# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Lodeiro, Carlos' _publ_contact_author_email clodeiro@uvigo.es _publ_section_title ; New dinuclear Nickel(II) and Iron(II) complexes with a macrocyclic ligand containing a N6S2 donor-set: Synthesis, Structural, MALDI-TOF-MS, Magnetic and Spectroscopic Studies. ; loop_ _publ_author_name C.NuA+-ez R.Bastida A.MacAas L.Valencia J.Ribas J.Capelo ; C.Lodeiro ; # Attachment '- 768500.cif' data_ba06cn1n _database_code_depnum_ccdc_archive 'CCDC 768499' #TrackingRef '- 768500.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '[Ni2 (C22 H34 N6 S2) Cl (H2 O)2](B F4)3 . 2 (H2 O)' _chemical_formula_sum 'C22 H42 B2 Cl F8 N6 Ni2 O4 S2' _chemical_formula_weight 845.23 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 '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' O O 0.0106 0.0060 '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/c loop_ _symmetry_equiv_pos_as_xyz '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, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 13.856 _cell_length_b 19.805 _cell_length_c 14.725 _cell_angle_alpha 90.00 _cell_angle_beta 111.43 _cell_angle_gamma 90.00 _cell_volume 3761.3 _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour blue _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.493 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1740 _exptl_absorpt_coefficient_mu 1.258 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.7438 _exptl_absorpt_correction_T_max 0.9514 _exptl_absorpt_process_details 'Sadabs (Sheldrick, 1996)' _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 X8 KappaAPEXII' _diffrn_measurement_method 'omega and phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16242 _diffrn_reflns_av_R_equivalents 0.0605 _diffrn_reflns_av_sigmaI/netI 0.0670 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.88 _diffrn_reflns_theta_max 26.38 _reflns_number_total 3849 _reflns_number_gt 2493 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'BRUKER APEX2' _computing_cell_refinement 'BRUKER APEX2' _computing_data_reduction 'BRUKER SHELXTL' _computing_structure_solution 'SIR-92 (Altornare, et al., 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-3 for Windows (Farrugia, 1999)' _computing_publication_material 'Wingx publication routines (Farrugia, 1999)' _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^)+(0.0488P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary 'heavy atom' _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens mixed _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3849 _refine_ls_number_parameters 239 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0780 _refine_ls_R_factor_gt 0.0460 _refine_ls_wR_factor_ref 0.1030 _refine_ls_wR_factor_gt 0.0946 _refine_ls_goodness_of_fit_ref 0.987 _refine_ls_restrained_S_all 0.987 _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 O2W O 0.3942(2) 0.58173(13) 0.3270(2) 0.0296(6) Uani 1 1 d . . . H1N H 0.285(2) 0.4900(16) 0.091(2) 0.015(9) Uiso 1 1 d . . . H2N H 0.322(3) 0.3335(18) 0.346(3) 0.032(11) Uiso 1 1 d . . . H21W H 0.385(3) 0.600(2) 0.276(3) 0.042(14) Uiso 1 1 d . . . H11W H 0.328(3) 0.493(2) 0.304(3) 0.050(14) Uiso 1 1 d . . . H22W H 0.462(4) 0.577(2) 0.361(3) 0.063(15) Uiso 1 1 d . . . H12W H 0.254(4) 0.461(3) 0.305(4) 0.07(2) Uiso 1 1 d . . . Ni Ni 0.32966(4) 0.38807(2) 0.19811(3) 0.02972(16) Uani 1 1 d . . . Cl1 Cl 0.5000 0.43580(6) 0.2500 0.0315(3) Uani 1 2 d S . . S S 0.35641(8) 0.30937(4) 0.07785(6) 0.0335(3) Uani 1 1 d . . . O1W O 0.2991(3) 0.45778(15) 0.2895(2) 0.0412(8) Uani 1 1 d . . . N1 N 0.1836(2) 0.35504(14) 0.1523(2) 0.0314(7) Uani 1 1 d . . . N2 N 0.3403(2) 0.31194(14) 0.3045(2) 0.0303(8) Uani 1 1 d . . . N3 N 0.2614(2) 0.45345(15) 0.0771(2) 0.0324(8) Uani 1 1 d . . . C1 C 0.1093(3) 0.39091(16) 0.0848(2) 0.0288(8) Uani 1 1 d . . . C2 C 0.0081(3) 0.36981(16) 0.0507(2) 0.0268(8) Uani 1 1 d . . . H2 H -0.0441 0.3948 0.0021 0.032 Uiso 1 1 calc R . . C3 C -0.0163(3) 0.31102(17) 0.0888(3) 0.0296(9) Uani 1 1 d . . . H3 H -0.0861 0.2957 0.0668 0.036 Uiso 1 1 calc R . . C4 C 0.0605(3) 0.27465(16) 0.1588(3) 0.0287(8) Uani 1 1 d . . . H4 H 0.0441 0.2345 0.1855 0.034 Uiso 1 1 calc R . . C5 C 0.1615(3) 0.29758(16) 0.1892(2) 0.0281(8) Uani 1 1 d . . . C6 C 0.2550(3) 0.26246(17) 0.2606(3) 0.0359(9) Uani 1 1 d . . . H6A H 0.2362 0.2411 0.3127 0.043 Uiso 1 1 calc R . . H6B H 0.2784 0.2266 0.2266 0.043 Uiso 1 1 calc R . . C7 C 0.4384(3) 0.27662(17) 0.3564(3) 0.0371(10) Uani 1 1 d . . . H7A H 0.4669 0.2587 0.3086 0.045 Uiso 1 1 calc R . . H7B H 0.4255 0.2380 0.3932 0.045 Uiso 1 1 calc R . . C8 C 0.4828(3) 0.32445(17) 0.0731(2) 0.0335(9) Uani 1 1 d . . . H8A H 0.4806 0.3169 0.0060 0.040 Uiso 1 1 calc R . . H8B H 0.5037 0.3718 0.0913 0.040 Uiso 1 1 calc R . . C9 C 0.2760(3) 0.35824(17) -0.0263(2) 0.0304(9) Uani 1 1 d . . . H9A H 0.2945 0.3469 -0.0834 0.036 Uiso 1 1 calc R . . H9B H 0.2025 0.3457 -0.0422 0.036 Uiso 1 1 calc R . . C10 C 0.2882(3) 0.43355(16) -0.0080(3) 0.0328(9) Uani 1 1 d . . . H10A H 0.3608 0.4467 0.0039 0.039 Uiso 1 1 calc R . . H10B H 0.2427 0.4579 -0.0667 0.039 Uiso 1 1 calc R . . C11 C 0.1488(3) 0.45571(16) 0.0561(3) 0.0314(9) Uani 1 1 d . . . H11A H 0.1117 0.4638 -0.0145 0.038 Uiso 1 1 calc R . . H11B H 0.1334 0.4939 0.0920 0.038 Uiso 1 1 calc R . . B B 0.3314(3) 0.63145(19) 0.0659(3) 0.0268(9) Uani 1 1 d . . . F1 F 0.38963(15) 0.57869(9) 0.05065(16) 0.0352(5) Uani 1 1 d . . . F2 F 0.38575(17) 0.65971(10) 0.15664(15) 0.0409(6) Uani 1 1 d . . . F3 F 0.31460(18) 0.68040(10) -0.00452(16) 0.0489(6) Uani 1 1 d . . . F4 F 0.23885(17) 0.60646(11) 0.0657(3) 0.0881(12) 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 O2W 0.0308(17) 0.0232(14) 