Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2001 ---------- X-Sun-Charset: us-ascii X-Sun-Content-Lines: 814 data_global _journal_coden_Cambridge 186 loop_ _publ_author_name 'Carmalt, Claire J.' 'Dinnage, Christopher W.' 'Parkin, I.' 'White, Andrew J. P.' 'Williams, David J.' _publ_contact_author_name 'Dr Claire J Carmalt' _publ_contact_author_address ; Department of Chemistry University College London Christopher Ingold Laboratories 20 Gordon Street London WC1H 0AJ ; _publ_contact_author_email C.J.CARMALT@UCL.AC.UK data_cc0010 _database_code_CSD 165273 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16 H37 N S3 Ti' _chemical_formula_weight 387.55 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ti' 'Ti' 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pbca loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 10.1445(8) _cell_length_b 15.861(4) _cell_length_c 28.332(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4558.6(12) _cell_formula_units_Z 8 _cell_measurement_temperature 183(2) _cell_measurement_reflns_used 26 _cell_measurement_theta_min 10.77 _cell_measurement_theta_max 28.00 _exptl_crystal_description blocks _exptl_crystal_colour Red _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.47 _exptl_crystal_size_min 0.33 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.129 _exptl_crystal_density_method ? _exptl_crystal_F_000 1680 _exptl_absorpt_coefficient_mu 5.694 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.3474 _exptl_absorpt_correction_T_max 0.7677 _exptl_special_details ; ? ; _diffrn_ambient_temperature 183(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3351 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0737 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 0 _diffrn_reflns_theta_min 3.12 _diffrn_reflns_theta_max 60.00 _reflns_number_total 3351 _reflns_number_observed 2199 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 367 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0849P)^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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00017(8) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2984 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1062 _refine_ls_R_factor_obs 0.0566 _refine_ls_wR_factor_all 0.1979 _refine_ls_wR_factor_obs 0.1368 _refine_ls_goodness_of_fit_all 1.039 _refine_ls_goodness_of_fit_obs 1.100 _refine_ls_restrained_S_all 1.281 _refine_ls_restrained_S_obs 1.100 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti Ti 0.18536(9) 0.58725(6) 0.13068(3) 0.0349(3) Uani 1 d . . S1 S 0.03528(14) 0.57768(10) 0.07031(4) 0.0430(3) Uani 1 d . . S2 S 0.13916(14) 0.69595(9) 0.18194(5) 0.0446(4) Uani 1 d . . S3 S 0.39041(15) 0.62456(11) 0.10487(6) 0.0548(4) Uani 1 d . . N N 0.1752(5) 0.4847(3) 0.16204(14) 0.0404(10) Uani 1 d . . C1 C 0.0613(6) 0.6594(4) 0.0238(2) 0.0489(14) Uani 1 d . . C2 C 0.1041(8) 0.7420(4) 0.0449(2) 0.060(2) Uani 1 d . . H2A H 0.1891(8) 0.7346(4) 0.0609(2) 0.090 Uiso 1 calc R . H2B H 0.0380(8) 0.7610(4) 0.0678(2) 0.090 Uiso 1 calc R . H2C H 0.1131(8) 0.7841(4) 0.0198(2) 0.090 Uiso 1 calc R . C3 C 0.1646(7) 0.6256(5) -0.0106(2) 0.062(2) Uani 1 d . . H3A H 0.1343(7) 0.5719(5) -0.0238(2) 0.093 Uiso 1 calc R . H3B H 0.2481(7) 0.6169(5) 0.0062(2) 0.093 Uiso 1 calc R . H3C H 0.1777(7) 0.6663(5) -0.0362(2) 0.093 Uiso 1 calc R . C4 C -0.0702(7) 0.6671(6) -0.0014(3) 0.071(2) Uani 1 d . . H4A H -0.0949(7) 0.6122(6) -0.0146(3) 0.107 Uiso 1 calc R . H4B H -0.0628(7) 0.7086(6) -0.0269(3) 0.107 Uiso 1 calc R . H4C H -0.1378(7) 0.6854(6) 0.0211(3) 0.107 Uiso 1 calc R . C5 C -0.0362(6) 0.7028(4) 0.2004(2) 0.0480(14) Uani 1 d . . C6 C -0.1090(8) 0.7564(7) 0.1656(4) 0.101(4) Uani 1 d . . H6A H -0.0675(8) 0.8121(7) 0.1639(4) 0.151 Uiso 1 calc R . H6B H -0.2009(8) 0.7625(7) 0.1757(4) 0.151 Uiso 1 calc R . H6C H -0.1063(8) 0.7297(7) 0.1345(4) 0.151 Uiso 1 calc R . C7 C -0.1009(6) 0.6161(5) 0.2030(3) 0.065(2) Uani 1 d . . H7A H -0.0533(6) 0.5810(5) 0.2258(3) 0.097 Uiso 1 calc R . H7B H -0.0982(6) 0.5894(5) 0.1718(3) 0.097 Uiso 1 calc R . H7C H -0.1928(6) 0.6223(5) 0.2131(3) 0.097 Uiso 1 calc R . C8 C -0.0328(8) 0.7421(6) 0.2495(3) 0.087(3) Uani 1 d . . H8A H 0.0157(8) 0.7049(6) 0.2710(3) 0.131 Uiso 1 calc R . H8B H -0.1231(8) 0.7495(6) 0.2611(3) 0.131 Uiso 1 calc R . H8C H 0.0111(8) 0.7970(6) 0.2480(3) 0.131 Uiso 1 calc R . C9 C 0.5267(6) 0.5462(5) 0.1022(2) 0.053(2) Uani 1 d . . C10 C 0.5748(11) 0.5315(9) 0.1518(3) 0.117(4) Uani 1 d . . H10A H 0.6045(11) 0.5850(9) 0.1654(3) 0.176 Uiso 1 calc R . H10B H 0.6483(11) 0.4914(9) 0.1513(3) 0.176 Uiso 1 calc R . H10C H 0.5028(11) 0.5085(9) 0.1709(3) 0.176 Uiso 1 calc R . C11 C 0.6365(9) 0.5906(7) 0.0751(4) 0.115(4) Uani 1 d . . H11A H 0.6614(9) 0.6424(7) 0.0917(4) 0.173 Uiso 1 calc R . H11B H 0.6055(9) 0.6047(7) 0.0433(4) 0.173 Uiso 1 calc R . H11C H 0.7132(9) 0.5532(7) 0.0729(4) 0.173 Uiso 1 calc R . C12 C 0.4802(11) 0.4657(7) 0.0799(5) 0.119(4) Uani 1 d . . H12A H 0.4496(11) 0.4771(7) 0.0477(5) 0.179 Uiso 1 calc R . H12B H 0.4076(11) 0.4422(7) 0.0985(5) 0.179 Uiso 1 calc R . H12C H 0.5531(11) 0.4251(7) 0.0789(5) 0.179 Uiso 1 calc R . C13 C 0.1557(7) 0.4066(4) 0.1344(2) 0.055(2) Uani 1 d . . H13A H 0.2163(7) 0.3626(4) 0.1463(2) 0.066 Uiso 1 calc R . H13B H 0.1786(7) 0.4176(4) 0.1010(2) 0.066 Uiso 1 calc R . C14 C 0.0152(9) 0.3737(5) 0.1369(2) 0.072(2) Uani 1 d . . H14A H 0.0077(9) 0.3222(5) 0.1180(2) 0.109 Uiso 1 calc R . H14B H -0.0453(9) 0.4165(5) 0.1245(2) 0.109 Uiso 1 calc R . H14C H -0.0075(9) 0.3614(5) 0.1698(2) 0.109 Uiso 1 calc R . C15 C 0.1707(6) 0.4713(4) 0.2134(2) 0.0455(13) Uani 1 d . . H15A H 0.0891(6) 0.4400(4) 0.2213(2) 0.055 Uiso 1 calc R . H15B H 0.1659(6) 0.5268(4) 0.2293(2) 0.055 Uiso 1 calc R . C16 C 0.2871(6) 0.4236(4) 0.2326(2) 0.054(2) Uani 1 d . . H16A H 0.2776(6) 0.4170(4) 0.2668(2) 0.081 Uiso 1 calc R . H16B H 0.3682(6) 0.4548(4) 0.2257(2) 0.081 Uiso 1 calc R . H16C H 0.2913(6) 0.3678(4) 0.2177(2) 0.081 Uiso 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 Ti 0.0360(4) 0.0361(5) 0.0327(4) -0.0009(4) -0.0009(4) -0.0001(4) S1 0.0478(7) 0.0445(7) 0.0368(6) 0.0062(6) -0.0071(5) -0.0059(6) S2 0.0418(7) 0.0422(7) 0.0497(7) -0.0106(6) 0.0046(6) -0.0032(6) S3 0.0403(7) 0.0520(8) 0.0722(10) 0.0045(7) 0.0085(7) -0.0023(7) N 0.047(2) 0.046(3) 0.028(2) 0.002(2) -0.001(2) 0.005(2) C1 0.058(3) 0.053(3) 0.035(3) 0.010(3) 0.004(3) -0.002(3) C2 0.082(4) 0.052(4) 0.046(3) 0.012(3) 0.009(3) 0.000(4) C3 0.064(4) 0.083(5) 0.040(3) 0.009(3) 0.011(3) 0.000(4) C4 0.064(4) 0.095(6) 0.054(4) 0.028(4) -0.008(3) 0.004(4) C5 0.041(3) 0.047(3) 0.055(3) 0.003(3) 0.007(3) 0.001(3) C6 0.058(4) 0.114(8) 0.131(8) 0.063(7) 0.033(5) 0.041(5) C7 0.044(3) 0.063(4) 0.087(5) -0.004(4) 0.010(3) -0.009(3) C8 0.083(5) 0.100(6) 0.078(5) -0.036(5) 0.040(5) -0.029(5) C9 0.043(3) 0.061(4) 0.057(3) 0.007(3) 0.006(3) 0.007(3) C10 0.087(6) 0.180(13) 0.086(6) 0.031(8) -0.017(6) 0.023(8) C11 0.071(5) 0.110(8) 0.164(10) 0.068(8) 0.065(6) 0.025(6) C12 0.098(7) 0.086(7) 0.174(12) -0.043(8) 0.017(8) 0.018(6) C13 0.085(4) 0.044(3) 0.036(3) -0.004(3) -0.008(3) 