# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Prof Peter Wolczanski' _publ_contact_author_address ; Dept. Chemistry & Chemical Biol. Cornell University Baker Laboratory Ithaca NY 14853 UNITED STATES OF AMERICA ; _publ_contact_author_email PTW2@CORNELL.EDU _publ_section_title ; First row wheels {(tBu3SiS)MX}12 (M = Co, X = Cl; M = Ni, X = Br) are common amidst simpler (e.g., [(tBu3SiS)Ni]2(µ-SSitBu3)2) and more complex (e.g., [(µ-SSitBu3)Ni]5(µ5-S) aggregates ; loop_ _publ_author_name 'Peter Wolczanski' 'David N. Hendrickson' 'Emil B. Lobkovsky' 'Evan Rumberger' ; O.L.Sydora ; data_Co12_(2) _database_code_depnum_ccdc_archive 'CCDC 220005' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C45 H90 Cl3 Co3 S3 Si3' _chemical_formula_weight 1094.76 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' Si Si 0.0817 0.0704 '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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M 'P-42(1)c ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' '-x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z+1/2' '-y+1/2, -x+1/2, z+1/2' 'y+1/2, x+1/2, z+1/2' _cell_length_a 23.287(3) _cell_length_b 23.287(3) _cell_length_c 24.155(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 13098(3) _cell_formula_units_Z 8 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour green _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.110 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4656 _exptl_absorpt_coefficient_mu 1.048 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.7439 _exptl_absorpt_correction_T_max 0.8586 _exptl_absorpt_process_details ? _exptl_special_details ; [Co(?-Cl)(?-SSitBu3)]12(C6H6)6 (2). A small green block crystal (0.3 x 0.2 x 0.15 mm), obtained from slow cooling a hot saturated benzene solution of 2, was extracted from the mother liquor, immersed in polyisobutylene, extracted out with a glass fiber, and placed under a 173 K nitrogen stream on the goniometer head of a Siemens SMART CCD Area Detector system equipped with a fine-focus molybdenum X-ray tube (? = 0.71073Å). Preliminary diffraction data revealed a tetragonal crystal system. A hemisphere routine was used for data collection. The data was subsequently processed with the Bruker SAINT program to yield 48,983 reflections of which 8,000 were symmetry independent (Rint = 0.1040). Lattice constants were determined to be: a = 23.287(3) Å, c = 24.155(4) Å; providing a cell volume of 13,098(3) Å3. The space group was determined to be P-421/c with the asymmetric unit consisting of C45H90Si3S3Co3 yielding a calculated density of 1.110 g/cm3. The data was corrected for absorption with SADABS. The structure was solved by direct methods, completed by subsequent difference Fourier syntheses and refined by full-matrix least-squares procedures (SHELXTL). All non-hydrogen atoms were refined with anisotropic displacement parameters and hydrogen atoms were included at calculated positions. Two and a half benzene molecules were found in the asymmetric unit. Data refinement indicated partial occupancy of the benzene sites. When the benzene molecules' occupancies were refined independently, the two benzene occupancies refined to 68 and 71%, while the half benzene's occupancy refined to 46%. These values gave a tBu3SiS:C6H6 ratio (1:0.54) very close to that obtained by experimental methods (1:0.5), so the occupancy values were set to 62.5% for the two benzene molecules and 50% for the half benzene molecule to correspond exactly to the experimental value. The final residuals were R1 = 0.0533, wR2 = 0.1255, and GOF(F2) = 1.013. ; _diffrn_ambient_temperature 173(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 48983 _diffrn_reflns_av_R_equivalents 0.1040 _diffrn_reflns_av_sigmaI/netI 0.0750 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.90 _diffrn_reflns_theta_max 21.96 _reflns_number_total 8000 _reflns_number_gt 6625 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _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^)+(0.0800P)^2^+7.6236P] 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 0.04(2) _refine_ls_number_reflns 8000 _refine_ls_number_parameters 571 _refine_ls_number_restraints 96 _refine_ls_R_factor_all 0.0717 _refine_ls_R_factor_gt 0.0533 _refine_ls_wR_factor_ref 0.1337 _refine_ls_wR_factor_gt 0.1254 _refine_ls_goodness_of_fit_ref 1.013 _refine_ls_restrained_S_all 1.014 _refine_ls_shift/su_max 0.102 _refine_ls_shift/su_mean 0.008 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Co1 Co 0.74509(3) 0.97199(3) 1.00429(3) 0.02074(19) Uani 1 1 d . . . Co2 Co 0.76599(3) 1.10573(3) 1.01198(3) 0.02125(19) Uani 1 1 d . . . Co3 Co 0.84699(3) 1.21008(3) 1.00929(3) 0.02097(19) Uani 1 1 d . . . Cl1 Cl 0.81021(6) 0.91760(6) 1.05423(5) 0.0257(4) Uani 1 1 d . . . Cl2 Cl 0.79643(6) 1.03520(6) 0.95041(5) 0.0301(4) Uani 1 1 d . . . Cl3 Cl 0.84186(6) 1.13169(6) 1.06800(6) 0.0293(4) Uani 1 1 d . . . S1 S 0.70620(6) 0.89063(6) 0.96398(5) 0.0221(4) Uani 1 1 d . . . S2 S 0.69578(6) 1.04603(6) 1.04684(5) 0.0204(4) Uani 1 1 d . . . S3 S 0.75305(6) 1.19910(6) 0.98236(5) 0.0232(4) Uani 1 1 d . . . Si1 Si 0.66625(7) 0.88060(7) 0.88243(6) 0.0265(4) Uani 1 1 d . . . Si2 Si 0.66553(7) 1.04255(6) 1.13261(6) 0.0208(4) Uani 1 1 d . . . Si3 Si 0.71427(7) 1.22375(7) 0.90292(6) 0.0267(4) Uani 1 1 d . . . C1 C 0.6676(3) 0.7992(2) 0.8685(2) 0.0352(17) Uani 1 1 d . . . C2 C 0.6528(3) 0.7641(3) 0.9229(3) 0.057(2) Uani 1 1 d . . . H2A H 0.6536 0.7229 0.9147 0.086 Uiso 1 1 calc R . . H2B H 0.6144 0.7748 0.9359 0.086 Uiso 1 1 calc R . . H2C H 0.6811 0.7728 0.9516 0.086 Uiso 1 1 calc R . . C3 C 0.7253(3) 0.7773(3) 0.8492(3) 0.055(2) Uani 1 1 d . . . H3A H 0.7230 0.7357 0.8429 0.083 Uiso 1 1 calc R . . H3B H 0.7543 0.7853 0.8775 0.083 Uiso 1 1 calc R . . H3C H 0.7359 0.7965 0.8146 0.083 Uiso 1 1 calc R . . C4 C 0.6236(3) 0.7817(3) 0.8228(3) 0.058(2) Uani 1 1 d . . . H4A H 0.6253 0.7401 0.8170 0.087 Uiso 1 1 calc R . . H4B H 0.6330 0.8015 0.7882 0.087 Uiso 1 1 calc R . . H4C H 0.5848 0.7925 0.8346 0.087 Uiso 1 1 calc R . . C5 C 0.7081(3) 0.9224(3) 0.8282(2) 0.0380(18) Uani 1 1 d . . . C6 C 0.7743(3) 0.9164(3) 0.8345(3) 0.051(2) Uani 1 1 d . . . H6A H 0.7935 0.9391 0.8057 0.077 Uiso 1 1 calc R . . H6B H 0.7852 0.8760 0.8307 0.077 Uiso 1 1 calc R . . H6C H 0.7860 0.9305 0.8710 0.077 Uiso 1 1 calc R . . C7 C 0.6897(3) 0.9020(3) 0.7679(2) 0.051(2) Uani 1 1 d . . . H7A H 0.7110 0.9241 0.7401 0.077 Uiso 1 1 calc R . . H7B H 0.6484 0.9083 0.7629 0.077 Uiso 1 1 calc R . . H7C H 0.6984 0.8611 0.7636 0.077 Uiso 1 1 calc R . . C8 C 0.6958(3) 0.9868(3) 0.8303(3) 0.049(2) Uani 1 1 d . . . H8A H 0.7180 1.0064 0.8015 0.073 Uiso 1 1 calc R . . H8B H 0.7067 1.0019 0.8667 0.073 Uiso 1 1 calc R . . H8C H 0.6547 0.9935 0.8241 0.073 Uiso 1 1 calc R . . C9 C 0.5901(2) 0.9106(3) 0.8947(2) 0.0348(18) Uani 1 1 d . . . C10 C 0.5929(3) 0.9704(3) 0.9214(3) 0.0417(19) Uani 1 1 d . . . H10A H 0.5539 0.9849 0.9273 0.063 Uiso 1 1 calc R . . H10B H 0.6138 0.9966 0.8968 0.063 Uiso 1 1 calc R . . H10C H 0.6129 0.9679 0.9570 0.063 Uiso 1 1 calc R . . C11 C 0.5564(3) 0.8722(3) 0.9340(3) 0.049(2) Uani 1 1 d . . . H11A H 0.5180 0.8884 0.9397 0.073 Uiso 1 1 calc R . . H11B H 0.5765 0.8699 0.9696 0.073 Uiso 1 1 calc R . . H11C H 0.5530 0.8337 0.9180 0.073 Uiso 1 1 calc R . . C12 C 0.5543(3) 0.9165(3) 0.8403(3) 0.057(2) Uani 1 1 d . . . H12A H 0.5162 0.9320 0.8491 0.086 Uiso 1 1 calc R . . H12B H 0.5501 0.8787 0.8229 0.086 Uiso 1 1 calc R . . H12C H 0.5741 0.9426 0.8148 0.086 Uiso 1 1 calc R . . C13 C 0.6222(2) 0.9725(2) 1.1343(2) 0.0266(16) Uani 1 1 d . . . C14 C 0.5790(3) 0.9715(3) 1.1834(2) 0.0383(19) Uani 1 1 d . . . H14A H 0.5572 0.9355 1.1827 0.057 Uiso 1 1 calc R . . H14B H 0.5525 1.0040 1.1801 0.057 Uiso 1 1 calc R . . H14C H 0.6001 0.9744 1.2184 0.057 Uiso 1 1 calc R . . C15 C 0.6619(3) 0.9186(2) 1.1395(2) 0.0315(17) Uani 1 1 d . . . H15A H 0.6382 0.8838 1.1402 0.047 Uiso 1 1 calc R . . H15B H 