# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 ####################################################################### # # 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_BNi8a _database_code_depnum_ccdc_archive 'CCDC 867595' #TrackingRef '- CIF-1.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C9 H24 Cl N5 Ni O5' _chemical_formula_weight 376.49 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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 16.315(5) _cell_length_b 6.425(5) _cell_length_c 8.559(5) _cell_angle_alpha 90.00 _cell_angle_beta 118.238(5) _cell_angle_gamma 90.00 _cell_volume 790.4(8) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 132 _cell_measurement_theta_min 2.22 _cell_measurement_theta_max 26.45 _exptl_crystal_description parallelepiped _exptl_crystal_colour green _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.582 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 396 _exptl_absorpt_coefficient_mu 1.424 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.8707 _exptl_absorpt_correction_T_max 0.9322 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6708 _diffrn_reflns_av_R_equivalents 0.0362 _diffrn_reflns_av_sigmaI/netI 0.0317 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.83 _diffrn_reflns_theta_max 28.49 _reflns_number_total 1929 _reflns_number_gt 1883 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART (Bruker,2000)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker,2000)' _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Mercury 1.4.1' _computing_publication_material '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^ > 2\s(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.Soft restraints on anions geometry and displacement parameters were used with the help of DFIX, DELU, DANG and SIMU instructions of SHELXL-97. EADP constraint was applied on carbon and nitrogen atoms of cyanate to have reasonable displacement parameters. ; _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^)+(0.0880P)^2^+4.2672P] 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 noref _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 0.42(4) _refine_ls_number_reflns 1929 _refine_ls_number_parameters 119 _refine_ls_number_restraints 26 _refine_ls_R_factor_all 0.0577 _refine_ls_R_factor_gt 0.0560 _refine_ls_wR_factor_ref 0.1577 _refine_ls_wR_factor_gt 0.1548 _refine_ls_goodness_of_fit_ref 1.117 _refine_ls_restrained_S_all 1.197 _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 1.0000 0.2223 0.5000 0.0148(2) Uani 1 2 d S . . O1 O 1.0229(8) -0.0961(19) 0.517(2) 0.0277(12) Uani 0.50 1 d P A -1 N3 N 0.9762(9) -0.453(2) 0.485(2) 0.0277(12) Uani 0.50 1 d P . -1 C1 C 1.1870(4) 0.214(3) 0.5403(9) 0.057(2) Uani 1 1 d . . . H1A H 1.2088 0.0726 0.5334 0.068 Uiso 1 1 calc R A . H1B H 1.2428 0.3047 