0.0302(17) 0.0001(12) 0.0059(13) -0.0054(11) Ni 0.0449(3) 0.0146(2) 0.0146(2) 0.00338(18) -0.00695(19) -0.0112(2) Cl1 0.0420(8) 0.0137(6) 0.0220(7) 0.000 -0.0083(6) 0.000 S 0.0533(6) 0.0160(5) 0.0153(5) 0.0010(3) -0.0065(4) -0.0107(4) O1W 0.057(2) 0.0242(17) 0.0312(17) -0.0057(12) 0.0020(16) -0.0166(15) N1 0.048(2) 0.0185(16) 0.0159(16) 0.0036(12) -0.0019(14) -0.0119(14) N2 0.047(2) 0.0150(16) 0.0145(16) 0.0043(12) -0.0061(15) -0.0081(14) N3 0.041(2) 0.0146(17) 0.0242(18) 0.0050(13) -0.0080(14) -0.0159(14) C1 0.047(2) 0.0155(18) 0.0154(18) 0.0016(14) 0.0013(16) -0.0088(16) C2 0.036(2) 0.0185(19) 0.0199(19) -0.0009(14) 0.0035(16) -0.0026(15) C3 0.043(2) 0.0230(19) 0.027(2) -0.0085(16) 0.0166(18) -0.0117(16) C4 0.053(3) 0.0141(18) 0.021(2) -0.0025(14) 0.0165(18) -0.0074(16) C5 0.050(2) 0.0139(18) 0.0131(18) -0.0009(13) 0.0035(17) -0.0093(16) C6 0.056(3) 0.0205(19) 0.020(2) 0.0033(15) 0.0010(18) -0.0138(17) C7 0.058(3) 0.019(2) 0.022(2) 0.0060(15) 0.0002(18) -0.0012(18) C8 0.053(3) 0.022(2) 0.0124(18) -0.0034(14) -0.0038(17) -0.0023(17) C9 0.042(2) 0.0244(19) 0.0105(18) 0.0042(14) -0.0068(15) -0.0103(16) C10 0.042(2) 0.022(2) 0.019(2) 0.0087(15) -0.0076(17) -0.0116(16) C11 0.041(2) 0.0171(18) 0.023(2) 0.0060(15) -0.0049(17) -0.0074(16) B 0.022(2) 0.018(2) 0.038(3) 0.0049(18) 0.0093(19) -0.0008(16) F1 0.0353(12) 0.0203(11) 0.0458(14) -0.0039(9) 0.0100(11) 0.0042(9) F2 0.0574(15) 0.0389(13) 0.0302(13) -0.0027(10) 0.0206(11) 0.0054(11) F3 0.0667(16) 0.0247(12) 0.0387(14) 0.0058(10) -0.0004(12) 0.0034(11) F4 0.0277(14) 0.0232(14) 0.217(4) 0.0194(17) 0.0494(19) 0.0008(11) _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 1.995(3) . ? Ni O1W 2.076(3) . ? Ni N3 2.125(3) . ? Ni N2 2.140(3) . ? Ni Cl1 2.3938(6) . ? Ni S 2.4865(10) . ? Cl1 Ni 2.3938(6) 2_655 ? S C8 1.803(4) . ? S C9 1.812(3) . ? N1 C1 1.344(4) . ? N1 C5 1.343(4) . ? N2 C7 1.471(5) . ? N2 C6 1.489(4) . ? N3 C11 1.477(5) . ? N3 C10 1.485(5) . ? C1 C2 1.371(5) . ? C1 C11 1.514(4) . ? C2 C3 1.387(4) . ? C3 C4 1.383(5) . ? C4 C5 1.381(5) . ? C5 C6 1.507(5) . ? C7 C8 1.529(5) 2_655 ? C8 C7 1.529(5) 2_655 ? C9 C10 1.514(5) . ? B F4 1.373(4) . ? B F3 1.376(4) . ? B F2 1.389(5) . ? B F1 1.388(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 N1 Ni O1W 90.86(14) . . ? N1 Ni N3 80.28(11) . . ? O1W Ni N3 90.27(12) . . ? N1 Ni N2 78.81(11) . . ? O1W Ni N2 88.27(13) . . ? N3 Ni N2 159.02(12) . . ? N1 Ni Cl1 175.85(9) . . ? O1W Ni Cl1 86.64(11) . . ? N3 Ni Cl1 96.41(9) . . ? N2 Ni Cl1 104.40(9) . . ? N1 Ni S 87.17(9) . . ? O1W Ni S 175.56(9) . . ? N3 Ni S 85.47(9) . . ? N2 Ni S 95.25(9) . . ? Cl1 Ni S 95.09(3) . . ? Ni Cl1 Ni 133.48(5) . 