0.6841 0.9211 1.1739 0.047 Uiso 1 1 calc R . . H15C H 0.6881 0.9171 1.1079 0.047 Uiso 1 1 calc R . . C16 C 0.5854(3) 0.9633(3) 1.0805(2) 0.0376(18) Uani 1 1 d . . . H16A H 0.5638 0.9274 1.0836 0.056 Uiso 1 1 calc R . . H16B H 0.6109 0.9614 1.0483 0.056 Uiso 1 1 calc R . . H16C H 0.5586 0.9954 1.0761 0.056 Uiso 1 1 calc R . . C17 C 0.7291(3) 1.0417(2) 1.1843(2) 0.0267(16) Uani 1 1 d . . . C18 C 0.7093(3) 1.0177(3) 1.2414(2) 0.0388(19) Uani 1 1 d . . . H18A H 0.7421 1.0168 1.2669 0.058 Uiso 1 1 calc R . . H18B H 0.6942 0.9788 1.2367 0.058 Uiso 1 1 calc R . . H18C H 0.6793 1.0426 1.2567 0.058 Uiso 1 1 calc R . . C19 C 0.7796(2) 1.0043(3) 1.1635(2) 0.0355(17) Uani 1 1 d . . . H19A H 0.8103 1.0042 1.1912 0.053 Uiso 1 1 calc R . . H19B H 0.7942 1.0200 1.1286 0.053 Uiso 1 1 calc R . . H19C H 0.7662 0.9649 1.1574 0.053 Uiso 1 1 calc R . . C20 C 0.7547(3) 1.1007(3) 1.1951(2) 0.0392(18) Uani 1 1 d . . . H20A H 0.7864 1.0973 1.2216 0.059 Uiso 1 1 calc R . . H20B H 0.7251 1.1261 1.2103 0.059 Uiso 1 1 calc R . . H20C H 0.7691 1.1168 1.1603 0.059 Uiso 1 1 calc R . . C21 C 0.6184(3) 1.1108(2) 1.1390(2) 0.0316(17) Uani 1 1 d . . . C22 C 0.5657(2) 1.1062(3) 1.1015(3) 0.0406(19) Uani 1 1 d . . . H22A H 0.5422 1.1409 1.1054 0.061 Uiso 1 1 calc R . . H22B H 0.5430 1.0726 1.1122 0.061 Uiso 1 1 calc R . . H22C H 0.5780 1.1022 1.0630 0.061 Uiso 1 1 calc R . . C23 C 0.6520(3) 1.1654(3) 1.1212(2) 0.0426(19) Uani 1 1 d . . . H23A H 0.6272 1.1992 1.1251 0.064 Uiso 1 1 calc R . . H23B H 0.6641 1.1616 1.0825 0.064 Uiso 1 1 calc R . . H23C H 0.6860 1.1699 1.1448 0.064 Uiso 1 1 calc R . . C24 C 0.5972(3) 1.1207(3) 1.1993(2) 0.0382(18) Uani 1 1 d . . . H24A H 0.5736 1.1556 1.2008 0.057 Uiso 1 1 calc R . . H24B H 0.6304 1.1252 1.2239 0.057 Uiso 1 1 calc R . . H24C H 0.5743 1.0877 1.2113 0.057 Uiso 1 1 calc R . . C25 C 0.6405(2) 1.1861(3) 0.9063(2) 0.0320(17) Uani 1 1 d . . . C26 C 0.6135(2) 1.1886(3) 0.9643(2) 0.0432(19) Uani 1 1 d . . . H26A H 0.5763 1.1691 0.9638 0.065 Uiso 1 1 calc R . . H26B H 0.6082 1.2288 0.9752 0.065 Uiso 1 1 calc R . . H26C H 0.6390 1.1695 0.9909 0.065 Uiso 1 1 calc R . . C27 C 0.6450(3) 1.1217(3) 0.8922(3) 0.053(2) Uani 1 1 d . . . H27A H 0.6069 1.1041 0.8944 0.079 Uiso 1 1 calc R . . H27B H 0.6708 1.1029 0.9186 0.079 Uiso 1 1 calc R . . H27C H 0.6603 1.1172 0.8546 0.079 Uiso 1 1 calc R . . C28 C 0.5977(2) 1.2139(3) 0.8657(3) 0.044(2) Uani 1 1 d . . . H28A H 0.5606 1.1943 0.8682 0.066 Uiso 1 1 calc R . . H28B H 0.6126 1.2107 0.8278 0.066 Uiso 1 1 calc R . . H28C H 0.5928 1.2546 0.8751 0.066 Uiso 1 1 calc R . . C29 C 0.7613(2) 1.1990(2) 0.8416(2) 0.0290(16) Uani 1 1 d . . . C30 C 0.7857(3) 1.1387(3) 0.8514(2) 0.0400(18) Uani 1 1 d . . . H30A H 0.8090 1.1272 0.8195 0.060 Uiso 1 1 calc R . . H30B H 0.7541 1.1114 0.8563 0.060 Uiso 1 1 calc R . . H30C H 0.8097 1.1389 0.8848 0.060 Uiso 1 1 calc R . . C31 C 0.7280(3) 1.1975(3) 0.7864(2) 0.051(2) Uani 1 1 d . . . H31A H 0.7536 1.1845 0.7567 0.076 Uiso 1 1 calc R . . H31B H 0.7138 1.2361 0.7778 0.076 Uiso 1 1 calc R . . H31C H 0.6955 1.1710 0.7897 0.076 Uiso 1 1 calc R . . C32 C 0.8122(2) 1.2387(3) 0.8319(2) 0.0388(18) Uani 1 1 d . . . H32A H 0.8347 1.2247 0.8004 0.058 Uiso 1 1 calc R . . H32B H 0.8364 1.2395 0.8651 0.058 Uiso 1 1 calc R . . H32C H 0.7983 1.2776 0.8240 0.058 Uiso 1 1 calc R . . C33 C 0.7086(3) 1.3061(3) 0.9072(2) 0.0359(18) Uani 1 1 d . . . C34 C 0.6892(3) 1.3339(3) 0.8514(3) 0.045(2) Uani 1 1 d . . . H34A H 0.6868 1.3757 0.8559 0.067 Uiso 1 1 calc R . . H34B H 0.6514 1.3189 0.8410 0.067 Uiso 1 1 calc R . . H34C H 0.7171 1.3247 0.8224 0.067 Uiso 1 1 calc R . . C35 C 0.7656(3) 1.3341(3) 0.9228(2) 0.0415(19) Uani 1 1 d . . . H35A H 0.7605 1.3758 0.9247 0.062 Uiso 1 1 calc R . . H35B H 0.7945 1.3249 0.8947 0.062 Uiso 1 1 calc R . . H35C H 0.7782 1.3197 0.9589 0.062 Uiso 1 1 calc R . . C36 C 0.6657(3) 1.3239(3) 0.9519(3) 0.045(2) Uani 1 1 d . . . H36A H 0.6636 1.3659 0.9535 0.068 Uiso 1 1 calc R . . H36B H 0.6784 1.3091 0.9879 0.068 Uiso 1 1 calc R . . H36C H 0.6278 1.3082 0.9430 0.068 Uiso 1 1 calc R . . C1S C 0.5085(6) 1.3679(7) 0.8454(7) 0.118(6) Uani 0.63 1 d PDU . . H1SA H 0.5007 1.3525 0.8098 0.141 Uiso 0.63 1 calc PR . . C2S C 0.5364(5) 1.4166(8) 0.8530(10) 0.147(8) Uani 0.63 1 d PDU . . H2SA H 0.5511 1.4384 0.8229 0.177 Uiso 0.63 1 calc PR . . C3S C 0.5422(6) 1.4317(6) 0.9008(8) 0.106(6) Uani 0.63 1 d PDU . . H3SA H 0.5632 1.4663 0.9061 0.128 Uiso 0.63 1 calc PR . . C4S C 0.5236(6) 1.4072(8) 0.9457(8) 0.120(6) Uani 0.63 1 d PDU . . H4SA H 0.5300 1.4242 0.9809 0.144 Uiso 0.63 1 calc PR . . C5S C 0.4955(7) 1.3580(8) 0.9414(8) 0.128(7) Uani 0.63 1 d PDU . . H5SA H 0.4799 1.3371 0.9717 0.153 Uiso 0.63 1 calc PR . . C6S C 0.4924(6) 1.3429(9) 0.8914(9) 0.129(7) Uani 0.63 1 d PDU . . H6SA H 0.4750 1.3064 0.8861 0.155 Uiso 0.63 1 calc PR . . C7S C 0.8412(8) 1.0697(8) 0.6737(9) 0.162(8) Uani 0.63 1 d PDU . . H7SA H 0.8629 1.0871 0.7025 0.194 Uiso 0.63 1 calc PR . . C8S C 0.7978(6) 1.0256(6) 0.6824(6) 0.109(6) Uani 0.63 1 d PDU . . H8SA H 0.7890 1.0120 0.7186 0.131 Uiso 0.63 1 calc PR . . C9S C 0.7727(5) 1.0063(6) 0.6413(6) 0.085(5) Uani 0.63 1 d PDU . . H9SA H 0.7453 0.9771 0.6492 0.102 Uiso 0.63 1 calc PR . . C10S C 0.7770(5) 1.0185(6) 0.5913(6) 0.083(5) Uani 0.63 1 d PDU . . H10D H 0.7534 1.0012 0.5639 0.099 Uiso 0.63 1 calc PR . . C11S C 0.8178(6) 1.0584(6) 0.5782(6) 0.097(5) Uani 0.63 1 d PDU . . H11D H 0.8248 1.0678 0.5405 0.116 Uiso 0.63 1 calc PR . . C12S C 0.8468(7) 1.0832(6) 0.6166(8) 0.107(6) Uani 0.63 1 d PDU . . H12D H 0.8734 1.1121 0.6063 0.128 Uiso 0.63 1 calc PR . . C13S C 0.9388(7) 1.0105(8) 1.0260(8) 0.093(6) Uani 0.50 1 d PU . . H13A H 0.8990 1.0183 1.0306 0.111 Uiso 0.50 1 calc PR . . C14S C 0.9467(6) 0.9819(8) 0.9793(8) 0.080(6) Uani 0.50 1 d PU . . H14D H 0.9088 0.9685 0.9859 0.097 Uiso 0.50 1 calc PR . . C15S C 0.9637(8) 0.9523(7) 1.0235(9) 0.096(6) Uani 0.50 1 d PU . . H15D H 0.9395 0.9195 1.0241 0.115 Uiso 0.50 1 calc PR . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Co1 0.0240(4) 0.0208(4) 0.0174(4) -0.0011(3) 0.0009(3) -0.0001(3) Co2 0.0224(4) 0.0209(4) 0.0204(4) 0.0037(3) -0.0016(3) -0.0031(3) Co3 0.0208(4) 0.0224(4) 0.0197(4) 0.0005(4) 0.0002(3) -0.0029(3) Cl1 0.0263(8) 0.0260(8) 0.0248(7) -0.0016(6) -0.0058(6) 0.0043(6) Cl2 0.0328(8) 0.0312(8) 0.0265(8) 0.0010(7) 0.0094(7) -0.0010(7) Cl3 0.0285(8) 0.0310(8) 0.0286(8) 0.0081(7) -0.0077(7) -0.0062(7) S1 0.0229(7) 0.0240(8) 0.0195(7) -0.0042(6) -0.0070(6) 0.0022(7) S2 0.0219(8) 0.0192(7) 0.0202(7) -0.0005(6) 0.0043(6) -0.0008(6) S3 0.0227(7) 0.0239(7) 0.0230(7) 0.0052(6) -0.0038(6) -0.0040(7) Si1 0.0276(9) 0.0308(9) 0.0211(8) -0.0063(7) -0.0059(7) 0.0027(8) Si2 0.0215(8) 0.0240(9) 0.0169(8) -0.0023(7) 0.0037(7) 0.0019(7) Si3 0.0227(8) 0.0325(9) 0.0247(8) 0.0118(7) -0.0057(7) -0.0026(8) C1 0.040(4) 0.031(3) 0.035(3) -0.014(3) -0.016(3) 0.000(3) C2 0.075(5) 0.032(4) 0.066(5) -0.014(4) -0.025(4) 0.003(4) C3 0.057(5) 0.048(4) 0.061(4) -0.024(4) -0.016(4) 0.007(4) C4 0.078(5) 0.049(4) 0.048(4) -0.022(4) -0.019(4) -0.014(4) C5 0.047(4) 0.057(4) 0.010(3) -0.004(3) -0.002(3) 0.002(4) C6 0.049(4) 0.073(5) 0.031(4) 0.003(4) 0.004(3) 0.002(4) C7 0.063(5) 0.072(5) 0.019(3) -0.003(3) -0.005(3) -0.004(4) C8 0.063(5) 0.050(4) 0.033(4) 0.003(3) -0.005(3) 0.003(4) C9 0.022(3) 0.052(4) 0.031(3) -0.008(3) -0.009(3) 0.005(3) C10 0.032(4) 0.050(4) 0.044(4) -0.004(3) -0.014(3) 0.010(3) C11 0.023(3) 0.064(5) 0.058(4) -0.017(4) 0.005(3) 0.005(4) C12 0.056(5) 0.067(5) 0.048(4) -0.015(4) -0.021(4) 0.008(4) C13 0.029(3) 0.031(3) 0.021(3) -0.001(3) 0.009(3) -0.002(3) C14 0.043(4) 0.043(4) 0.029(3) 0.008(3) 0.015(3) -0.005(3) C15 0.035(4) 0.015(3) 0.044(4) 0.000(3) 0.013(3) -0.005(3) C16 0.033(4) 0.043(4) 0.037(4) -0.010(3) 0.011(3) -0.021(3) C17 0.033(3) 0.028(3) 0.020(3) -0.006(3) 0.002(3) -0.002(3) C18 0.045(4) 0.053(4) 0.018(3) 0.000(3) -0.002(3) 0.001(3) C19 0.039(4) 0.039(4) 0.029(3) 0.005(3) -0.011(3) 0.010(3) C20 0.044(4) 0.039(4) 0.034(3) -0.009(3) 