0.5940 0.068 Uiso 1 1 calc R . . C2 C 1.1299(5) 0.2857(13) 0.3606(10) 0.0424(16) Uani 1 1 d . A . H2C H 1.1531 0.2232 0.2832 0.051 Uiso 1 1 calc R . . H2D H 1.1359 0.4387 0.3568 0.051 Uiso 1 1 calc R . . C3 C 1.1832(5) -0.0231(11) 0.7266(10) 0.0418(16) Uani 1 1 d D . . H3A H 1.1650 -0.0610 0.8168 0.063 Uiso 1 1 calc R A . H3B H 1.2511 -0.0314 0.7778 0.063 Uiso 1 1 calc R . . H3C H 1.1541 -0.1191 0.6261 0.063 Uiso 1 1 calc R . . C4 C 1.1896(5) 0.3223(12) 0.8254(9) 0.0432(17) Uani 1 1 d D . . H4A H 1.1526 0.2974 0.8864 0.065 Uiso 1 1 calc R A . H4B H 1.1889 0.4712 0.8000 0.065 Uiso 1 1 calc R . . H4C H 1.2538 0.2768 0.9012 0.065 Uiso 1 1 calc R . . C5 C 1.0000 -0.278(3) 0.5000 0.0195(10) Uani 1 2 d S . . N1 N 1.1502(3) 0.2063(14) 0.6609(5) 0.0346(11) Uani 1 1 d D A . N2 N 1.0298(3) 0.2311(16) 0.2902(5) 0.0294(10) Uani 1 1 d . A . H2A H 1.0179 0.1035 0.2350 0.035 Uiso 1 1 calc R . . H2B H 0.9931 0.3289 0.2085 0.035 Uiso 1 1 calc R . . Cl1 Cl 1.0000 -0.2785(9) 0.0000 0.0324(4) Uani 1 2 d SD . . O2 O 0.9403(10) -0.447(2) 0.000(2) 0.083(7) Uani 0.50 1 d PD B -1 O3 O 1.0697(7) -0.274(5) 0.1840(14) 0.134(11) Uani 0.50 1 d PD B -1 O4 O 1.0329(13) -0.303(3) -0.125(2) 0.094(6) Uani 0.50 1 d PD B -1 O5 O 0.9394(10) -0.0979(16) -0.031(3) 0.063(5) Uani 0.50 1 d PD B -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 Ni1 0.0190(4) 0.0117(3) 0.0139(3) 0.000 0.0079(2) 0.000 O1 0.030(3) 0.0100(17) 0.043(3) -0.0006(18) 0.017(3) 0.0009(13) N3 0.030(3) 0.0100(17) 0.043(3) -0.0006(18) 0.017(3) 0.0009(13) C1 0.024(3) 0.104(7) 0.044(3) 0.028(8) 0.019(2) 0.017(6) C2 0.039(3) 0.055(4) 0.041(3) -0.001(3) 0.027(3) -0.002(3) C3 0.028(3) 0.037(3) 0.047(4) 0.006(3) 0.007(3) 0.009(2) C4 0.031(3) 0.045(4) 0.039(4) -0.013(3) 0.004(3) 0.007(3) C5 0.021(2) 0.011(2) 0.024(2) 0.000 0.009(2) 0.000 N1 0.026(2) 0.056(3) 0.0211(18) -0.005(4) 0.0101(15) 0.006(3) N2 0.033(2) 0.034(3) 0.0266(18) -0.016(4) 0.0181(16) -0.005(4) Cl1 0.0352(8) 0.0343(8) 0.0227(7) 0.000 0.0097(6) 0.000 O2 0.053(9) 0.100(15) 0.090(12) 0.074(11) 0.028(8) 0.012(9) O3 0.031(5) 0.31(3) 0.041(6) -0.064(18) -0.002(5) 0.014(17) O4 0.170(16) 0.075(14) 0.087(9) 0.012(10) 0.101(11) -0.035(12) O5 0.050(8) 0.010(4) 0.119(15) 0.005(6) 0.031(8) 0.009(5) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 N2 2.072(4) 2_756 ? Ni1 N2 2.072(4) . ? Ni1 O1 2.072(13) 2_756 ? Ni1 O1 2.072(13) . ? Ni1 N3 2.117(16) 2_766 ? Ni1 N3 2.117(16) 1_565 ? Ni1 N1 2.173(5) 2_756 ? Ni1 N1 2.173(5) . ? O1 C5 1.22(2) . ? N3 C5 1.17(2) . ? N3 Ni1 2.117(16) 1_545 ? C1 N1 1.420(7) . ? C1 C2 1.444(10) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 N2 1.490(8) . ? C2 H2C 0.9900 . ? C2 H2D 0.9900 . ? C3 N1 1.578(9) . ? C3 H3A 0.9800 . ? C3 H3B 0.9800 . ? C3 H3C 0.9800 . ? C4 N1 1.447(7) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 N3 1.17(2) 2_756 ? C5 O1 1.22(2) 2_756 ? N2 H2A 0.9200 . ? N2 H2B 0.9200 . ? Cl1 O4 1.415(8) 2_755 ? Cl1 O4 1.415(8) . ? Cl1 O3 1.442(9) 2_755 ? Cl1 O3 1.442(9) . ? Cl1 O2 1.457(8) . ? Cl1 O2 1.457(8) 2_755 ? Cl1 O5 1.464(9) 2_755 ? Cl1 O5 1.464(9) . ? 