2_655 ? C8 S C9 100.63(17) . . ? C8 S Ni 108.86(12) . . ? C9 S Ni 93.58(12) . . ? C1 N1 C5 121.4(3) . . ? C1 N1 Ni 119.0(2) . . ? C5 N1 Ni 119.6(2) . . ? C7 N2 C6 110.4(3) . . ? C7 N2 Ni 121.2(2) . . ? C6 N2 Ni 108.3(2) . . ? C11 N3 C10 113.7(3) . . ? C11 N3 Ni 107.8(2) . . ? C10 N3 Ni 112.0(2) . . ? N1 C1 C2 121.0(3) . . ? N1 C1 C11 113.4(3) . . ? C2 C1 C11 125.6(3) . . ? C1 C2 C3 118.4(3) . . ? C4 C3 C2 120.3(3) . . ? C5 C4 C3 118.9(3) . . ? N1 C5 C4 120.1(3) . . ? N1 C5 C6 114.1(3) . . ? C4 C5 C6 125.8(3) . . ? N2 C6 C5 110.0(3) . . ? N2 C7 C8 110.7(3) . 2_655 ? C7 C8 S 109.5(3) 2_655 . ? C10 C9 S 112.4(2) . . ? N3 C10 C9 111.4(3) . . ? N3 C11 C1 112.2(3) . . ? F4 B F3 110.6(3) . . ? F4 B F2 109.0(3) . . ? F3 B F2 108.9(3) . . ? F4 B F1 109.0(3) . . ? F3 B F1 110.9(3) . . ? F2 B F1 108.5(3) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.38 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.644 _refine_diff_density_min -0.817 _refine_diff_density_rms 0.081 # SQUEEZE RESULTS loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons 1 0.000 0.537 0.250 145.5 50.5 2 0.000 0.463 0.750 145.4 51.7 3 0.500 0.037 0.250 145.5 50.5 4 0.500 0.963 0.750 145.4 51.7 # Attachment '- 768499.cif' data_ba19cn2n _database_code_depnum_ccdc_archive 'CCDC 768500' #TrackingRef '- 768499.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '[Ni2 (C22 H34 N6 S2) (CH3CN)4](BF4)4 . 3.5 (CH3CN)' _chemical_formula_sum 'C18.50 H28.25 B2 F8 N6.75 Ni S' _chemical_formula_weight 609.62 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Ni Ni 0.3393 1.1124 '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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 13.079 _cell_length_b 18.517 _cell_length_c 13.181 _cell_angle_alpha 90.00 _cell_angle_beta 114.84 _cell_angle_gamma 90.00 _cell_volume 2897.0 _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1805 _cell_measurement_theta_min 2,88 _cell_measurement_theta_max 20,62 _exptl_crystal_description plate _exptl_crystal_colour mauve _exptl_crystal_size_max 0.36 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.398 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1250 _exptl_absorpt_coefficient_mu 0.813 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.7584 _exptl_absorpt_correction_T_max 0.9453 _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 X8 KappaAPEXII' _diffrn_measurement_method 'omega and phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 24504 _diffrn_reflns_av_R_equivalents 0.0604 _diffrn_reflns_av_sigmaI/netI 0.0676 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.84 _diffrn_reflns_theta_max 26.37 _reflns_number_total 5899 _reflns_number_gt 3613 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'BRUKER APEX' _computing_cell_refinement 'BRUKER APEX' _computing_data_reduction 'BRUKER SHELXTL' _computing_structure_solution 'SIR-92 (Altornare, Cascarano, Giacovazzo, and Gualardi, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-3 for Windows (Farrugia, 1999)' _computing_publication_material 'Wingx