0.007(3) -0.008(3) C21 0.041(4) 0.027(3) 0.027(3) 0.002(3) 0.013(3) 0.005(3) C22 0.032(4) 0.039(4) 0.051(4) 0.002(3) 0.002(3) 0.005(3) C23 0.045(4) 0.039(4) 0.044(4) 0.004(3) 0.003(3) 0.009(3) C24 0.044(4) 0.038(4) 0.032(3) -0.013(3) 0.017(3) 0.001(3) C25 0.025(3) 0.040(4) 0.031(3) 0.016(3) -0.011(3) -0.008(3) C26 0.016(3) 0.065(4) 0.048(4) 0.026(3) 0.000(3) -0.013(3) C27 0.046(4) 0.064(5) 0.049(4) 0.013(4) -0.008(3) -0.016(4) C28 0.024(3) 0.057(4) 0.052(4) 0.012(4) -0.018(3) -0.011(3) C29 0.037(3) 0.029(3) 0.022(3) 0.009(3) -0.009(3) -0.013(3) C30 0.052(4) 0.041(4) 0.027(3) -0.002(3) 0.005(3) -0.002(3) C31 0.044(4) 0.074(5) 0.034(4) 0.014(4) -0.008(3) -0.014(4) C32 0.032(4) 0.054(4) 0.030(3) 0.003(3) 0.010(3) -0.009(3) C33 0.030(3) 0.040(4) 0.037(4) 0.003(3) 0.002(3) 0.002(3) C34 0.036(4) 0.045(4) 0.053(4) 0.020(4) -0.006(3) -0.005(3) C35 0.042(4) 0.036(4) 0.047(4) 0.007(3) 0.002(3) 0.007(3) C36 0.035(4) 0.035(4) 0.067(5) 0.008(4) -0.012(4) 0.003(3) C1S 0.094(11) 0.130(12) 0.129(11) -0.070(10) -0.025(9) 0.033(10) C2S 0.118(13) 0.148(14) 0.175(15) 0.022(13) 0.004(12) 0.067(11) C3S 0.086(10) 0.068(9) 0.165(13) -0.037(9) -0.036(10) 0.039(8) C4S 0.085(10) 0.124(12) 0.150(13) -0.037(11) -0.025(10) 0.051(9) C5S 0.068(10) 0.150(14) 0.166(14) 0.032(12) 0.029(10) 0.029(10) C6S 0.045(8) 0.142(13) 0.201(16) -0.003(13) -0.022(11) 0.039(9) C7S 0.147(15) 0.179(16) 0.160(14) -0.057(13) -0.023(13) 0.000(13) C8S 0.109(11) 0.127(12) 0.091(10) 0.036(9) 0.037(9) -0.015(10) C9S 0.071(9) 0.071(8) 0.113(10) 0.031(8) 0.030(8) 0.034(7) C10S 0.065(8) 0.078(9) 0.104(10) -0.010(8) 0.015(8) 0.046(7) C11S 0.098(10) 0.097(9) 0.096(9) 0.061(8) 0.006(8) 0.046(8) C12S 0.081(10) 0.065(9) 0.174(14) 0.022(10) 0.046(10) -0.008(8) C13S 0.062(10) 0.077(11) 0.139(14) -0.016(11) -0.026(10) 0.006(9) C14S 0.023(7) 0.079(11) 0.139(14) 0.013(10) 0.032(9) -0.007(8) C15S 0.074(11) 0.052(10) 0.163(15) -0.019(11) -0.040(11) -0.028(9) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Co1 Cl2 2.2999(16) . ? Co1 S2 2.3123(15) . ? Co1 S1 2.3148(15) . ? Co1 Cl1 2.3149(15) . ? Co2 S2 2.3053(15) . ? Co2 Cl3 2.3061(16) . ? Co2 S3 2.3089(15) . ? Co2 Cl2 2.3264(16) . ? Co3 S1 2.2912(16) 3_577 ? Co3 S3 2.2965(15) . ? Co3 Cl1 2.2983(15) 3_577 ? Co3 Cl3 2.3148(15) . ? Cl1 Co3 2.2983(15) 4_757 ? S1 Si1 2.191(2) . ? S1 Co3 2.2912(15) 4_757 ? S2 Si2 2.1898(19) . ? S3 Si3 2.197(2) . ? Si1 C5 1.902(6) . ? Si1 C9 1.929(6) . ? Si1 C1 1.926(6) . ? Si2 C13 1.919(6) . ? Si2 C17 1.937(6) . ? Si2 C21 1.938(6) . ? Si3 C33 1.924(6) . ? Si3 C29 1.931(6) . ? Si3 C25 1.931(6) . ? C1 C3 1.511(9) . ? C1 C4 1.558(8) . ? C1 C2 1.586(9) . ? C5 C8 1.527(9) . ? C5 C6 1.556(9) . ? C5 C7 1.590(8) . ? C9 C11 1.519(9) . ? C9 C10 1.536(8) . ? C9 C12 1.563(8) . ? C13 C14 1.557(8) . ? C13 C15 1.564(8) . ? C13 C16 1.570(8) . ? C17 C20 1.521(8) . ? C17 C19 1.547(8) . ? C17 C18 1.558(7) . ? C21 C22 1.527(8) . ? C21 C24 1.556(7) . ? C21 C23 1.554(8) . ? C25 C28 1.541(8) . ? C25 C26 1.536(8) . ? C25 C27 1.540(9) . ? C29 C32 1.520(8) . ? C29 C30 1.535(8) . ? C29 C31 1.543(8) . ? C33 C35 1.524(8) . ? C33 C36 1.528(9) . ? C33 C34 1.563(9) . ? C1S C6S 1.31(2) . ? C1S C2S 1.32(2) . ? C2S C3S 1.21(3) . ? C3S C4S 1.30(2) . ? C4S C5S 1.32(2) . ? C5S C6S 1.26(3) . ? C7S C12S 1.42(3) . ? C7S C8S 1.46(2) . ? C8S C9S 1.24(2) . ? C9S C10S 1.246(18) . ? C10S C11S 1.365(19) . ? C11S C12S 1.28(2) . ? C13S C14S 1.42(2) 3_577 ? C13S C15S 1.47(2) . ? C14S C15S 1.27(2) 3_577 ? C14S C13S 1.42(2) 4_757 ? C15S C14S 1.27(2) 4_757 ? 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 Cl2 Co1 S2 91.86(5) . . ? Cl2 Co1 S1 119.28(6) . . ? S2 Co1 S1 127.08(6) . . ? Cl2 Co1 Cl1 107.73(6) . . ? S2 Co1 Cl1 120.11(6) . . ? S1 Co1 Cl1 91.58(5) . . ? S2 Co2 Cl3 119.15(6) . . ? S2 Co2 S3 126.05(6) . . ? Cl3 Co2 S3 92.00(5) . . ? S2 Co2 Cl2 91.37(5) . . ? Cl3 Co2 Cl2 109.07(6) . . ? S3 Co2 Cl2 120.43(6) . . ? S1 Co3 S3 126.66(6) 3_577 . ? S1 Co3 Cl1 92.62(5) 3_577 3_577 ? S3 Co3 Cl1 118.01(6) . 3_577 ? S1 Co3 Cl3 121.41(6) 3_577 . ? S3 Co3 Cl3 92.10(5) . . ? Cl1 Co3 Cl3 106.49(6) 3_577 . ? Co3 Cl1 Co1 84.77(5) 4_757 . ? Co1 Cl2 Co2 86.08(5) . . ? Co2 Cl3 Co3 83.50(5) . . ? Si1 S1 Co3 124.57(8) . 4_757 ? Si1 S1 Co1 129.17(8) . . ? Co3 S1 Co1 84.93(5) 4_757 . ? Si2 S2 Co2 126.58(7) . . ? Si2 S2 Co1 123.55(7) . . ? Co2 S2 Co1 86.28(5) . . ? Si3 S3 Co3 127.58(7) . . ? Si3 S3 Co2 124.78(8) . . ? Co3 S3 Co2 83.84(5) . . ? C5 Si1 C9 113.1(3) . . ? C5 Si1 C1 112.0(3) . . ? C9 Si1 C1 113.5(3) . . ? C5 Si1 S1 110.3(2) . . ? C9 Si1 S1 102.32(18) . . ? C1 Si1 S1 104.81(19) . . ? C13 Si2 C17 112.3(2) . . ? C13 Si2 C21 113.4(3) . . ? C17 Si2 C21 113.0(2) . . ? C13 Si2 S2 102.72(17) . . ? C17 Si2 S2 111.38(18) . . ? C21 Si2 S2 103.11(17) . . ? C33 Si3 C29 112.2(3) . . ? C33 Si3 C25 112.9(3) . . ? C29 Si3 C25 113.7(3) . . ? C33 Si3 S3 103.93(19) . . ? C29 Si3 S3 111.03(18) . . ? C25 Si3 S3 102.13(18) . . ? C3 C1 C4 106.1(5) . . ? C3 C1 C2 106.0(5) . . ? C4 C1 C2 107.9(5) . . ? C3 C1 Si1 113.7(4) . . ? C4 C1 Si1 111.8(4) . . ? C2 C1 Si1 111.0(4) . . ? C8 C5 C6 105.7(5) . . ? C8 C5 C7 105.9(5) . . ? C6 C5 C7 109.3(5) . . ? C8 C5 Si1 112.6(4) . . ? C6 C5 Si1 113.2(4) . . ? C7 C5 Si1 109.9(4) . . ? C11 C9 C10 107.1(5) . . ? C11 C9 C12 107.6(5) . . ? C10 C9 C12 107.1(5) . . ? C11 C9 Si1 111.0(4) . . ? C10 C9 Si1 110.7(4) . . ? C12 C9 Si1 113.1(4) . . ? C14 C13 C15 107.9(5) . . ? C14 C13 C16 106.0(5) . . ? C15 C13 C16 106.3(5) . . ? C14 C13 Si2 111.6(4) . . ? C15 C13 Si2 112.0(4) . . ? C16 C13 Si2 112.7(4) . . ? C20 C17 C19 105.5(5) . . ? C20 C17 C18 106.7(4) . . ? C19 C17 C18 108.2(5) . . ? C20 C17 Si2 113.6(4) . . ? C19 C17 Si2 112.1(4) . . ? C18 C17 Si2 110.4(4) . . ? C22 C21 C24 108.1(5) . . ? C22 C21 C23 107.4(5) . . ? C24 C21 C23 107.2(5) . . ? C22 C21 Si2 110.6(4) . . ? C24 C21 Si2 112.0(4) . . ? C23 C21 Si2 111.3(4) . . ? C28 C25 C26 107.5(5) . . ? C28 C25 C27 108.3(5) . . ? C26 C25 C27 105.5(5) . . ? C28 C25 Si3 110.9(4) . . ? C26 C25 Si3 112.6(4) . . ? C27 C25 Si3 111.8(4) . . ? C32 C29 C30 107.0(5) . . ? C32 C29 C31 105.9(5) . . ? C30 C29 C31 107.4(5) . . ? C32 C29 Si3 112.3(4) . . ? C30 C29 Si3 111.4(4) . . ? C31 C29 Si3 112.6(4) . . ? C35 C33 C36 106.1(5) . . ? C35 C33 C34 106.6(5) . . ? C36 C33 C34 107.8(5) . . ? C35 C33 Si3 112.4(4) . . ? C36 C33 Si3 110.7(4) . . ? C34 C33 Si3 112.7(4) . . ? C6S C1S C2S 114.0(19) . . ? C3S C2S C1S 116(2) . . ? C2S C3S C4S 129.0(18) . . ? C3S C4S C5S 118.7(19) . . ? C6S C5S C4S 110(2) . . ? C5S C6S C1S 132(2) . . ? C12S C7S C8S 111.1(16) . . ? C9S C8S C7S 117.9(16) . . ? C8S C9S C10S 131.1(15) . . ? C9S C10S C11S 115.9(15) . . ? C12S C11S C10S 120.2(15) . . ? C11S C12S C7S 123.7(16) . . ? C14S C13S C15S 111.3(15) 3_577 . ? C15S C14S C13S 128.6(15) 3_577 4_757 ? C14S C15S C13S 119.2(16) 4_757 . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 21.96 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.633 _refine_diff_density_min -0.393 _refine_diff_density_rms 0.087 #===END data_Ni12_(5) _database_code_depnum_ccdc_archive 'CCDC 220006' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H54 Br2 Ni2 S2 Si2' _chemical_formula_weight 740.21 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' Si Si 0.0817 0.0704 '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' 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 Hexagonal _symmetry_space_group_name_H-M 'P6(3)mc ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' '-x, -y, z+1/2' 'y, -x+y, z+1/2' 'x-y, x, z+1/2' '-y, -x, z' '-x+y, y, z' 'x, x-y, z' 'y, x, z+1/2' 'x-y, -y, z+1/2' '-x, -x+y, z+1/2' _cell_length_a 26.128(16) _cell_length_b 26.128(16) _cell_length_c 24.69(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 14597(18) _cell_formula_units_Z 12 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.6 _exptl_crystal_size_mid 0.6 _exptl_crystal_size_min 0.5 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.010 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4608 _exptl_absorpt_coefficient_mu 2.559 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; [Ni(?