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 Ni1 N2 176.9(6) 2_756 . ? N2 Ni1 O1 88.8(5) 2_756 2_756 ? N2 Ni1 O1 94.2(5) . 2_756 ? N2 Ni1 O1 94.2(5) 2_756 . ? N2 Ni1 O1 88.8(5) . . ? O1 Ni1 O1 18.4(6) 2_756 . ? N2 Ni1 N3 91.9(6) 2_756 2_766 ? N2 Ni1 N3 85.0(5) . 2_766 ? O1 Ni1 N3 179.2(8) 2_756 2_766 ? O1 Ni1 N3 161.4(2) . 2_766 ? N2 Ni1 N3 85.0(5) 2_756 1_565 ? N2 Ni1 N3 91.9(6) . 1_565 ? O1 Ni1 N3 161.4(2) 2_756 1_565 ? O1 Ni1 N3 179.2(8) . 1_565 ? N3 Ni1 N3 18.8(7) 2_766 1_565 ? N2 Ni1 N1 83.88(17) 2_756 2_756 ? N2 Ni1 N1 96.27(16) . 2_756 ? O1 Ni1 N1 78.3(4) 2_756 2_756 ? O1 Ni1 N1 96.3(4) . 2_756 ? N3 Ni1 N1 101.8(4) 2_766 2_756 ? N3 Ni1 N1 83.6(4) 1_565 2_756 ? N2 Ni1 N1 96.27(16) 2_756 . ? N2 Ni1 N1 83.88(17) . . ? O1 Ni1 N1 96.3(4) 2_756 . ? O1 Ni1 N1 78.3(4) . . ? N3 Ni1 N1 83.6(4) 2_766 . ? N3 Ni1 N1 101.8(4) 1_565 . ? N1 Ni1 N1 174.6(5) 2_756 . ? C5 O1 Ni1 155.0(8) . . ? C5 N3 Ni1 153.4(10) . 1_545 ? N1 C1 C2 120.3(6) . . ? N1 C1 H1A 107.2 . . ? C2 C1 H1A 107.2 . . ? N1 C1 H1B 107.2 . . ? C2 C1 H1B 107.2 . . ? H1A C1 H1B 106.9 . . ? C1 C2 N2 112.8(6) . . ? C1 C2 H2C 109.0 . . ? N2 C2 H2C 109.0 . . ? C1 C2 H2D 109.0 . . ? N2 C2 H2D 109.0 . . ? H2C C2 H2D 107.8 . . ? N1 C3 H3A 109.5 . . ? N1 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? N1 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? N1 C4 H4A 109.5 . . ? N1 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? N1 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? N3 C5 N3 34.4(14) . 2_756 ? N3 C5 O1 178.1(13) . . ? N3 C5 O1 147.1(4) 2_756 . ? N3 C5 O1 147.1(4) . 2_756 ? N3 C5 O1 178.1(13) 2_756 2_756 ? O1 C5 O1 31.6(12) . 2_756 ? C1 N1 C4 122.9(9) . . ? C1 N1 C3 95.9(8) . . ? C4 N1 C3 102.4(5) . . ? C1 N1 Ni1 106.0(3) . . ? C4 N1 Ni1 116.1(4) . . ? C3 N1 Ni1 111.2(5) . . ? C2 N2 Ni1 108.5(3) . . ? C2 N2 H2A 110.0 . . ? Ni1 N2 H2A 110.0 . . ? C2 N2 H2B 110.0 . . ? Ni1 N2 H2B 110.0 . . ? H2A N2 H2B 108.4 . . ? O4 Cl1 O4 167.0(16) 2_755 . ? O4 Cl1 O3 116.2(9) 2_755 2_755 ? O4 Cl1 O3 64.0(9) . 2_755 ? O4 Cl1 O3 64.0(9) 2_755 . ? O4 Cl1 O3 116.2(9) . . ? O3 Cl1 O3 178(3) 2_755 . ? O4 Cl1 O2 54.8(11) 2_755 . ? O4 Cl1 O2 114.1(11) . . ? O3 Cl1 O2 80.3(12) 2_755 . ? O3 Cl1 O2 101.3(12) . . ? O4 Cl1 O2 114.1(11) 2_755 2_755 ? O4 Cl1 O2 54.8(11) . 2_755 ? O3 Cl1 O2 101.3(12) 2_755 2_755 ? O3 Cl1 O2 80.3(12) . 2_755 ? O2 Cl1 O2 83.8(17) . 2_755 ? O4 Cl1 O5 114.6(10) 2_755 2_755 ? O4 Cl1 O5 76.3(10) . 2_755 ? O3 Cl1 O5 107.5(12) 2_755 2_755 ? O3 Cl1 O5 70.8(15) . 2_755 ? O2 Cl1 O5 169.3(12) . 