publication routines (Farrugia, 1999)' _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^)+(0.0913P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens mixed _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5899 _refine_ls_number_parameters 447 _refine_ls_number_restraints 96 _refine_ls_R_factor_all 0.1007 _refine_ls_R_factor_gt 0.0546 _refine_ls_wR_factor_ref 0.1621 _refine_ls_wR_factor_gt 0.1437 _refine_ls_goodness_of_fit_ref 1.002 _refine_ls_restrained_S_all 1.003 _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 Ni1 Ni 0.29057(4) 0.02101(2) 0.32493(4) 0.04389(18) Uani 1 1 d . . . N1 N 0.1389(3) -0.01247(16) 0.2171(3) 0.0504(8) Uani 1 1 d . . . N2 N 0.3268(3) -0.09145(15) 0.3105(3) 0.0455(7) Uani 1 1 d . . . N3 N 0.2026(3) 0.11883(17) 0.2931(3) 0.0538(9) Uani 1 1 d . . . N1S N 0.3528(3) 0.04364(18) 0.2073(3) 0.0567(9) Uani 1 1 d . . . N2S N 0.2480(3) -0.00739(17) 0.4560(3) 0.0516(8) Uani 1 1 d . . . N3S N 0.6471(6) -0.0993(4) 0.2123(6) 0.135(2) Uani 1 1 d . . . N4S N 0.4390(8) -0.3927(5) -0.0327(9) 0.132(3) Uani 0.75 1 d P . . S S 0.45032(8) 0.09430(5) 0.45625(8) 0.0482(3) Uani 1 1 d . . . C1 C 0.0523(4) 0.0320(2) 0.1943(4) 0.0615(11) Uani 1 1 d . . . C2 C -0.0557(4) 0.0091(3) 0.1245(5) 0.0828(15) Uani 1 1 d . . . H2 H -0.1172 0.0395 0.1084 0.099 Uiso 1 1 calc R . . C3 C -0.0703(5) -0.0598(3) 0.0790(5) 0.0944(17) Uani 1 1 d . . . H3 H -0.1420 -0.0757 0.0313 0.113 Uiso 1 1 calc R . . C4 C 0.0221(4) -0.1050(3) 0.1049(4) 0.0782(14) Uani 1 1 d . . . H4 H 0.0137 -0.1514 0.0755 0.094 Uiso 1 1 calc R . . C5 C 0.1267(3) -0.0788(2) 0.1756(3) 0.0543(10) Uani 1 1 d . . . C6 C 0.2344(4) -0.1209(2) 0.2082(4) 0.0626(11) Uani 1 1 d . . . H6A H 0.2211 -0.1708 0.2211 0.075 Uiso 1 1 calc R . . H6B H 0.2572 -0.1197 0.1471 0.075 Uiso 1 1 calc R . . C7 C 0.4367(3) -0.1174(2) 0.3141(4) 0.0540(10) Uani 1 1 d . . . H7A H 0.4375 -0.1093 0.2417 0.065 Uiso 1 1 calc R . . H7B H 0.4430 -0.1690 0.3281 0.065 Uiso 1 1 calc R . . C8 C 0.4636(3) 0.0804(2) 0.5978(3) 0.0503(9) Uani 1 1 d . . . H8A H 0.3957 0.0979 0.6023 0.060 Uiso 1 1 calc R . . H8B H 0.4691 0.0290 0.6133 0.060 Uiso 1 1 calc R . . C9 C 0.3726(4) 0.1792(2) 0.4187(4) 0.0611(11) Uani 1 1 d . . . H9A H 0.4032 0.2120 0.4818 0.073 Uiso 1 1 calc R . . H9B H 0.3836 0.2010 0.3570 0.073 Uiso 1 1 calc R . . C10 C 0.2489(4) 0.1703(2) 0.3857(4) 0.0641(12) Uani 1 1 d . . . H10A H 0.2364 0.1527 0.4490 0.077 Uiso 1 1 calc R . . H10B H 0.2112 0.2165 0.3631 0.077 Uiso 1 1 calc R . . C11 C 0.0810(4) 0.1024(2) 0.2561(4) 0.0695(12) Uani 1 1 d . . . H11A H 0.0361 0.1408 0.2077 0.083 Uiso 1 1 calc R . . H11B H 0.0635 0.0999 0.3206 0.083 Uiso 1 1 calc R . . C1S C 0.3946(4) 0.0547(2) 0.1502(4) 0.0642(11) Uani 1 1 d . . . C2S C 0.4485(6) 0.0673(4) 0.0749(6) 0.124(3) Uani 1 1 d . . . H2S1 H 0.5140 0.0372 0.0964 0.186 Uiso 1 1 calc R . . H2S2 H 0.4703 0.1171 