-Br)(?-SSitBu3)]12(C6H14)n (5). A red block crystal (0.5 x 0.6 x 0.6 mm), obtained from slow evaporation of a saturated pentane solution of 5, was extracted from the mother liquor, immersed in polyisobutylene, extracted out with a glass fiber, and placed under a 173 K nitrogen stream on the goniometer head of a Siemens SMART CCD Area Detector system equipped with a fine-focus molybdenum X-ray tube (? = 0.71073 Å). Preliminary diffraction data revealed a hexagonal crystal system. A hemisphere routine was used for data collection. The data was subsequently processed with the Bruker SAINT program to yield 9,646 reflections of which 3,730 were symmetry independent (Rint = 0.1259). Lattice constants were determined to be: a = 26. 128(16) Å, c = 24.69(2) Å; providing a cell volume of 14,597(18) Å3. The space group was determined to be P63mc with the asymmetric unit consisting of C24H54Si2S2Br2Ni2 yielding a calculated density of 1.010 g/cm3. The data was corrected for absorption with SADABS. The structure was solved by direct methods, completed by subsequent difference Fourier syntheses and refined by full-matrix least-squares procedures (SHELXTL). All non-hydrogen and non-carbon atoms were refined with anisotropic displacement parameters and hydrogen atoms were included at calculated positions. Constraints were applied to the geometries of the tBu3Si fragments on each tBu3SiS ligand such that chemically equivalent inter- and intra-atomic distances were constrained to equal the same least-squares variables (e.g., all d(SiCq) are equivalent; all d(CqC) are equivalent, etc.). The unit cell had two cavities containing a large amount of severely disordered solvent molecules. The difference Fourier map in this region showed a number of peaks, but no consistent model could be assembled. Therefore, this part of the structure was modeled using the SQUEEZE procedure of the PLATON program [Spek, A.L. et al. (1990), Acta. Cryst., A46, 194-201]. Two cavities (per cell) of 3012Å3 each (cell volume = 14,597 Å3) each occupied by 464 electrons. The final model consisted of the ordered part only, without the disordered solvent contribution, and was refined against new data provided with the fcf file. The final residuals were R1 = 0.1491, wR2 = 0.3646, and GOF(F2) = 1.128. ; _diffrn_ambient_temperature 173(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 9646 _diffrn_reflns_av_R_equivalents 0.1259 _diffrn_reflns_av_sigmaI/netI 0.2481 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 1.22 _diffrn_reflns_theta_max 22.20 _reflns_number_total 3730 _reflns_number_gt 1627 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _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 ; Constraints were applied to the geometries of the tBu3Si fragments on each tBu3SiS ligand such that chemically equivalent inter- and intra- atomic distances were constrained to equal the same least-squares variables. The unit cell had two cavities containing a large amount of severely disordered solvent molecules. The difference Fourier map in this region showed a number of peaks, but no consistent model could be assembled. Therefore, this part of the structure was modeled using the SQUEEZE procedure of the PLATON program [Spek, A.L. (1990). Acta. Cryst., A46, C34]. Two cavities (per cell) of 3012Ang^3 each (cell volume=14597 Ang^3) each occupied 464 electrons. The final model consisted of the ordered part only, without the disordered solvent contribution and was refined against new data provided with the fcf file. All carbons were refined isotropically because not all carbons were stable to anisotropic refinement. 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^)+(0.2000P)^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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.09(7) _refine_ls_number_reflns 3730 _refine_ls_number_parameters 192 _refine_ls_number_restraints 67 _refine_ls_R_factor_all 0.2261 _refine_ls_R_factor_gt 0.1491 _refine_ls_wR_factor_ref 0.4001 _refine_ls_wR_factor_gt 0.3646 _refine_ls_goodness_of_fit_ref 1.128 _refine_ls_restrained_S_all 1.137 _refine_ls_shift/su_max 1.947 _refine_ls_shift/su_mean 0.171 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.91275(10) 0.45637(5) 0.83488(12) 0.0892(10) Uani 1 2 d S . . Br2 Br 0.85442(6) 0.51236(7) 0.94880(7) 0.0793(7) Uani 1 1 d . . . Br3 Br 0.78113(5) 0.56226(10) 0.84284(10) 0.0911(11) Uani 1 2 d S . . Ni4 Ni 0.94532(7) 0.53520(10) 0.90224(8) 0.0833(10) Uani 1 1 d . . . Ni5 Ni 0.86466(8) 0.60119(9) 0.90504(10) 0.0770(9) Uani 1 1 d . . . S2 S 0.8242(2) 0.6485(4) 0.9499(3) 0.111(3) Uani 1 2 d S . . S1 S 0.95574(19) 0.6264(2) 0.8759(2) 0.100(2) Uani 1 1 d . . . Si1 Si 1.0017(2) 0.6761(3) 0.8009(2) 0.126(4) Uani 1 1 d D . . C9 C 1.0760(4) 0.6798(4) 0.8012(5) 0.199(13) Uiso 1 1 d D . . C12 C 1.1002(6) 0.7213(5) 0.7540(4) 0.101(7) Uiso 1 1 d D . . H12A H 1.1404 0.7296 0.7461 0.152 Uiso 1 1 calc R . . H12B H 1.1011 0.7583 0.7628 0.152 Uiso 1 1 calc R . . H12C H 1.0751 0.7032 0.7222 0.152 Uiso 1 1 calc R . . C11 C 1.0749(6) 0.6211(4) 0.7869(6) 0.105(7) Uiso 1 1 d D . . H11A H 1.1152 0.6275 0.7883 0.158 Uiso 1 1 calc R . . H11B H 1.0589 0.6084 0.7503 0.158 Uiso 1 1 calc R . . H11C H 1.0500 0.5904 0.8130 0.158 Uiso 1 1 calc R . . C10 C 1.1195(6) 0.7089(6) 0.8477(4) 0.123(7) Uiso 1 1 d D . . H10A H 1.1550 0.7061 0.8409 0.185 Uiso 1 1 calc R . . H10B H 1.1011 0.6887 0.8817 0.185 Uiso 1 1 calc R . . H10C H 1.1304 0.7506 0.8503 0.185 Uiso 1 1 calc R . . C5 C 1.0063(4) 0.7529(3) 0.8125(5) 0.098(7) Uiso 1 1 d D . . C8 C 1.0290(6) 0.8077(6) 0.7727(5) 0.185(12) Uiso 1 1 d D . . H8A H 1.0252 0.8393 0.7904 0.277 Uiso 1 1 calc R . . H8B H 1.0052 0.7955 0.7396 0.277 Uiso 1 1 calc R . . H8C H 1.0705 0.8222 0.7636 0.277 Uiso 1 1 calc R . . C7 C 1.0502(5) 0.7698(6) 0.8588(5) 0.138(8) Uiso 1 1 d D . . H7A H 1.0606 0.8092 0.8723 0.207 Uiso 1 1 calc R . . H7B H 1.0859 0.7704 0.8458 0.207 Uiso 1 1 calc R . . H7C H 1.0324 0.7409 0.8881 0.207 Uiso 1 1 calc R . . C6 C 0.9505(4) 0.7503(6) 0.8372(6) 0.112(7) Uiso 1 1 d D . . H6A H 0.9572 0.7905 0.8413 0.168 Uiso 1 1 calc R . . H6B H 0.9423 0.7310 0.8727 0.168 Uiso 1 1 calc R . . H6C H 0.9166 0.7277 0.8131 0.168 Uiso 1 1 calc R . . C1 C 0.9504(4) 0.6369(4) 0.7416(4) 0.064(5) Uiso 1 1 d D . . C4 C 0.9802(6) 0.6562(7) 0.6851(4) 0.221(14) Uiso 1 1 d D . . H4A H 0.9514 0.6331 0.6569 0.331 Uiso 1 1 calc R . . H4B H 1.0137 0.6493 0.6831 0.331 Uiso 1 1 calc R . . H4C H 0.9942 0.6983 0.6796 0.331 Uiso 1 1 calc R . . C3 C 0.9036(3) 0.6581(4) 0.7403(6) 0.088(6) Uiso 1 1 d D . . H3A H 0.8759 0.6386 0.7104 0.133 Uiso 1 1 calc R . . H3B H 0.9239 0.7010 0.7351 0.133 Uiso 1 1 calc R . . H3C H 0.8818 0.6480 0.7746 0.133 Uiso 1 1 calc R . . C2 C 0.9159(5) 0.5694(4) 0.7432(6) 0.076(5) Uiso 1 1 d D . . H2A H 0.8921 0.5542 0.7103 0.114 Uiso 1 1 calc R . . H2B H 0.8899 0.5561 0.7750 0.114 Uiso 1 1 calc R . . H2C H 0.9436 0.5545 0.7454 0.114 Uiso 1 1 calc R . . S3 S 1.0001(2) 0.50007(12) 0.9376(3) 0.104(3) Uani 1 2 d S . . Si3 Si 1.0375(3) 0.51877(16) 1.0237(3) 0.116(4) Uani 1 2 d SD . . C34 C 1.0839(4) 0.4811(4) 1.0271(5) 0.121(8) Uiso 1 1 d D . . Si2 Si 0.84128(13) 0.6826(3) 1.0345(2) 0.089(3) Uani 1 2 d SD . . C24 C 0.7989(4) 0.7232(4) 1.0320(5) 0.165(10) Uiso 1 1 d D . . C20 C 0.8065(3) 0.6130(6) 1.0803(4) 0.147(13) Uiso 1 2 d SD . . C36 C 1.1177(5) 0.4942(5) 1.0831(4) 0.044(4) Uiso 1 1 d D . . H36A H 1.1416 0.4749 1.0838 0.066 Uiso 1 1 calc R . . H36B H 1.0890 0.4789 1.1128 0.066 Uiso 1 1 calc R . . H36C H 1.1435 0.5370 1.0874 0.066 Uiso 1 1 calc R . . C21 C 0.8170(3) 0.6340(6) 1.1421(4) 0.151(13) Uiso 1 2 d SD . . H21A H 0.7993(5) 0.5986(9) 1.1633(6) 0.226 Uiso 1 2 d SD . . H21B H 0.8591(6) 0.646(2) 1.1478(9) 0.226 Uiso 1 1 d D . . C25 C 0.7385(4) 0.7076(7) 1.0133(7) 0.239(15) Uiso 1 1 d D . . H25A H 0.7317 0.7406 1.0208 0.358 Uiso 1 1 calc R . . H25B H 0.7089 0.6723 1.0325 0.358 Uiso 1 1 calc R . . H25C H 0.7351 0.6998 0.9742 0.358 Uiso 1 1 calc R . . C35 C 1.0661(7) 0.4159(4) 1.0159(6) 0.110(8) Uiso 1 1 d D . . H35A H 1.1002 0.4106 1.0218 0.165 Uiso 1 1 calc R . . H35B H 1.0527 0.4060 0.9783 0.165 Uiso 1 1 calc R . . H35C H 1.0340 0.3900 1.0404 0.165 Uiso 1 1 calc R . . C42 C 0.9664(4) 0.48319(19) 1.0663(5) 0.109(10) Uiso 1 2 d SD . . C37 C 1.1367(6) 0.5170(6) 0.9844(5) 0.153(9) Uiso 1 1 d D . . H37A H 1.1632 0.5005 0.9842 0.229 Uiso 1 1 calc R . . H37B H 1.1589 0.5587 0.9949 0.229 Uiso 1 1 calc R . . H37C H 1.1201 0.5136 0.9481 0.229 Uiso 1 1 calc R . . C22 C 0.8548(4) 0.5903(4) 1.0749(7) 0.158(10) Uiso 1 1 d D . . H22A H 0.8419 0.5548 1.0970 0.237 Uiso 1 1 calc R . . H22B H 0.8935 0.6215 1.0875 0.237 Uiso 1 1 calc R . . H22C H 0.8578 0.5812 1.0369 0.237 Uiso 1 1 calc R . . C26 C 0.8107(7) 0.7653(6) 1.0837(5) 0.40(2) Uiso 1 1 d D . . H26A H 0.7867 0.7844 1.0805 0.601 Uiso 1 1 calc R . . H26B H 0.8526 0.7955 1.0851 0.601 Uiso 1 1 calc R . . H26C H 0.7998 0.7415 1.1168 0.601 Uiso 1 1 calc R . . C43 C 0.9608(5) 0.5356(5) 1.0939(6) 0.163(10) Uiso 1 1 d D . . H43A H 0.9252 0.5189 1.1165 0.245 Uiso 1 1 calc R . . H43B H 0.9581 0.5606 1.0657 0.245 Uiso 1 1 calc R . . H43C H 0.9956 0.5595 1.1165 0.245 Uiso 1 1 calc R . . C27 C 0.8409(6) 0.7764(6) 0.9861(5) 0.246(16) Uiso 1 1 d D . . H27A H 0.8241 0.8021 0.9801 0.369 Uiso 1 1 calc R . . H27B H 0.8416 0.7578 0.9518 0.369 Uiso 1 1 calc R . . H27C H 0.8813 0.8000 1.0000 0.369 Uiso 1 1 calc R . . C44 C 0.9072(5) 0.4536(2) 1.0323(6) 0.36(3) Uiso 1 2 d SD . . H44A H 0.8750(6) 0.4375(3) 1.0586(11) 0.540 Uiso 1 2 d SD . . H44B H 0.9071(8) 0.4839(8) 1.0105(9) 0.540 Uiso 1 1 d D . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Br1 0.0433(16) 0.1226(19) 0.0751(18) 0.0010(8) 0.0020(16) 0.0216(8) Br2 0.0684(8) 0.1057(11) 0.0657(10) 0.0059(11) 0.0260(10) 0.0449(7) Br3 0.148(2) 0.0354(15) 0.0524(14) 0.0002(15) 0.0001(7) 0.0177(7) Ni4 0.0167(9) 0.1266(17) 0.0627(14) 0.0077(15) 0.0034(12) 0.0029(10) Ni5 0.0521(10) 0.0809(13) 0.0839(15) 0.0129(14) 0.0042(14) 0.0226(9) S2 0.102(3) 0.224(9) 0.049(4) -0.023(6) -0.012(3) 0.112(4) S1 0.052(3) 0.129(4) 0.077(3) -0.025(3) -0.023(3) 0.016(2) Si1 0.065(4) 0.173(6) 0.038(3) -0.013(4) 0.002(3) -0.017(4) S3 0.011(3) 0.161(6) 0.089(5) -0.0128(17) -0.026(3) 0.0053(16) Si3 0.138(9) 0.147(6) 0.060(5) -0.008(3) -0.017(6) 0.069(4) Si2 0.154(7) 0.046(5) 0.033(4) -0.012(4) -0.0060(19) 0.023(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 Ni4 2.445(3) . ? Br1 Ni4 2.446(3) 9 ? Br2 Ni4 2.429(3) . ? Br2 Ni5 2.450(3) . ? Br3 Ni5 2.436(3) . ? Br3 Ni5 2.436(3) 8_655 ? Ni4 S3 2.229(5) . ? Ni4 S1 2.350(7) . ? Ni5 S1 2.247(6) . ? Ni5 S2 2.277(6) . ? S2 Si2 2.225(10) . ? S2 Ni5 2.275(6) 8_655 ? S1 Si1 2.235(7) . ? Si1 C9 1.893(12) . ? Si1 C1 1.902(10) . ? Si1 C5 1.971(12) . ? C9 C12 1.500(15) . ? C9 C10 1.524(15) . ? C9 C11 1.563(16) . ? C5 C7 1.521(15) . ? C5 C6 1.550(15) . ? C5 C8 1.587(15) . ? C1 C2 1.528(11) . ? C1 C4 1.555(14) . ? C1 C3 1.578(15) . ? S3 Ni4 2.230(5) 9 ? S3 Si3 2.287(10) . ? Si3 C34 1.907(13) . ? Si3 C34 1.909(13) 9 ? Si3 C42 1.924(13) . ? C34 C35 1.549(15) . ? C34 C37 1.612(15) . ? C34 C36 1.583(14) . ? Si2 C24 1.879(13) 8_655 ? Si2 C24 1.877(13) . ? Si2 C20 1.937(13) . ? Si2 C27 2.731(16) 8_655 ? C24 C25 1.494(15) . ? C24 C26 1.610(16) . ? C24 C27 1.703(15) . ? C20 C21 1.599(14) . ? C20 C22 1.646(13) 8_655 ? C20 C22 1.649(13) . ? C42 C44 1.580(15) . ? C42 C43 1.601(14) . ? C42 C43 1.600(14) 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 Ni4 Br1 Ni4 83.86(16) . 9 ? Ni4 Br2 Ni5 85.89(10) . . ? Ni5 Br3 Ni5 86.79(15) . 8_655 ? S3 Ni4 S1 138.84(17) . . ? S3 Ni4 Br2 117.6(2) . . ? S1 Ni4 Br2 89.06(16) . . ? S3 Ni4 Br1 86.84(18) . . ? S1 Ni4 Br1 118.71(17) . . ? Br2 Ni4 Br1 103.25(10) . . ? S1 Ni5 S2 135.1(3) . . ? S1 Ni5 Br3 121.11(18) . . ? S2 Ni5 Br3 88.37(17) . . ? S1 Ni5 Br2 90.96(19) . . ? S2 Ni5 Br2 116.1(2) . . ? Br3 Ni5 Br2 103.40(10) . . ? Si2 S2 Ni5 128.3(2) . 8_655 ? Si2 S2 Ni5 128.3(2) . . ? Ni5 S2 Ni5 94.7(3) 8_655 . ? Si1 S1 Ni5 128.2(3) . . ? Si1 S1 Ni4 125.1(3) . . ? Ni5 S1 Ni4 92.60(18) . . ? C9 Si1 C1 117.3(6) . . ? C9 Si1 C5 114.1(5) . . ? C1 Si1 C5 109.1(6) . . ? C9 Si1 S1 105.4(5) . . ? C1 Si1 S1 107.2(4) . . ? C5 Si1 S1 102.3(4) . . ? C12 C9 C10 106.5(8) . . ? C12 C9 C11 109.2(11) . . ? C10 C9 C11 107.6(11) . . ? C12 C9 Si1 94.9(9) . . ? C10 C9 Si1 121.2(10) . . ? C11 C9 Si1 115.7(7) . . ? C7 C5 C6 106.0(10) . . ? C7 C5 C8 108.4(8) . . ? C6 C5 C8 101.6(10) . . ? C7 C5 Si1 93.3(9) . . ? C6 C5 Si1 115.8(7) . . ? C8 C5 Si1 129.3(9) . . ? C2 C1 C4 108.0(10) . . ? C2 C1 C3 107.0(8) . . ? C4 C1 C3 102.6(11) . . ? C2 C1 Si1 116.9(8) . . ? C4 C1 Si1 114.4(6) . . ? C3 C1 Si1 106.8(8) . . ? Ni4 S3 Ni4 94.3(3) . 9 ? Ni4 S3 Si3 124.8(2) . . ? Ni4 S3 Si3 124.7(2) 9 . ? C34 Si3 C34 113.0(6) . 9 ? C34 Si3 C42 115.9(4) . . ? C34 Si3 C42 115.8(4) 9 . ? C34 Si3 S3 104.2(4) . . ? C34 Si3 S3 104.1(4) 9 . ? C42 Si3 S3 101.5(5) . . ? C35 C34 C37 102.8(11) . . ? C35 C34 C36 102.9(10) . . ? C37 C34 C36 102.8(8) . . ? C35 C34 Si3 129.8(9) . . ? C37 C34 Si3 104.5(9) . . ? C36 C34 Si3 110.9(9) . . ? C24 Si2 C24 121.4(6) 8_655 . ? C24 Si2 C20 114.6(4) 8_655 . ? C24 Si2 C20 114.5(4) . . ? C24 Si2 S2 98.0(4) 8_655 . ? C24 Si2 S2 98.0(4) . . ? C20 Si2 S2 105.5(5) . . ? C24 Si2 C27 38.0(4) 8_655 8_655 ? C24 Si2 C27 90.0(5) . 8_655 ? C20 Si2 C27 152.4(3) . 8_655 ? S2 Si2 C27 81.9(4) . 8_655 ? C25 C24 C26 104.2(12) . . ? C25 C24 C27 100.2(10) . . ? C26 C24 C27 98.3(8) . . ? C25 C24 Si2 134.3(10) . . ? C26 C24 Si2 113.3(10) . . ? C27 C24 Si2 99.3(8) . . ? C21 C20 C22 99.8(7) . 8_655 ? C21 C20 C22 99.8(7) . . ? C22 C20 C22 142.3(11) 8_655 . ? C21 C20 Si2 108.4(9) . . ? C22 C20 Si2 102.0(6) 8_655 . ? C22 C20 Si2 101.9(6) . . ? C44 C42 C43 99.2(6) . . ? C44 C42 C43 99.2(6) . 9 ? C43 C42 C43 128.7(14) . 9 ? C44 C42 Si3 114.7(9) . . ? C43 C42 Si3 107.4(5) . . ? C43 C42 Si3 107.4(5) 9 . ? _diffrn_measured_fraction_theta_max 0.850 _diffrn_reflns_theta_full 22.20 _diffrn_measured_fraction_theta_full 0.850 _refine_diff_density_max 0.925 _refine_diff_density_min -0.984 _refine_diff_density_rms 0.165 #===END data_Ni5_(6) _database_code_depnum_ccdc_archive 'CCDC 220007' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C66 H149 Ni5 S6 Si5' _chemical_formula_weight 1569.21 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' Si Si 0.0817 0.0704 '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' 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 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 14.193(8) _cell_length_b 16.493(10) _cell_length_c 36.54(2) _cell_angle_alpha 90.00 _cell_angle_beta 98.564(11) _cell_angle_gamma 90.00 _cell_volume 8459(9) _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 plate _exptl_crystal_colour red _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.232 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3404 _exptl_absorpt_coefficient_mu 1.345 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.6152 _exptl_absorpt_correction_T_max 0.8772 _exptl_absorpt_process_details ? _exptl_special_details ; Ni5(µ5-S)(?-SSitBu3)5(C6H14) (6). A red rod crystal (0.4 x 0.15 x 0.1 mm), obtained from slow evaporation of a saturated hexane solution of 6, was extracted from the mother liquor, immersed in polyisobutylene, extracted out with a glass fiber, and placed under a 173 K nitrogen stream on the goniometer head of a Siemens SMART CCD Area Detector system equipped with a fine-focus molybdenum X-ray tube (? = 0.71073Å). Preliminary diffraction data revealed a monoclinic crystal system. A hemisphere routine was used for data collection. The data was subsequently processed with the Bruker SAINT program to yield 48,883 reflections of which 11,776 were symmetry independent (Rint = 0.1174). Lattice constants were determined to be: a = 14. 