -1 H35A H 0.0573 0.4701 -0.1117 0.071 Uiso 0.50 1 calc PR A -1 C36 C 0.1760(3) 0.5589(4) -0.09397(6) 0.0492(15) Uani 0.50 1 d PG A -1 H36A H 0.2094 0.6205 -0.1012 0.059 Uiso 0.50 1 calc PR A -1 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 Ni 0.0390(2) 0.0390(2) 0.0392(3) 0.000 0.000 0.01952(11) Se 0.03313(16) 0.04218(16) 0.04471(15) 0.01332(11) 0.00392(10) 0.01814(13) N1 0.0474(16) 0.0474(16) 0.045(2) 0.000 0.000 0.0237(8) O1 0.141(3) 0.141(3) 0.049(2) 0.000 0.000 0.0705(15) B 0.0294(16) 0.0294(16) 0.037(3) 0.000 0.000 0.0147(8) N11 0.0286(11) 0.0286(11) 0.0353(10) 0.0043(8) 0.0029(8) 0.0142(9) N12 0.0315(11) 0.0337(11) 0.0419(11) 0.0045(8) 0.0042(8) 0.0193(10) C11 0.0281(13) 0.0281(13) 0.0404(13) 0.0010(10) -0.0015(10) 0.0136(11) C12 0.0436(15) 0.0362(15) 0.0419(14) 0.0112(10) 0.0080(11) 0.0250(12) C13 0.0459(16) 0.0402(15) 0.0450(14) 0.0114(11) 0.0049(11) 0.0292(13) C21 0.0335(14) 0.0420(15) 0.0378(14) 0.0056(10) 0.0044(9) 0.0239(12) C22 0.0438(16) 0.0458(16) 0.0423(14) 0.0012(11) 0.0018(11) 0.0291(14) C23 0.0507(18) 0.0599(19) 0.0419(15) 0.0017(12) 0.0034(12) 0.0380(16) C24 0.0449(17) 0.074(2) 0.0463(16) 0.0134(14) 0.0099(12) 0.0398(17) C25 0.0320(15) 0.0508(18) 0.0538(16) 0.0078(12) -0.0001(11) 0.0191(13) C26 0.0373(15) 0.0418(15) 0.0406(14) 0.0046(10) 0.0005(10) 0.0231(13) C27 0.052(2) 0.056(2) 0.073(2) -0.0158(15) 0.0013(14) 0.0251(17) C28 0.054(2) 0.112(3) 0.073(2) 0.0113(19) 0.0241(15) 0.048(2) C29 0.0444(18) 0.0453(17) 0.0624(18) -0.0037(13) -0.0018(13) 0.0196(15) P1 0.0478(10) 0.0478(10) 0.0353(12) 0.000 0.000 0.0239(5) C31 0.035(3) 0.040(4) 0.051(4) 0.005(3) 0.006(2) 0.022(3) C32 0.046(5) 0.037(6) 0.073(5) 0.012(4) 0.023(4) 0.021(5) C33 0.035(7) 0.026(5) 0.128(7) 0.003(4) 0.023(6) 0.013(4) C34 0.042(6) 0.030(7) 0.180(16) -0.028(6) 0.004(7) 0.021(3) C35 0.029(6) 0.050(6) 0.094(6) -0.024(4) -0.016(4) 0.017(5) C36 0.040(4) 0.055(4) 0.055(4) -0.004(3) -0.004(3) 0.025(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 Ni N1 1.633(4) . ? Ni Se 2.4489(3) 2_665 ? Ni Se 2.4489(3) . ? Ni Se 2.4489(3) 3_565 ? Se C11 1.864(2) . ? N1 O1 1.156(5) . ? B N11 1.547(2) 2_665 ? B N11 1.547(2) 3_565 ? B N11 1.547(2) . ? N11 C11 1.351(3) . ? N11 C12 1.389(3) . ? N12 C11 1.355(3) . ? N12 C13 1.386(3) . ? N12 C21 1.443(3) . ? C12 C13 1.338(3) . ? C21 C26 1.378(3) . ? C21 C22 1.393(3) . ? C22 C23 1.389(3) . ? C22 C27 1.496(4) . ? C23 C24 1.376(4) . ? C24 C25 1.389(4) . ? C24 C28 1.516(4) . ? C25 C26 1.402(3) . ? C26 C29 1.506(3) . ? P1 C31 1.819(4) 3_565 ? P1 C31 1.819(4) . ? P1 C31 1.819(4) 2_665 ? P1 C36 2.077(16) 11_564 ? P1 C36 2.077(5) 10_454 ? P1 C36 2.077(6) 12_554 ? P1 P1 2.516(4) 10_454 ? C31 C32 1.3900 . ? C31 C36 1.3900 . ? C32 C33 1.3900 . ? C33 C34 1.3900 . ? C34 C35 1.3900 . ? C35 C36 1.3900 . ? C36 P1 2.077(5) 10_454 ? 