0.0790 0.186 Uiso 1 1 calc R . . H2S3 H 0.3966 0.0560 -0.0002 0.186 Uiso 1 1 calc R . . C3S C 0.2317(4) -0.0291(2) 0.5265(4) 0.0610(11) Uani 1 1 d . . . C4S C 0.2144(6) -0.0573(3) 0.6218(5) 0.113(2) Uani 1 1 d . . . H4S1 H 0.2220 -0.1089 0.6243 0.170 Uiso 1 1 calc R . . H4S2 H 0.1403 -0.0446 0.6139 0.170 Uiso 1 1 calc R . . H4S3 H 0.2695 -0.0369 0.6897 0.170 Uiso 1 1 calc R . . C5S C 0.6304(6) -0.1585(6) 0.1887(6) 0.106(2) Uani 1 1 d . . . C6S C 0.6081(7) -0.2324(4) 0.1577(7) 0.141(3) Uani 1 1 d . . . H6S1 H 0.5360 -0.2366 0.0952 0.212 Uiso 1 1 calc R . . H6S2 H 0.6078 -0.2596 0.2196 0.212 Uiso 1 1 calc R . . H6S3 H 0.6655 -0.2509 0.1374 0.212 Uiso 1 1 calc R . . C7S C 0.4398(7) -0.3585(6) -0.0987(8) 0.096(3) Uani 0.75 1 d P . . C8S C 0.4456(7) -0.3129(6) -0.1788(7) 0.112(3) Uani 0.75 1 d P . . H8S1 H 0.4567 -0.2642 -0.1512 0.169 Uiso 0.75 1 calc PR . . H8S2 H 0.3767 -0.3158 -0.2454 0.169 Uiso 0.75 1 calc PR . . H8S3 H 0.5075 -0.3270 -0.1955 0.169 Uiso 0.75 1 calc PR . . B1 B 0.2352(17) 0.2399(10) 0.0617(14) 0.067(4) Uani 0.616(13) 1 d PDU A 1 F1 F 0.3169(8) 0.2235(6) 0.1595(6) 0.141(4) Uani 0.616(13) 1 d PDU A 1 F2 F 0.1347(9) 0.2333(7) 0.0745(12) 0.137(5) Uani 0.616(13) 1 d PDU A 1 F3 F 0.2431(11) 0.3108(4) 0.0452(9) 0.110(4) Uani 0.616(13) 1 d PDU A 1 F4 F 0.2346(9) 0.1991(4) -0.0203(7) 0.112(3) Uani 0.616(13) 1 d PDU A 1 B1' B 0.214(2) 0.2489(13) 0.050(2) 0.068(6) Uani 0.384(13) 1 d PDU A 2 F1' F 0.158(2) 0.2276(12) 0.108(2) 0.155(8) Uani 0.384(13) 1 d PDU A 2 F2' F 0.2837(19) 0.1907(9) 0.061(3) 0.242(16) Uani 0.384(13) 1 d PDU A 2 F3' F 0.1455(16) 0.2505(11) -0.0588(9) 0.178(9) Uani 0.384(13) 1 d PDU A 2 F4' F 0.2747(17) 0.3082(10) 0.077(2) 0.135(8) Uani 0.384(13) 1 d PDU A 2 B2 B 0.275(2) -0.159(2) -0.069(3) 0.098(6) Uani 0.484(19) 1 d PDU B 1 F5 F 0.240(2) -0.1320(8) -0.1641(9) 0.181(7) Uani 0.484(19) 1 d PDU B 1 F6 F 0.334(2) -0.2185(11) -0.064(2) 0.321(13) Uani 0.484(19) 1 d PDU B 1 F7 F 0.3411(19) -0.1148(16) 0.0178(16) 0.229(10) Uani 0.484(19) 1 d PDU B 1 F8 F 0.1825(16) -0.1853(12) -0.0557(17) 0.179(7) Uani 0.484(19) 1 d PDU B 1 B2' B 0.2941(18) -0.155(2) -0.054(3) 0.068(4) Uani 0.516(19) 1 d PDU B 2 F5' F 0.3634(8) -0.1970(8) 0.0165(14) 0.153(6) Uani 0.516(19) 1 d PDU B 2 F6' F 0.3126(10) -0.0870(5) -0.0171(14) 0.125(5) Uani 0.516(19) 1 d PDU B 2 F7' F 0.3077(17) -0.1615(10) -0.1517(13) 0.162(7) Uani 0.516(19) 1 d PDU B 2 F8' F 0.1860(8) -0.1721(7) -0.0697(14) 0.115(5) Uani 0.516(19) 1 d PDU B 2 H2N H 0.306(3) -0.107(2) 0.367(4) 0.062(12) Uiso 1 1 d . . . H3N H 0.209(3) 0.139(2) 0.236(3) 0.055(12) Uiso 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 Ni1 0.0498(3) 0.0367(3) 0.0439(3) -0.0006(2) 0.0185(2) -0.0001(2) N1 0.052(2) 0.0453(18) 0.0461(19) 0.0032(14) 0.0129(16) -0.0022(15) N2 0.052(2) 0.0399(16) 0.0426(19) -0.0065(14) 0.0179(16) -0.0030(14) N3 0.059(2) 