193(8) Å, b = 16.493(10), c = 36.54(2) Å, and ? = 98.564(11); providing a cell volume of 8,459(9) Å3. The space group was determined to be P21/n with the asymmetric unit consisting of C66H148Si5S5Ni5 yielding a calculated density of 1.231 g/cm3. The data was corrected for absorption with SADABS. The structure was solved by direct methods, completed by subsequent difference Fourier syntheses and refined by full-matrix least-squares procedures (SHELXTL). All non-hydrogen and non-carbon atoms were refined with anisotropic displacement parameters and hydrogen atoms were included at calculated positions. The final residuals were R1 = 0.1105, wR2 = 0.2356, and GOF(F2) = 1.138. ; _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 '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 48883 _diffrn_reflns_av_R_equivalents 0.1174 _diffrn_reflns_av_sigmaI/netI 0.1177 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -40 _diffrn_reflns_limit_l_max 40 _diffrn_reflns_theta_min 2.05 _diffrn_reflns_theta_max 23.26 _reflns_number_total 11776 _reflns_number_gt 7703 _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 ; The carbon atoms were refined isotropically because not all carbon atoms were stable to anisotropic refinement. This was due to some rotational disorder in the tBu groups that could not be modeled. C13-C14 and C5S-C6S bond distances were restrained to acceptable C-C distances. 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^)+(0.0338P)^2^+262.7571P] 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 11776 _refine_ls_number_parameters 409 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.1710 _refine_ls_R_factor_gt 0.1170 _refine_ls_wR_factor_ref 0.2647 _refine_ls_wR_factor_gt 0.2432 _refine_ls_goodness_of_fit_ref 1.102 _refine_ls_restrained_S_all 1.118 _refine_ls_shift/su_max 0.197 _refine_ls_shift/su_mean 0.003 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 0.60240(12) 0.54285(11) 0.16668(5) 0.0227(5) Uani 1 1 d . . . Ni2 Ni 0.70366(12) 0.44987(11) 0.13518(5) 0.0212(4) Uani 1 1 d . . . Ni3 Ni 0.82957(12) 0.54157(11) 0.11804(5) 0.0218(5) Uani 1 1 d . . . Ni4 Ni 0.77575(12) 0.68398(11) 0.12028(5) 0.0221(5) Uani 1 1 d . . . Ni5 Ni 0.63328(13) 0.68470(11) 0.15026(5) 0.0227(5) Uani 1 1 d . . . S1 S 0.5986(3) 0.4104(2) 0.17012(10) 0.0238(9) Uani 1 1 d . . . S2 S 0.8375(3) 0.4085(2) 0.11792(10) 0.0230(9) Uani 1 1 d . . . S3 S 0.9151(3) 0.6479(2) 0.10767(10) 0.0261(9) Uani 1 1 d . . . S4 S 0.6922(3) 0.7927(2) 0.12722(10) 0.0251(9) Uani 1 1 d . . . S5 S 0.5341(3) 0.6496(2) 0.18742(10) 0.0258(9) Uani 1 1 d . . . S6 S 0.6847(2) 0.5789(2) 0.12333(10) 0.0214(8) Uani 1 1 d . . . Si1 Si 0.4612(3) 0.3601(3) 0.14455(12) 0.0253(10) Uani 1 1 d . . . Si2 Si 0.8506(3) 0.3589(3) 0.06255(11) 0.0260(10) Uani 1 1 d . . . Si3 Si 1.0305(3) 0.6872(3) 0.15100(11) 0.0248(10) Uani 1 1 d . . . Si4 Si 0.6102(3) 0.8392(3) 0.07554(12) 0.0325(11) Uani 1 1 d . . . Si5 Si 0.5759(3) 0.6877(3) 0.24584(11) 0.0281(10) Uani 1 1 d . . . C1 C 0.4902(12) 0.2424(11) 0.1391(5) 0.042(4) Uiso 1 1 d . . . C2 C 0.5776(14) 0.2281(13) 0.1278(6) 0.066(6) Uiso 1 1 d . . . H2A H 0.5872 0.1708 0.1258 0.099 Uiso 1 1 calc R . . H2B H 0.6273 0.2506 0.1456 0.099 Uiso 1 1 calc R . . H2C H 0.5789 0.2532 0.1042 0.099 Uiso 1 1 calc R . . C3 C 0.5002(13) 0.2096(12) 0.1843(5) 0.053(5) Uiso 1 1 d . . . H3A H 0.5144 0.1527 0.1853 0.080 Uiso 1 1 calc R . . H3B H 0.4413 0.2191 0.1935 0.080 Uiso 1 1 calc R . . H3C H 0.5506 0.2388 0.1991 0.080 Uiso 1 1 calc R . . C4 C 0.4072(14) 0.1984(13) 0.1201(5) 0.064(6) Uiso 1 1 d . . . H4A H 0.4232 0.1422 0.1181 0.096 Uiso 1 1 calc R . . H4B H 0.3890 0.2208 0.0959 0.096 Uiso 1 1 calc R . . H4C H 0.3552 0.2034 0.1341 0.096 Uiso 1 1 calc R . . C5 C 0.4200(10) 0.4074(9) 0.0959(4) 0.030(4) Uiso 1 1 d . . . C6 C 0.4862(13) 0.3754(12) 0.0680(5) 0.053(5) Uiso 1 1 d . . . H6A H 0.4660 0.3984 0.0440 0.079 Uiso 1 1 calc R . . H6B H 0.4821 0.3174 0.0665 0.079 Uiso 1 1 calc R . . H6C H 0.5509 0.3910 0.0766 0.079 Uiso 1 1 calc R . . C7 C 0.4257(12) 0.5001(10) 0.0959(5) 0.042(4) Uiso 1 1 d . . . H7A H 0.4049 0.5201 0.0713 0.063 Uiso 1 1 calc R . . H7B H 0.4903 0.5167 0.1039 0.063 Uiso 1 1 calc R . . H7C H 0.3855 0.5216 0.1125 0.063 Uiso 1 1 calc R . . C8 C 0.3168(11) 0.3824(10) 0.0805(4) 0.037(4) Uiso 1 1 d . . . H8A H 0.2987 0.4063 0.0565 0.056 Uiso 1 1 calc R . . H8B H 0.2746 0.4010 0.0969 0.056 Uiso 1 1 calc R . . H8C H 0.3130 0.3244 0.0784 0.056 Uiso 1 1 calc R . . C9 C 0.3713(11) 0.3897(10) 0.1800(4) 0.034(4) Uiso 1 1 d . . . C10 C 0.3347(13) 0.4706(11) 0.1734(5) 0.053(5) Uiso 1 1 d . . . H10A H 0.2925 0.4830 0.1909 0.080 Uiso 1 1 calc R . . H10B H 0.3005 0.4742 0.1488 0.080 Uiso 1 1 calc R . . H10C H 0.3866 0.5085 0.1763 0.080 Uiso 1 1 calc R . . C11 C 0.4206(13) 0.3797(12) 0.2193(5) 0.058(5) Uiso 1 1 d . . . H11A H 0.3775 0.3944 0.2361 0.087 Uiso 1 1 calc R . . H11B H 0.4756 0.4142 0.2234 0.087 Uiso 1 1 calc R . . H11C H 0.4399 0.3243 0.2234 0.087 Uiso 1 1 calc R . . C12 C 0.2858(13) 0.3279(12) 0.1729(5) 0.058(5) Uiso 1 1 d . . . H12A H 0.2407 0.3399 0.1893 0.087 Uiso 1 1 calc R . . H12B H 0.3094 0.2737 0.1774 0.087 Uiso 1 1 calc R . . H12C H 0.2552 0.3325 0.1477 0.087 Uiso 1 1 calc R . . C13 C 0.7855(9) 0.2477(9) 0.0610(4) 0.026(4) Uiso 1 1 d D . . C15 C 0.8086(15) 0.2119(13) 0.0965(6) 0.068(6) Uiso 1 1 d . . . H15A H 0.7751 0.1615 0.0971 0.102 Uiso 1 1 calc R . . H15B H 0.7903 0.2478 0.1149 0.102 Uiso 1 1 calc R . . H15C H 0.8760 0.2022 0.1016 0.102 Uiso 1 1 calc R . . C16 C 0.8285(16) 0.1951(15) 0.0329(6) 0.083(7) Uiso 1 1 d . . . H16A H 0.7970 0.1435 0.0306 0.125 Uiso 1 1 calc R . . H16B H 0.8953 0.1872 0.0414 0.125 Uiso 1 1 calc R . . H16C H 0.8202 0.2218 0.0093 0.125 Uiso 1 1 calc R . . C17 C 0.9889(12) 0.3466(11) 0.0644(5) 0.041(4) Uiso 1 1 d . . . C18 C 1.0289(15) 0.2836(13) 0.0922(6) 0.074(6) Uiso 1 1 d . . . H18A H 1.0965 0.2795 0.0926 0.111 Uiso 1 1 calc R . . H18B H 0.9998 0.2321 0.0854 0.111 Uiso 1 1 calc R . . H18C H 1.0159 0.2988 0.1163 0.111 Uiso 1 1 calc R . . C19 C 1.0172(14) 0.3249(13) 0.0265(5) 0.063(6) Uiso 1 1 d . . . H19A H 1.0852 0.3199 0.0288 0.094 Uiso 1 1 calc R . . H19B H 0.9959 0.3669 0.0090 0.094 Uiso 1 1 calc R . . H19C H 0.9881 0.2744 0.0180 0.094 Uiso 1 1 calc R . . C20 C 1.0400(13) 0.4266(12) 0.0782(5) 0.057(5) Uiso 1 1 d . . . H20A H 1.1076 0.4201 0.0792 0.085 Uiso 1 1 calc R . . H20B H 1.0260 0.4392 0.1025 0.085 Uiso 1 1 calc R . . H20C H 1.0181 0.4698 0.0615 0.085 Uiso 1 1 calc R . . C21 C 0.7948(10) 0.4297(9) 0.0230(4) 0.025(3) Uiso 1 1 d . . . C22 C 0.7846(12) 0.3867(10) -0.0142(4) 0.041(4) Uiso 1 1 d . . . H22A H 0.7567 0.4231 -0.0333 0.061 Uiso 1 1 calc R . . H22B H 0.7443 0.3401 -0.0137 0.061 Uiso 1 1 calc R . . H22C H 0.8462 0.3699 -0.0191 0.061 Uiso 1 1 calc R . . C23 C 0.8571(11) 0.5048(10) 0.0206(5) 0.038(4) Uiso 1 1 d . . . H23A H 0.8278 0.5393 0.0010 0.057 Uiso 1 1 calc R . . H23B H 0.9188 0.4883 0.0157 0.057 Uiso 1 1 calc R . . H23C H 0.8636 0.5337 0.0436 0.057 Uiso 1 1 calc R . . C24 C 0.6967(11) 0.4600(10) 0.0288(4) 0.039(4) Uiso 1 1 d . . . H24A H 0.6718 0.4953 0.0087 0.059 Uiso 1 1 calc R . . H24B H 0.7018 0.4892 0.0517 0.059 Uiso 1 1 calc R . . H24C H 0.6547 0.4146 0.0295 0.059 Uiso 1 1 calc R . . C25 C 1.1396(10) 0.6793(10) 0.1254(4) 0.031(4) Uiso 1 1 d . . . C26 C 1.1416(12) 0.5989(10) 0.1050(5) 0.046(5) Uiso 1 1 d . . . H26A H 1.1968 0.5970 0.0927 0.069 Uiso 1 1 calc R . . H26B H 1.0851 0.5941 0.0871 0.069 Uiso 1 1 calc R . . H26C H 1.1440 0.5551 0.1224 0.069 Uiso 1 1 calc R . . C27 C 1.2362(11) 0.6842(11) 0.1536(5) 0.044(4) Uiso 1 1 d . . . H27A H 1.2893 0.6810 0.1401 0.066 Uiso 1 1 calc R . . H27B H 1.2391 0.6400 0.1708 0.066 Uiso 1 1 calc R . . H27C H 1.2386 0.7346 0.1668 0.066 Uiso 1 1 calc R . . C28 C 1.1418(12) 0.7467(10) 0.0967(5) 0.045(5) Uiso 1 1 d . . . H28A H 1.1978 0.7410 0.0851 0.067 Uiso 1 1 calc R . . H28B H 1.1428 0.7985 0.1087 0.067 Uiso 1 1 calc R . . H28C H 1.0861 0.7429 0.0783 0.067 Uiso 1 1 calc R . . C29 C 1.0046(11) 0.7993(10) 0.1640(4) 0.038(4) Uiso 1 1 d . . . C30 C 1.0977(12) 0.8412(11) 0.1819(5) 0.049(5) Uiso 1 1 d . . . H30A H 1.0840 0.8959 0.1884 0.073 Uiso 1 1 calc R . . H30B H 1.1426 0.8416 0.1647 0.073 Uiso 1 1 calc R . . H30C H 1.1242 0.8121 0.2038 0.073 Uiso 1 1 calc R . . C31 C 0.9651(12) 0.8490(11) 0.1291(5) 0.044(4) Uiso 1 1 d . . . H31A H 0.9527 0.9035 0.1362 0.065 Uiso 1 1 calc R . . H31B H 0.9070 0.8247 0.1172 0.065 Uiso 1 1 calc R . . H31C H 1.0111 0.8495 0.1124 0.065 Uiso 1 1 calc R . . C32 C 0.9351(12) 0.8041(11) 0.1893(5) 0.050(5) Uiso 1 1 d . . . H32A H 0.9247 0.8599 0.1950 0.074 Uiso 1 1 calc R . . H32B H 0.9584 0.7753 0.2116 0.074 Uiso 1 1 calc R . . H32C H 0.8761 0.7804 0.1780 0.074 Uiso 1 1 calc R . . C33 C 1.0378(11) 0.6141(10) 0.1932(4) 0.033(4) Uiso 1 1 d . . . C34 C 1.0704(12) 0.5268(10) 0.1837(5) 0.042(4) Uiso 1 1 d . . . H34A H 1.0735 0.4929 0.2052 0.062 Uiso 1 1 calc R . . H34B H 1.1321 0.5296 0.1760 0.062 Uiso 1 1 calc R . . H34C H 1.0254 0.5045 0.1640 0.062 Uiso 1 1 calc R . . C35 C 1.1055(12) 0.6476(11) 0.2266(5) 0.049(5) Uiso 1 1 d . . . H35A H 1.1076 0.6108 0.2471 0.074 Uiso 1 1 calc R . . H35B H 1.0829 0.6995 0.2335 0.074 Uiso 1 1 calc R . . H35C H 1.1683 0.6535 0.2201 0.074 Uiso 1 1 calc R . . C36 C 0.9396(11) 0.6028(10) 0.2059(5) 0.041(4) Uiso 1 1 d . . . H36A H 0.9459 0.5672 0.2269 0.061 Uiso 1 1 calc R . . H36B H 0.8958 0.5798 0.1861 0.061 Uiso 1 1 calc R . . H36C H 0.9161 0.6545 0.2126 0.061 Uiso 1 1 calc R . . C37 C 0.6331(16) 0.9520(15) 0.0831(7) 0.077(7) Uiso 1 1 d . . . C38 C 0.7394(18) 0.9735(17) 0.0937(7) 0.103(9) Uiso 1 1 d . . . H38A H 0.7461 1.0312 0.0965 0.155 Uiso 1 1 calc R . . H38B H 0.7741 0.9553 0.0746 0.155 Uiso 1 1 calc R . . H38C H 0.7641 0.9475 0.1166 0.155 Uiso 1 1 calc R . . C39 C 0.600(2) 1.0040(18) 0.0473(8) 0.123(11) Uiso 1 1 d . . . H39A H 0.6145 1.0601 0.0525 0.185 Uiso 1 1 calc R . . H39B H 0.5328 0.9976 0.0399 0.185 Uiso 1 1 calc R . . H39C H 0.6332 0.9860 0.0277 0.185 Uiso 1 1 calc R . . C40 C 0.5827(19) 0.9864(17) 0.1139(8) 0.112(10) Uiso 1 1 d . . . H40A H 0.5961 1.0433 0.1167 0.168 Uiso 1 1 calc R . . H40B H 0.6050 0.9589 0.1367 0.168 Uiso 1 1 calc R . . H40C H 0.5152 0.9785 0.1076 0.168 Uiso 1 1 calc R . . C41 C 0.4787(14) 0.8085(13) 0.0739(6) 0.061(6) Uiso 1 1 d . . . C42 C 0.4611(17) 0.7218(14) 0.0667(7) 0.086(7) Uiso 1 1 d . . . H42A H 0.3946 0.7105 0.0663 0.129 Uiso 1 1 calc R . . H42B H 0.4978 0.6905 0.0860 0.129 Uiso 1 1 calc R . . H42C H 0.4794 0.7077 0.0433 0.129 Uiso 1 1 calc R . . C43 C 0.4109(17) 0.8635(15) 0.0447(7) 0.087(8) Uiso 1 1 d . . . H43A H 0.3458 0.8470 0.0442 0.131 Uiso 1 1 calc R . . H43B H 0.4287 0.8571 0.0206 0.131 Uiso 1 1 calc R . . H43C H 0.4176 0.9194 0.0520 0.131 Uiso 1 1 calc R . . C44 C 0.4444(15) 0.8228(14) 0.1122(6) 0.073(6) Uiso 1 1 d . . . H44A H 0.3790 0.8065 0.1107 0.109 Uiso 1 1 calc R . . H44B H 0.4501 0.8793 0.1185 0.109 Uiso 1 1 calc R . . H44C H 0.4830 0.7915 0.1309 0.109 Uiso 1 1 calc R . . C45 C 0.6638(15) 0.7956(13) 0.0334(6) 0.064(6) Uiso 1 1 d . . . C46 C 0.6659(17) 0.7057(14) 0.0318(7) 0.086(7) Uiso 1 1 d . . . H46A H 0.6933 0.6889 0.0106 0.129 Uiso 1 1 calc R . . H46B H 0.6021 0.6851 0.0300 0.129 Uiso 1 1 calc R . . H46C H 0.7035 0.6851 0.0539 0.129 Uiso 1 1 calc R . . C47 C 0.7627(18) 0.8281(16) 0.0334(7) 0.102(9) Uiso 1 1 d . . . H47A H 0.7886 0.8061 0.0127 0.153 Uiso 1 1 calc R . . H47B H 0.8023 0.8129 0.0559 0.153 Uiso 1 1 calc R . . H47C H 0.7603 0.8861 0.0315 0.153 Uiso 1 1 calc R . . C48 C 0.6006(18) 0.8245(16) -0.0032(7) 0.098(8) Uiso 1 1 d . . . H48A H 0.6261 0.8032 -0.0242 0.147 Uiso 1 1 calc R . . H48B H 0.6004 0.8826 -0.0043 0.147 Uiso 1 1 calc R . . H48C H 0.5366 0.8052 -0.0037 0.147 Uiso 1 1 calc R . . C49 C 0.6296(11) 0.7959(10) 0.2458(4) 0.034(4) Uiso 1 1 d . . . C50 C 0.7331(12) 0.7919(11) 0.2379(5) 0.047(5) Uiso 1 1 d . . . H50A H 0.7589 0.8457 0.2379 0.071 Uiso 1 1 calc R . . H50B H 0.7343 0.7673 0.2141 0.071 Uiso 1 1 calc R . . H50C H 0.7707 0.7601 0.2567 0.071 Uiso 1 1 calc R . . C51 C 0.5734(12) 0.8510(11) 0.2157(5) 0.045(5) Uiso 1 1 d . . . H51A H 0.6022 0.9038 0.2168 0.068 Uiso 1 1 calc R . . H51B H 0.5086 0.8556 0.2201 0.068 Uiso 1 1 calc R . . H51C H 0.5749 0.8276 0.1918 0.068 Uiso 1 1 calc R . . C52 C 0.6305(13) 0.8390(11) 0.2832(5) 0.054(5) Uiso 1 1 d . . . H52A H 0.6572 0.8923 0.2820 0.081 Uiso 1 1 calc R . . H52B H 0.6684 0.8083 0.3024 0.081 Uiso 1 1 calc R . . H52C H 0.5666 0.8433 0.2887 0.081 Uiso 1 1 calc R . . C53 C 0.4539(11) 0.6868(10) 0.2639(4) 0.035(4) Uiso 1 1 d . . . C54 C 0.3903(12) 0.7599(11) 0.2486(5) 0.048(5) Uiso 1 1 d . . . H54A H 0.3307 0.7574 0.2580 0.072 Uiso 1 1 calc R . . H54B H 0.3787 0.7575 0.2221 0.072 Uiso 1 1 calc R . . H54C H 0.4222 0.8097 0.2563 0.072 Uiso 1 1 calc R . . C55 C 0.4662(12) 0.6919(11) 0.3072(5) 0.049(5) Uiso 1 1 d . . . H55A H 0.4046 0.6919 0.3150 0.074 Uiso 1 1 calc R . . H55B H 0.4993 0.7409 0.3153 0.074 Uiso 1 1 calc R . . H55C H 0.5021 0.6460 0.3176 0.074 Uiso 1 1 calc R . . C56 C 0.4001(12) 0.6097(10) 0.2527(5) 0.045(5) Uiso 1 1 d . . . H56A H 0.3398 0.6107 0.2616 0.068 Uiso 1 1 calc R . . H56B H 0.4365 0.5640 0.2631 0.068 Uiso 1 1 calc R . . H56C H 0.3898 0.6054 0.2262 0.068 Uiso 1 1 calc R . . C57 C 0.6640(11) 0.6089(9) 0.2705(4) 0.031(4) Uiso 1 1 d . . . C58 C 0.7443(11) 0.5882(10) 0.2488(5) 0.037(4) Uiso 1 1 d . . . H58A H 0.7856 0.5488 0.2622 0.055 Uiso 1 1 calc R . . H58B H 0.7799 0.6363 0.2453 0.055 Uiso 1 1 calc R . . H58C H 0.7179 0.5663 0.2251 0.055 Uiso 1 1 calc R . . C59 C 0.7096(12) 0.6417(11) 0.3090(5) 0.047(5) Uiso 1 1 d . . . H59A H 0.7532 0.6022 0.3211 0.071 Uiso 1 1 calc R . . H59B H 0.6605 0.6521 0.3238 0.071 Uiso 1 1 calc R . . H59C H 0.7432 0.6911 0.3058 0.071 Uiso 1 1 calc R . . C60 C 0.6150(12) 0.5264(11) 0.2778(5) 0.049(5) Uiso 1 1 d . . . H60A H 0.6619 0.4896 0.2900 0.073 Uiso 1 1 calc R . . H60B H 0.5863 0.5034 0.2547 0.073 Uiso 1 1 calc R . . H60C H 0.5669 0.5357 0.2933 0.073 Uiso 1 1 calc R . . C1S C 1.333(3) 0.979(3) 0.1887(12) 0.21(2) Uiso 1 1 d . . . H1SA H 1.3355 0.9944 0.2141 0.318 Uiso 1 1 calc R . . H1SB H 1.3936 0.9889 0.1809 0.318 Uiso 1 1 calc R . . H1SC H 1.3183 0.9220 0.1862 0.318 Uiso 1 1 calc R . . C2S C 1.259(3) 1.026(2) 0.1655(10) 0.151(13) Uiso 1 1 d . . . H2SA H 1.2748 1.0831 0.1687 0.181 Uiso 1 1 calc R . . H2SB H 1.1990 1.0179 0.1750 0.181 Uiso 1 1 calc R . . C3S C 1.242(2) 1.009(2) 0.1257(9) 0.120(11) Uiso 1 1 d . . . H3SA H 1.2981 1.0245 0.1152 0.144 Uiso 1 1 calc R . . H3SB H 1.2340 0.9506 0.1222 0.144 Uiso 1 1 calc R . . C4S C 1.161(4) 1.048(3) 0.1058(16) 0.25(3) Uiso 1 1 d . . . H4SA H 1.1607 1.1047 0.1134 0.304 Uiso 1 1 calc R . . H4SB H 1.1035 1.0227 0.1112 0.304 Uiso 1 1 calc R . . C5S C 1.165(4) 1.044(4) 0.0658(18) 0.28(3) Uiso 1 1 d D . . H5SA H 1.2321 1.0345 0.0640 0.340 Uiso 1 1 calc R . . H5SB H 1.1512 1.0980 0.0566 0.340 Uiso 1 1 calc R . . C6S C 1.111(5) 0.988(4) 0.0369(17) 0.36(4) Uiso 1 1 d D . . H6SA H 1.1169 1.0069 0.0126 0.435 Uiso 1 1 calc R . . H6SB H 1.0445 0.9871 0.0398 0.435 Uiso 1 1 calc R . . H6SC H 1.1360 0.9337 0.0400 0.435 Uiso 1 1 calc R . . C14 C 0.6791(12) 0.2608(14) 0.0484(6) 0.073(6) Uiso 1 1 d D . . H14A H 0.6466 0.2096 0.0477 0.110 Uiso 1 1 calc R . . H14B H 0.6696 0.2844 0.0241 0.110 Uiso 1 1 calc R . . H14C H 0.6542 0.2964 0.0654 0.110 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 0.0244(10) 0.0234(11) 0.0208(10) -0.0016(9) 0.0053(8) -0.0010(9) Ni2 0.0222(10) 0.0204(10) 0.0206(10) 0.0018(8) 0.0021(8) 0.0005(8) Ni3 0.0196(9) 0.0226(11) 0.0231(10) 0.0001(9) 0.0026(8) 0.0007(8) Ni4 0.0209(10) 0.0191(11) 0.0258(11) 0.0005(9) 0.0021(8) -0.0013(8) Ni5 0.0249(10) 0.0219(11) 0.0210(10) -0.0015(9) 0.0027(8) 0.0014(9) S1 0.024(2) 0.023(2) 0.023(2) 0.0035(17) 0.0002(16) -0.0018(17) S2 0.026(2) 0.022(2) 0.021(2) 0.0018(17) 0.0011(16) 0.0024(17) S3 0.026(2) 0.030(2) 0.022(2) -0.0013(17) 0.0030(17) -0.0016(17) S4 0.028(2) 0.020(2) 0.025(2) -0.0008(16) -0.0027(17) 0.0017(17) S5 0.026(2) 0.031(2) 0.021(2) -0.0041(17) 0.0053(16) 