2_755 ? O2 Cl1 O5 101.3(7) 2_755 2_755 ? O4 Cl1 O5 76.3(10) 2_755 . ? O4 Cl1 O5 114.6(10) . . ? O3 Cl1 O5 70.8(15) 2_755 . ? O3 Cl1 O5 107.5(12) . . ? O2 Cl1 O5 101.3(7) . . ? O2 Cl1 O5 169.3(12) 2_755 . ? O5 Cl1 O5 75.2(13) 2_755 . ? _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 28.49 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 1.903 _refine_diff_density_min -0.632 _refine_diff_density_rms 0.144 data_BNi8B _database_code_depnum_ccdc_archive 'CCDC 867596' #TrackingRef '- CIF-2.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C9 H24 F6 N5 Ni O P' _chemical_formula_weight 422.01 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 '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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 16.846(3) _cell_length_b 6.5212(10) _cell_length_c 9.0652(14) _cell_angle_alpha 90.00 _cell_angle_beta 119.112(4) _cell_angle_gamma 90.00 _cell_volume 870.1(2) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 132 _cell_measurement_theta_min 3.37 _cell_measurement_theta_max 26.98 _exptl_crystal_description parallelepiped _exptl_crystal_colour green _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.611 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 436 _exptl_absorpt_coefficient_mu 1.273 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.8419 _exptl_absorpt_correction_T_max 0.9050 _exptl_absorpt_process_details SADABS _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 APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8961 _diffrn_reflns_av_R_equivalents 0.2318 _diffrn_reflns_av_sigmaI/netI 0.1612 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.71 _diffrn_reflns_theta_max 28.00 _reflns_number_total 2074 _reflns_number_gt 1064 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART (Bruker,2000)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker,2000)' _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Mercury 1.4.1' _computing_publication_material '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^ > 2\s(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.Soft restraints on anions geometry and displacement parameters were used with the help of DFIX, DELU, DANG and SIMU instructions of SHELXL-97. EADP constraint was applied on carbon and nitrogen atoms of cyanate to have reasonable displacement parameters. ; _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^)+(0.0677P)^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 noref _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 0.42(6) _refine_ls_number_reflns 2074 _refine_ls_number_parameters 109 _refine_ls_number_restraints 33 _refine_ls_R_factor_all 0.1192 _refine_ls_R_factor_gt 0.0666 _refine_ls_wR_factor_ref 0.1752 _refine_ls_wR_factor_gt 0.1525 _refine_ls_goodness_of_fit_ref 0.895 _refine_ls_restrained_S_all 0.933 _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 0.3171(7) 