0.0425(18) 0.056(2) 0.0070(16) 0.0205(19) 0.0056(15) N1S 0.066(2) 0.058(2) 0.049(2) 0.0012(16) 0.0262(19) -0.0013(16) N2S 0.057(2) 0.0479(18) 0.052(2) 0.0019(15) 0.0242(18) -0.0021(15) N3S 0.143(6) 0.164(7) 0.105(5) -0.028(5) 0.060(4) -0.018(5) N4S 0.129(7) 0.125(7) 0.140(8) -0.011(6) 0.054(7) -0.009(5) S 0.0552(6) 0.0401(5) 0.0490(6) -0.0045(4) 0.0216(5) -0.0014(4) C1 0.053(3) 0.056(2) 0.068(3) 0.007(2) 0.018(2) 0.006(2) C2 0.058(3) 0.076(3) 0.092(4) 0.001(3) 0.010(3) 0.003(2) C3 0.064(3) 0.086(4) 0.101(4) -0.002(3) 0.002(3) -0.017(3) C4 0.069(3) 0.060(3) 0.081(4) -0.006(2) 0.008(3) -0.004(2) C5 0.054(3) 0.050(2) 0.050(3) 0.0018(18) 0.013(2) -0.0071(18) C6 0.063(3) 0.052(2) 0.057(3) -0.013(2) 0.010(2) -0.0032(19) C7 0.057(3) 0.047(2) 0.052(3) -0.0072(18) 0.017(2) 0.0054(18) C8 0.058(2) 0.044(2) 0.050(2) -0.0066(17) 0.024(2) 0.0006(17) C9 0.070(3) 0.040(2) 0.066(3) -0.0023(19) 0.021(2) 0.0004(19) C10 0.071(3) 0.038(2) 0.078(3) 0.002(2) 0.026(3) 0.0120(19) C11 0.059(3) 0.058(3) 0.078(3) 0.003(2) 0.016(3) 0.015(2) C1S 0.075(3) 0.063(3) 0.060(3) 0.006(2) 0.034(3) 0.008(2) C2S 0.166(7) 0.132(6) 0.132(6) 0.028(4) 0.120(6) 0.031(5) C3S 0.067(3) 0.052(2) 0.062(3) -0.003(2) 0.024(2) -0.010(2) C4S 0.162(6) 0.109(5) 0.087(4) 0.021(4) 0.069(5) -0.030(4) C5S 0.092(5) 0.161(8) 0.072(5) 0.007(5) 0.042(4) 0.003(5) C6S 0.144(7) 0.118(6) 0.153(8) 0.016(5) 0.054(6) 0.015(5) C7S 0.076(5) 0.116(8) 0.090(7) -0.016(5) 0.029(5) -0.005(5) C8S 0.092(6) 0.162(9) 0.099(7) -0.021(6) 0.054(6) -0.008(6) B1 0.080(8) 0.048(6) 0.079(7) 0.004(5) 0.039(6) 0.012(6) F1 0.150(7) 0.148(8) 0.093(5) 0.037(4) 0.020(4) 0.033(5) F2 0.100(5) 0.153(9) 0.186(12) -0.063(7) 0.088(7) -0.036(5) F3 0.188(11) 0.050(4) 0.126(7) 0.025(4) 0.100(7) 0.017(5) F4 0.164(9) 0.090(6) 0.108(6) -0.034(4) 0.083(6) -0.004(5) B1' 0.054(13) 0.065(13) 0.079(9) -0.018(10) 0.021(8) -0.004(7) F1' 0.25(2) 0.129(12) 0.131(12) 0.037(10) 0.126(15) -0.030(11) F2' 0.20(2) 0.089(9) 0.46(5) 0.06(2) 0.16(3) 0.079(12) F3' 0.209(16) 0.212(18) 0.070(6) 0.011(8) 0.016(7) -0.055(13) F4' 0.086(8) 0.105(10) 0.224(19) -0.059(11) 0.075(10) -0.044(7) B2 0.145(19) 0.102(16) 0.057(9) 0.015(8) 0.051(12) 0.051(11) F5 0.32(2) 0.160(11) 0.075(6) 0.047(6) 0.094(9) 0.014(10) F6 0.45(3) 0.285(19) 0.27(3) 0.064(14) 0.19(2) 0.27(2) F7 0.24(2) 0.35(3) 0.104(9) -0.089(17) 0.082(11) -0.086(19) F8 0.219(14) 0.198(15) 0.125(10) 0.066(10) 0.079(9) -0.027(9) B2' 0.065(7) 0.076(8) 0.069(11) 0.004(7) 0.035(8) 0.009(6) F5' 0.109(7) 0.147(9) 0.179(12) 0.084(9) 0.037(7) 0.036(6) F6' 0.099(6) 0.089(5) 0.191(13) -0.046(6) 0.064(7) -0.017(4) F7' 0.251(16) 0.163(12) 0.132(9) -0.039(7) 0.140(11) -0.061(10) F8' 0.073(5) 0.095(6) 0.184(14) -0.022(7) 0.060(7) -0.014(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 Ni1 N1 1.993(3) . ? Ni1 N1S 2.075(3) . ? Ni1 N3 2.092(3) . ? Ni1 N2S 2.093(3) . ? Ni1 N2 