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 Ni Se 114.594(12) . 2_665 ? N1 Ni Se 114.594(12) . . ? Se Ni Se 103.897(14) 2_665 . ? N1 Ni Se 114.594(12) . 3_565 ? Se Ni Se 103.897(14) 2_665 3_565 ? Se Ni Se 103.897(14) . 3_565 ? C11 Se Ni 100.55(7) . . ? O1 N1 Ni 180.0 . . ? N11 B N11 113.33(14) 2_665 3_565 ? N11 B N11 113.33(14) 2_665 . ? N11 B N11 113.33(14) 3_565 . ? C11 N11 C12 107.87(19) . . ? C11 N11 B 133.7(2) . . ? C12 N11 B 118.3(2) . . ? C11 N12 C13 109.12(18) . . ? C11 N12 C21 128.09(18) . . ? C13 N12 C21 122.78(19) . . ? N11 C11 N12 107.52(18) . . ? N11 C11 Se 129.00(17) . . ? N12 C11 Se 123.47(16) . . ? C13 C12 N11 108.7(2) . . ? C12 C13 N12 106.7(2) . . ? C26 C21 C22 122.9(2) . . ? C26 C21 N12 118.7(2) . . ? C22 C21 N12 118.3(2) . . ? C23 C22 C21 117.0(2) . . ? C23 C22 C27 121.3(2) . . ? C21 C22 C27 121.7(2) . . ? C24 C23 C22 122.6(3) . . ? C23 C24 C25 118.5(2) . . ? C23 C24 C28 120.8(3) . . ? C25 C24 C28 120.8(3) . . ? C24 C25 C26 121.4(3) . . ? C21 C26 C25 117.6(2) . . ? C21 C26 C29 121.9(2) . . ? C25 C26 C29 120.4(2) . . ? C31 P1 C31 102.36(17) 3_565 . ? C31 P1 C31 102.36(17) 3_565 2_665 ? C31 P1 C31 102.36(17) . 2_665 ? C31 P1 C36 23.3(3) 3_565 11_564 ? C31 P1 C36 92.3(4) . 11_564 ? C31 P1 C36 125.4(3) 2_665 11_564 ? C31 P1 C36 125.4(2) 3_565 10_454 ? C31 P1 C36 23.3(2) . 10_454 ? C31 P1 C36 92.3(3) 2_665 10_454 ? C36 P1 C36 115.0(2) 11_564 10_454 ? C31 P1 C36 92.3(7) 3_565 12_554 ? C31 P1 C36 125.4(4) . 12_554 ? C31 P1 C36 23.3(4) 2_665 12_554 ? C36 P1 C36 115.0(4) 11_564 12_554 ? C36 P1 C36 115.0(4) 10_454 12_554 ? C31 P1 P1 64.11(14) 3_565 10_454 ? C31 P1 P1 64.12(14) . 10_454 ? C31 P1 P1 64.12(14) 2_665 10_454 ? C36 P1 P1 76.8(3) 11_564 10_454 ? C36 P1 P1 76.83(14) 10_454 10_454 ? C36 P1 P1 76.8(3) 12_554 10_454 ? C32 C31 C36 120.0 . . ? C32 C31 P1 113.3(2) . . ? C36 C31 P1 126.7(2) . . ? C31 C32 C33 120.0 . . ? C34 C33 C32 120.0 . . ? C33 C34 C35 120.0 . . ? C36 C35 C34 120.0 . . ? C35 C36 C31 120.0 . . ? C35 C36 P1 143.1(3) . 10_454 ? C31 C36 P1 83.99(18) . 10_454 ? _diffrn_measured_fraction_theta_max 0.932 _diffrn_reflns_theta_full 28.31 _diffrn_measured_fraction_theta_full 0.932 _refine_diff_density_max 0.694 _refine_diff_density_min -0.330 _refine_diff_density_rms 0.067