0.0025(17) S6 0.023(2) 0.020(2) 0.021(2) -0.0008(16) 0.0029(16) -0.0003(16) Si1 0.019(2) 0.024(2) 0.032(2) 0.003(2) 0.0026(19) 0.0011(18) Si2 0.032(2) 0.026(2) 0.021(2) 0.0002(19) 0.0028(19) 0.000(2) Si3 0.019(2) 0.030(3) 0.026(2) -0.004(2) 0.0043(18) -0.0040(19) Si4 0.043(3) 0.023(3) 0.028(2) 0.005(2) -0.008(2) 0.001(2) Si5 0.026(2) 0.038(3) 0.021(2) -0.009(2) 0.0049(18) 0.001(2) _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 S6 2.186(4) . ? Ni1 S1 2.190(4) . ? Ni1 S5 2.198(4) . ? Ni1 Ni5 2.471(3) . ? Ni1 Ni2 2.497(3) . ? Ni2 S6 2.180(4) . ? Ni2 S2 2.197(4) . ? Ni2 S1 2.202(4) . ? Ni2 Ni3 2.491(3) . ? Ni3 S6 2.182(4) . ? Ni3 S3 2.198(4) . ? Ni3 S2 2.198(4) . ? Ni3 Ni4 2.475(3) . ? Ni4 S6 2.175(4) . ? Ni4 S3 2.180(4) . ? Ni4 S4 2.185(4) . ? Ni4 Ni5 2.439(3) . ? Ni5 S5 2.175(4) . ? Ni5 S6 2.182(4) . ? Ni5 S4 2.188(4) . ? S1 Si1 2.195(5) . ? S2 Si2 2.216(6) . ? S3 Si3 2.199(5) . ? S4 Si4 2.203(6) . ? S5 Si5 2.219(6) . ? Si1 C5 1.950(16) . ? Si1 C1 2.001(18) . ? Si1 C9 2.009(16) . ? Si2 C21 1.934(15) . ? Si2 C17 1.964(17) . ? Si2 C13 2.050(15) . ? Si3 C25 1.930(15) . ? Si3 C33 1.948(16) . ? Si3 C29 1.957(17) . ? Si4 C37 1.90(2) . ? Si4 C41 1.93(2) . ? Si4 C45 1.95(2) . ? Si5 C57 1.931(16) . ? Si5 C49 1.940(16) . ? Si5 C53 1.943(16) . ? C1 C2 1.39(2) . ? C1 C4 1.47(2) . ? C1 C3 1.72(2) . ? C5 C7 1.53(2) . ? C5 C8 1.54(2) . ? C5 C6 1.58(2) . ? C9 C10 1.44(2) . ? C9 C11 1.51(2) . ? C9 C12 1.58(2) . ? C13 C14 1.527(16) . ? C13 C15 1.42(2) . ? C13 C16 1.54(3) . ? C17 C18 1.50(3) . ? C17 C19 1.54(2) . ? C17 C20 1.55(2) . ? C21 C22 1.52(2) . ? C21 C24 1.52(2) . ? C21 C23 1.53(2) . ? C25 C26 1.52(2) . ? C25 C28 1.53(2) . ? C25 C27 1.59(2) . ? C29 C32 1.45(2) . ? C29 C31 1.55(2) . ? C29 C30 1.55(2) . ? C33 C35 1.54(2) . ? C33 C36 1.54(2) . ? C33 C34 1.57(2) . ? C37 C40 1.53(3) . ? C37 C38 1.54(3) . ? C37 C39 1.58(3) . ? C41 C42 1.47(3) . ? C41 C44 1.57(3) . ? C41 C43 1.61(3) . ? C45 C46 1.48(3) . ? C45 C47 1.50(3) . ? C45 C48 1.57(3) . ? C49 C52 1.54(2) . ? C49 C50 1.54(2) . ? C49 C51 1.55(2) . ? C53 C56 1.51(2) . ? C53 C54 1.56(2) . ? C53 C55 1.57(2) . ? C57 C58 1.52(2) . ? C57 C59 1.55(2) . ? C57 C60 1.57(2) . ? C1S C2S 1.48(5) . ? C2S C3S 1.47(4) . ? C3S C4S 1.42(5) . ? C4S C5S 1.47(6) . ? C5S C6S 1.53(2) . ? 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 S6 Ni1 S1 109.48(16) . . ? S6 Ni1 S5 110.04(16) . . ? S1 Ni1 S5 139.76(17) . . ? S6 Ni1 Ni5 55.47(11) . . ? S1 Ni1 Ni5 164.93(14) . . ? S5 Ni1 Ni5 55.16(12) . . ? S6 Ni1 Ni2 55.01(11) . . ? S1 Ni1 Ni2 55.57(12) . . ? S5 Ni1 Ni2 164.66(14) . . ? Ni5 Ni1 Ni2 109.53(9) . . ? S6 Ni2 S2 109.44(15) . . ? S6 Ni2 S1 109.25(16) . . ? S2 Ni2 S1 139.79(16) . . ? S6 Ni2 Ni3 55.22(11) . . ? S2 Ni2 Ni3 55.49(12) . . ? S1 Ni2 Ni3 153.99(14) . . ? S6 Ni2 Ni1 55.22(11) . . ? S2 Ni2 Ni1 154.78(13) . . ? S1 Ni2 Ni1 55.12(12) . . ? Ni3 Ni2 Ni1 103.11(9) . . ? S6 Ni3 S3 110.01(16) . . ? S6 Ni3 S2 109.33(16) . . ? S3 Ni3 S2 140.06(16) . . ? S6 Ni3 Ni4 55.24(11) . . ? S3 Ni3 Ni4 55.22(12) . . ? S2 Ni3 Ni4 164.57(14) . . ? S6 Ni3 Ni2 55.14(12) . . ? S3 Ni3 Ni2 164.40(14) . . ? S2 Ni3 Ni2 55.46(12) . . ? Ni4 Ni3 Ni2 109.35(9) . . ? S6 Ni4 S3 110.99(16) . . ? S6 Ni4 S4 108.12(16) . . ? S3 Ni4 S4 140.70(17) . . ? S6 Ni4 Ni5 56.09(11) . . ? S3 Ni4 Ni5 159.30(14) . . ? S4 Ni4 Ni5 56.17(12) . . ? S6 Ni4 Ni3 55.53(12) . . ? S3 Ni4 Ni3 55.92(12) . . ? S4 Ni4 Ni3 163.34(14) . . ? Ni5 Ni4 Ni3 107.46(9) . . ? S5 Ni5 S6 111.09(16) . . ? S5 Ni5 S4 140.96(17) . . ? S6 Ni5 S4 107.74(16) . . ? S5 Ni5 Ni4 159.41(14) . . ? S6 Ni5 Ni4 55.82(11) . . ? S4 Ni5 Ni4 56.03(12) . . ? S5 Ni5 Ni1 56.05(12) . . ? S6 Ni5 Ni1 55.63(12) . . ? S4 Ni5 Ni1 162.90(14) . . ? Ni4 Ni5 Ni1 107.07(9) . . ? Ni1 S1 Si1 112.3(2) . . ? Ni1 S1 Ni2 69.31(13) . . ? Si1 S1 Ni2 120.0(2) . . ? Ni2 S2 Ni3 69.05(13) . . ? Ni2 S2 Si2 124.8(2) . . ? Ni3 S2 Si2 112.4(2) . . ? Ni4 S3 Ni3 68.86(13) . . ? Ni4 S3 Si3 111.7(2) . . ? Ni3 S3 Si3 118.8(2) . . ? Ni4 S4 Ni5 67.79(13) . . ? Ni4 S4 Si4 114.4(2) . . ? Ni5 S4 Si4 115.4(2) . . ? Ni5 S5 Ni1 68.79(13) . . ? Ni5 S5 Si5 114.9(2) . . ? Ni1 S5 Si5 119.3(2) . . ? Ni4 S6 Ni2 136.99(19) . . ? Ni4 S6 Ni5 68.09(13) . . ? Ni2 S6 Ni5 136.96(19) . . ? Ni4 S6 Ni3 69.22(13) . . ? Ni2 S6 Ni3 69.64(13) . . ? Ni5 S6 Ni3 130.41(18) . . ? Ni4 S6 Ni1 129.76(18) . . ? Ni2 S6 Ni1 69.77(13) . . ? Ni5 S6 Ni1 68.90(13) . . ? Ni3 S6 Ni1 126.84(18) . . ? C5 Si1 C1 109.6(7) . . ? C5 Si1 C9 111.0(7) . . ? C1 Si1 C9 117.3(7) . . ? C5 Si1 S1 111.4(5) . . ? C1 Si1 S1 103.1(5) . . ? C9 Si1 S1 104.1(5) . . ? C21 Si2 C17 112.6(7) . . ? C21 Si2 C13 112.8(6) . . ? C17 Si2 C13 110.7(7) . . ? C21 Si2 S2 112.2(5) . . ? C17 Si2 S2 103.1(5) . . ? C13 Si2 S2 104.8(5) . . ? C25 Si3 C33 113.0(7) . . ? C25 Si3 C29 112.0(7) . . ? C33 Si3 C29 112.5(7) . . ? C25 Si3 S3 101.3(5) . . ? C33 Si3 S3 109.5(5) . . ? C29 Si3 S3 107.8(5) . . ? C37 Si4 C41 113.9(10) . . ? C37 Si4 C45 113.4(10) . . ? C41 Si4 C45 111.6(9) . . ? C37 Si4 S4 99.1(7) . . ? C41 Si4 S4 108.7(7) . . ? C45 Si4 S4 109.2(7) . . ? C57 Si5 C49 113.1(7) . . ? C57 Si5 C53 112.6(7) . . ? C49 Si5 C53 112.1(7) . . ? C57 Si5 S5 108.7(5) . . ? C49 Si5 S5 108.0(5) . . ? C53 Si5 S5 101.6(5) . . ? C2 C1 C4 117.8(17) . . ? C2 C1 C3 106.4(15) . . ? C4 C1 C3 104.1(14) . . ? C2 C1 Si1 113.6(14) . . ? C4 C1 Si1 111.4(13) . . ? C3 C1 Si1 101.5(11) . . ? C7 C5 C8 108.3(13) . . ? C7 C5 C6 107.3(13) . . ? C8 C5 C6 107.5(13) . . ? C7 C5 Si1 112.9(11) . . ? C8 C5 Si1 111.4(10) . . ? C6 C5 Si1 109.2(11) . . ? C10 C9 C11 111.4(15) . . ? C10 C9 C12 108.7(14) . . ? C11 C9 C12 108.8(14) . . ? C10 C9 Si1 111.5(12) . . ? C11 C9 Si1 109.8(11) . . ? C12 C9 Si1 106.5(11) . . ? C14 C13 C15 114.8(15) . . ? C14 C13 C16 110.5(15) . . ? C15 C13 C16 108.3(15) . . ? C14 C13 Si2 107.7(12) . . ? C15 C13 Si2 107.8(12) . . ? C16 C13 Si2 107.5(12) . . ? C18 C17 C19 108.9(16) . . ? C18 C17 C20 104.9(15) . . ? C19 C17 C20 108.5(15) . . ? C18 C17 Si2 111.7(13) . . ? C19 C17 Si2 112.6(12) . . ? C20 C17 Si2 109.9(12) . . ? C22 C21 C24 108.0(12) . . ? C22 C21 C23 107.7(12) . . ? C24 C21 C23 106.9(12) . . ? C22 C21 Si2 111.1(10) . . ? C24 C21 Si2 112.1(10) . . ? C23 C21 Si2 110.8(10) . . ? C26 C25 C28 107.1(13) . . ? C26 C25 C27 106.5(13) . . ? C28 C25 C27 107.6(13) . . ? C26 C25 Si3 111.7(11) . . ? C28 C25 Si3 112.5(11) . . ? C27 C25 Si3 111.1(10) . . ? C32 C29 C31 107.3(14) . . ? C32 C29 C30 108.9(14) . . ? C31 C29 C30 107.1(14) . . ? C32 C29 Si3 112.1(12) . . ? C31 C29 Si3 111.0(11) . . ? C30 C29 Si3 110.2(11) . . ? C35 C33 C36 106.9(13) . . ? C35 C33 C34 109.7(13) . . ? C36 C33 C34 105.4(13) . . ? C35 C33 Si3 111.0(11) . . ? C36 C33 Si3 111.6(11) . . ? C34 C33 Si3 112.0(11) . . ? C40 C37 C38 106(2) . . ? C40 C37 C39 107(2) . . ? C38 C37 C39 104(2) . . ? C40 C37 Si4 112.4(18) . . ? C38 C37 Si4 113.7(17) . . ? C39 C37 Si4 112.8(17) . . ? C42 C41 C44 103.8(18) . . ? C42 C41 C43 111.3(19) . . ? C44 C41 C43 105.8(17) . . ? C42 C41 Si4 113.6(16) . . ? C44 C41 Si4 111.2(14) . . ? C43 C41 Si4 110.7(14) . . ? C46 C45 C47 109(2) . . ? C46 C45 C48 106.4(19) . . ? C47 C45 C48 107.8(19) . . ? C46 C45 Si4 114.2(16) . . ? C47 C45 Si4 110.1(16) . . ? C48 C45 Si4 108.7(15) . . ? C52 C49 C50 107.7(13) . . ? C52 C49 C51 107.1(14) . . ? C50 C49 C51 107.2(13) . . ? C52 C49 Si5 112.1(11) . . ? C50 C49 Si5 110.3(11) . . ? C51 C49 Si5 112.3(11) . . ? C56 C53 C54 108.1(13) . . ? C56 C53 C55 107.2(14) . . ? C54 C53 C55 107.0(14) . . ? C56 C53 Si5 110.7(11) . . ? C54 C53 Si5 111.7(11) . . ? C55 C53 Si5 111.9(11) . . ? C58 C57 C59 107.9(13) . . ? C58 C57 C60 106.2(13) . . ? C59 C57 C60 106.5(13) . . ? C58 C57 Si5 113.0(11) . . ? C59 C57 Si5 110.0(11) . . ? C60 C57 Si5 113.0(11) . . ? C1S C2S C3S 117(3) . . ? C4S C3S C2S 114(4) . . ? C3S C4S C5S 110(5) . . ? C4S C5S C6S 129(6) . . ? _diffrn_measured_fraction_theta_max 0.969 _diffrn_reflns_theta_full 23.26 _diffrn_measured_fraction_theta_full 0.969 _refine_diff_density_max 4.788 _refine_diff_density_min -0.691 _refine_diff_density_rms 0.162 #===END