2.162(3) . ? Ni1 S 2.4830(11) . ? N1 C5 1.327(5) . ? N1 C1 1.328(5) . ? N2 C6 1.485(5) . ? N2 C7 1.498(5) . ? N3 C10 1.464(5) . ? N3 C11 1.486(5) . ? N1S C1S 1.119(5) . ? N2S C3S 1.112(5) . ? N3S C5S 1.136(9) . ? N4S C7S 1.079(11) . ? S C8 1.818(4) . ? S C9 1.825(4) . ? C1 C2 1.389(6) . ? C1 C11 1.499(6) . ? C2 C3 1.388(7) . ? C3 C4 1.390(7) . ? C4 C5 1.380(6) . ? C5 C6 1.505(6) . ? C7 C8 1.499(5) 3_656 ? C8 C7 1.499(5) 3_656 ? C9 C10 1.499(6) . ? C1S C2S 1.457(6) . ? C3S C4S 1.463(6) . ? C5S C6S 1.424(11) . ? C7S C8S 1.379(12) . ? B1 F4 1.32(2) . ? B1 F1 1.319(17) . ? B1 F3 1.341(18) . ? B1 F2 1.399(19) . ? B1' F1' 1.32(2) . ? B1' F4' 1.32(3) . ? B1' F3' 1.33(2) . ? B1' F2' 1.38(2) . ? B2 F5 1.25(4) . ? B2 F6 1.33(4) . ? B2 F7 1.38(3) . ? B2 F8 1.376(16) . ? B2' F5' 1.26(4) . ? B2' F6' 1.34(4) . ? B2' F7' 1.37(3) . ? B2' F8' 1.379(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 N1 Ni1 N1S 96.63(13) . . ? N1 Ni1 N3 80.07(13) . . ? N1S Ni1 N3 91.77(14) . . ? N1 Ni1 N2S 88.87(13) . . ? N1S Ni1 N2S 172.70(13) . . ? N3 Ni1 N2S 93.92(13) . . ? N1 Ni1 N2 80.03(12) . . ? N1S Ni1 N2 87.69(12) . . ? N3 Ni1 N2 159.90(14) . . ? N2S Ni1 N2 88.53(12) . . ? N1 Ni1 S 164.02(9) . . ? N1S Ni1 S 86.06(10) . . ? N3 Ni1 S 84.10(10) . . ? N2S Ni1 S 89.98(9) . . ? N2 Ni1 S 115.88(9) . . ? C5 N1 C1 122.5(4) . . ? C5 N1 Ni1 119.6(3) . . ? C1 N1 Ni1 117.9(3) . . ? C6 N2 C7 108.4(3) . . ? C6 N2 Ni1 107.9(2) . . ? C7 N2 Ni1 123.3(2) . . ? C10 N3 C11 114.7(3) . . ? C10 N3 Ni1 113.4(3) . . ? C11 N3 Ni1 108.1(2) . . ? C1S N1S Ni1 174.5(4) . . ? C3S N2S Ni1 172.5(3) . . ? C8 S C9 101.67(18) . . ? C8 S Ni1 109.13(13) . . ? C9 S Ni1 94.15(15) . . ? N1 C1 C2 119.6(4) . . ? N1 C1 C11 114.9(4) . . ? C2 C1 C11 125.3(4) . . ? C1 C2 C3 119.0(5) . . ? C2 C3 C4 120.0(5) . . ? C5 C4 C3 117.9(5) . . ? N1 C5 C4 121.2(4) . . ? N1 C5 C6 115.1(4) . . ? C4 C5 C6 123.7(4) . . ? N2 C6 C5 112.1(3) . . ? N2 C7 C8 112.9(3) . 3_656 ? C7 C8 S 114.0(3) 3_656 . ? C10 C9 S 113.2(3) . . ? N3 C10 C9 109.4(3) . . ? N3 C11 C1 110.2(3) . . ? N1S C1S C2S 178.6(5) . . ? N2S C3S C4S 178.0(5) . . ? N3S C5S C6S 179.2(11) . . ? N4S C7S C8S 176.9(12) . . ? F4 B1 F1 113.2(15) . . ? F4 B1 F3 113.8(11) . . ? F1 B1 F3 107.3(17) . . ? F4 B1 F2 111.6(17) . . ? F1 B1 F2 106.1(11) . . ? F3 B1 F2 104.2(15) . . ? F1' B1' F4' 121(3) . . ? F1' B1' F3' 110(2) . . ? F4' B1' F3' 109.2(16) . . ? F1' B1' F2' 102.1(19) . . ? F4' B1' F2' 109(2) . . ? F3' B1' F2' 104(2) . . ? F5 B2 F6 110(3) . . ? F5 B2 F7 116(3) . . ? F6 B2 F7 107(3) . . ? F5 B2 F8 108(2) . . ? F6 B2 F8 103(3) . . ? F7 B2 F8 113(2) . . ? F5' B2' F6' 110(2) . . ? F5' B2' F7' 108(2) . . ? F6' B2' F7' 111(2) . . ? F5' B2' F8' 110(2) . . ? F6' B2' F8' 107(2) . . ? F7' B2' F8' 112(2) . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.433 _refine_diff_density_min -0.312 _refine_diff_density_rms 0.068