0.0979(18) 0.4496(13) 0.095(3) Uani 1 1 d DU . . H1A H 0.2543 0.1420 0.4004 0.115 Uiso 1 1 calc R . . H1B H 0.3177 -0.0506 0.4552 0.115 Uiso 1 1 calc R . . C2 C 0.3655(5) 0.176(4) 0.6161(10) 0.089(3) Uani 1 1 d U . . H2A H 0.3467 0.1022 0.6870 0.107 Uiso 1 1 calc R . . H2B H 0.3497 0.3191 0.6154 0.107 Uiso 1 1 calc R . . C3 C 0.3138(11) 0.030(3) 0.1828(18) 0.172(8) Uani 1 1 d DU . . H3A H 0.3564 0.0230 0.1411 0.258 Uiso 1 1 calc R . . H3B H 0.2579 0.0890 0.0979 0.258 Uiso 1 1 calc R . . H3C H 0.3026 -0.1053 0.2097 0.258 Uiso 1 1 calc R . . C4 C 0.3196(10) 0.371(2) 0.263(2) 0.147(7) Uani 1 1 d DU . . H4A H 0.3497 0.4727 0.3497 0.220 Uiso 1 1 calc R . . H4B H 0.2552 0.3805 0.2199 0.220 Uiso 1 1 calc R . . H4C H 0.3334 0.3942 0.1737 0.220 Uiso 1 1 calc R . . C5 C 0.5000 0.644(3) 0.5000 0.046(3) Uani 1 2 d S . . N1 N 0.3521(4) 0.1603(18) 0.3373(7) 0.0635(16) Uani 1 1 d D . . N2 N 0.4658(4) 0.158(2) 0.6907(6) 0.0588(14) Uani 1 1 d . . . H2C H 0.4851 0.0404 0.7495 0.071 Uiso 1 1 calc R . . H2D H 0.4932 0.2631 0.7620 0.071 Uiso 1 1 calc R . . N3 N 0.4813 0.830(3) 0.473(4) 0.062(3) Uani 0.50 1 d PU . -1 O1 O 0.5164(14) 0.474(3) 0.514(5) 0.062(3) Uani 0.50 1 d P . -1 F1 F 0.4381(6) 0.8383(16) 0.0109(11) 0.195(8) Uani 1 1 d D . . F2 F 0.5603(4) 0.674(2) 0.1975(5) 0.124(3) Uani 1 1 d D . . F3 F 0.5610(7) 0.4854(12) 0.0000(13) 0.155(5) Uani 1 1 d D . . P1 P 0.5000 0.6638(11) 0.0000 0.0567(6) Uani 1 2 d SD . . Ni1 Ni 0.5000 0.1618(4) 0.5000 0.0483(4) 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 0.070(5) 0.128(8) 0.102(5) -0.015(6) 0.052(4) -0.008(5) C2 0.076(4) 0.127(8) 0.087(4) -0.023(7) 0.058(4) -0.005(7) C3 0.104(11) 0.192(15) 0.161(12) -0.113(10) 0.019(9) 0.033(9) C4 0.068(8) 0.123(11) 0.167(12) 0.079(10) -0.007(7) 0.018(7) C5 0.062(5) 0.018(7) 0.065(5) 0.000 0.036(4) 0.000 N1 0.059(3) 0.074(4) 0.057(3) 0.030(7) 0.028(3) 0.001(8) N2 0.073(4) 0.057(3) 0.053(3) 0.016(8) 0.036(3) -0.005(8) N3 0.064(8) 0.035(3) 0.076(7) -0.002(4) 0.025(7) -0.002(3) O1 0.064(8) 0.035(3) 0.076(7) -0.002(4) 0.025(7) -0.002(3) F1 0.108(8) 0.281(16) 0.143(9) -0.123(11) 0.019(7) 0.070(9) F2 0.158(5) 0.125(6) 0.057(3) -0.017(7) 0.028(3) 0.040(8) F3 0.141(11) 0.105(7) 0.190(10) -0.039(9) 0.058(10) 0.048(7) P1 0.0687(15) 0.0525(12) 0.0546(13) 0.000 0.0345(12) 0.000 Ni1 0.0573(7) 0.0370(6) 0.0546(7) 0.000 0.0304(5) 0.000 _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.416(14) . ? C1 N1 1.461(10) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C2 N2 1.489(9) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 N1 1.490(8) . ? C3 H3A 0.9600 . ? C3 H3B 0.9600 . ? C3 H3C 0.9600 . ? C4 N1 1.510(9) . ? C4 H4A 0.9600 . ? C4 H4B 0.9600 . ? C4 H4C 0.9600 . ? C5 O1 1.13(3) 2_656 ? C5 O1 1.13(3) . ? C5 N3 1.24(3) . ? C5 N3 1.24(3) 2_656 ? N1 Ni1 2.192(5) . ? N2 Ni1 2.071(5) . ? N2 H2C 0.9000 . ? N2 H2D 0.9000 . ? N3 Ni1 2.19(2) 1_565 ? O1 Ni1 2.053(18) . ? F1 P1 1.579(8) . ? F2 P1 1.572(4) . ? F3 P1 1.551(9) . ? P1 F3 1.551(9) 2_655 ? P1 F2 1.572(4) 2_655 ? P1 F1 1.579(8) 2_655 ? Ni1 O1 2.053(18) 2_656 ? Ni1 N2 2.071(5) 2_656 ? Ni1 N3 2.19(2) 1_545 ? Ni1 N3 2.19(2) 2_646 ? Ni1 N1 2.192(5) 2_656 ? 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 N1 115.2(10) . . ? C2 C1 H1A 108.5 . . ? N1 C1 H1A 108.5 . . ? C2 C1 H1B 108.5 . . ? N1 C1 H1B 108.5 . . ? H1A C1 H1B 107.5 . . ? C1 C2 N2 113.2(9) . . ? C1 C2 H2A 108.9 . . ? N2 C2 H2A 108.9 . . ? C1 C2 H2B 108.9 . . ? N2 C2 H2B 108.9 . . ? H2A C2 H2B 107.8 . . ? N1 C3 H3A 109.5 . . ? N1 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? N1 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? N1 C4 H4A 109.5 . . ? N1 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? N1 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? O1 C5 O1 25(2) 2_656 . ? O1 C5 N3 154.6(10) 2_656 . ? O1 C5 N3 175(3) . . ? O1 C5 N3 175(3) 2_656 2_656 ? O1 C5 N3 154.6(10) . 2_656 ? N3 C5 N3 27.1(12) . 2_656 ? C1 N1 C3 111.1(10) . . ? C1 N1 C4 112.4(9) . . ? C3 N1 C4 101.8(12) . . ? C1 N1 Ni1 104.2(5) . . ? C3 N1 Ni1 117.7(8) . . ? C4 N1 Ni1 110.0(8) . . ? C2 N2 Ni1 109.6(4) . . ? C2 N2 H2C 109.7 . . ? Ni1 N2 H2C 109.7 . . ? C2 N2 H2D 109.7 . . ? Ni1 N2 H2D 109.7 . . ? H2C N2 H2D 108.2 . . ? C5 N3 Ni1 158.8(9) . 1_565 ? C5 O1 Ni1 161.0(17) . . ? F3 P1 F3 82.9(7) 2_655 . ? F3 P1 F2 95.4(7) 2_655 . ? F3 P1 F2 88.4(5) . . ? F3 P1 F2 88.4(5) 2_655 2_655 ? F3 P1 F2 95.4(7) . 2_655 ? F2 P1 F2 174.9(11) . 2_655 ? F3 P1 F1 176.1(6) 2_655 2_655 ? F3 P1 F1 94.8(5) . 2_655 ? F2 P1 F1 87.6(6) . 2_655 ? F2 P1 F1 88.7(4) 2_655 2_655 ? F3 P1 F1 94.8(5) 2_655 . ? F3 P1 F1 176.1(6) . . ? F2 P1 F1 88.7(4) . . ? F2 P1 F1 87.6(6) 2_655 . ? F1 P1 F1 87.7(8) 2_655 . ? O1 Ni1 O1 13.5(12) . 2_656 ? O1 Ni1 N2 88.8(13) . 2_656 ? O1 Ni1 N2 92.5(12) 2_656 2_656 ? O1 Ni1 N2 92.5(12) . . ? O1 Ni1 N2 88.8(13) 2_656 . ? N2 Ni1 N2 178.7(9) 2_656 . ? O1 Ni1 N3 177.3(18) . 1_545 ? O1 Ni1 N3 165.8(6) 2_656 1_545 ? N2 Ni1 N3 88.7(10) 2_656 1_545 ? N2 Ni1 N3 90.0(11) . 1_545 ? O1 Ni1 N3 165.8(6) . 2_646 ? O1 Ni1 N3 177.3(18) 2_656 2_646 ? N2 Ni1 N3 90.0(11) 2_656 2_646 ? N2 Ni1 N3 88.7(10) . 2_646 ? N3 Ni1 N3 15.3(7) 1_545 2_646 ? O1 Ni1 N1 83.6(7) . 2_656 ? O1 Ni1 N1 96.9(7) 2_656 2_656 ? N2 Ni1 N1 82.8(2) 2_656 2_656 ? N2 Ni1 N1 97.2(2) . 2_656 ? N3 Ni1 N1 97.2(4) 1_545 2_656 ? N3 Ni1 N1 82.3(3) 2_646 2_656 ? O1 Ni1 N1 96.9(7) . . ? O1 Ni1 N1 83.6(7) 2_656 . ? N2 Ni1 N1 97.2(2) 2_656 . ? N2 Ni1 N1 82.8(2) . . ? N3 Ni1 N1 82.3(3) 1_545 . ? N3 Ni1 N1 97.2(4) 2_646 . ? N1 Ni1 N1 179.5(7) 2_656 . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 28.00 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.637 _refine_diff_density_min -0.372 _refine_diff_density_rms 0.088