0.009(3) C14 0.116(7) 0.055(4) 0.046(3) 0.003(3) -0.008(4) -0.026(5) C15 0.066(4) 0.043(3) 0.028(2) 0.000(2) -0.001(3) 0.008(3) C16 0.064(4) 0.056(4) 0.043(3) 0.003(3) -0.016(3) 0.003(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti N 1.856(5) . ? Ti S3 2.283(2) . ? Ti S1 2.295(2) . ? Ti S2 2.302(2) . ? S1 C1 1.866(6) . ? S2 C5 1.858(6) . ? S3 C9 1.861(7) . ? N C15 1.472(6) . ? N C13 1.480(7) . ? C1 C2 1.504(10) . ? C1 C4 1.518(9) . ? C1 C3 1.528(9) . ? C5 C6 1.496(10) . ? C5 C7 1.525(9) . ? C5 C8 1.526(10) . ? C9 C12 1.502(12) . ? C9 C10 1.507(11) . ? C9 C11 1.524(10) . ? C13 C14 1.519(10) . ? C15 C16 1.504(8) . ? 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 N Ti S3 115.5(2) . . ? N Ti S1 105.18(15) . . ? S3 Ti S1 112.52(7) . . ? N Ti S2 110.06(14) . . ? S3 Ti S2 101.16(7) . . ? S1 Ti S2 112.62(7) . . ? C1 S1 Ti 112.7(2) . . ? C5 S2 Ti 114.6(2) . . ? C9 S3 Ti 121.2(2) . . ? C15 N C13 113.5(4) . . ? C15 N Ti 127.0(4) . . ? C13 N Ti 119.2(3) . . ? C2 C1 C4 111.7(6) . . ? C2 C1 C3 111.2(6) . . ? C4 C1 C3 109.3(5) . . ? C2 C1 S1 111.5(4) . . ? C4 C1 S1 105.3(4) . . ? C3 C1 S1 107.7(5) . . ? C6 C5 C7 109.4(7) . . ? C6 C5 C8 112.3(8) . . ? C7 C5 C8 109.4(6) . . ? C6 C5 S2 108.7(5) . . ? C7 C5 S2 111.9(4) . . ? C8 C5 S2 105.0(5) . . ? C12 C9 C10 111.2(9) . . ? C12 C9 C11 114.3(8) . . ? C10 C9 C11 107.7(8) . . ? C12 C9 S3 110.6(6) . . ? C10 C9 S3 107.8(6) . . ? C11 C9 S3 104.8(5) . . ? N C13 C14 112.8(5) . . ? N C15 C16 113.9(5) . . ? _refine_diff_density_max 0.296 _refine_diff_density_min -0.364 _refine_diff_density_rms 0.073 data_CC0012 _database_code_CSD 165274 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C34 H42 N S4 Ta' _chemical_formula_weight 773.88 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ta' 'Ta' -0.7052 6.5227 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/a loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 32.088(7) _cell_length_b 32.088(7) _cell_length_c 13.126(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 13515.4(56) _cell_formula_units_Z 16 _cell_measurement_temperature 203(2) _cell_measurement_reflns_used 21 _cell_measurement_theta_min 5.11 _cell_measurement_theta_max 12.56 _exptl_crystal_description blocks _exptl_crystal_colour Orange/red _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.67 _exptl_crystal_size_min 0.60 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.521 _exptl_crystal_density_method ? _exptl_crystal_F_000 6240 _exptl_absorpt_coefficient_mu 3.524 _exptl_absorpt_correction_type Ellipsoidal _exptl_absorpt_correction_T_min 0.1883 _exptl_absorpt_correction_T_max 0.2165 _exptl_special_details ; ? ; _diffrn_ambient_temperature 203(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 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 3.28 _diffrn_reflns_number 6188 _diffrn_reflns_av_R_equivalents 0.0330 _diffrn_reflns_av_sigmaI/netI 0.0594 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 38 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 38 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.80 _diffrn_reflns_theta_max 25.00 _reflns_number_total 5949 _reflns_number_observed 4529 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 388 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0247P)^2^+10.8914P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.000046(8) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 5561 _refine_ls_number_parameters 362 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0605 _refine_ls_R_factor_obs 0.0373 _refine_ls_wR_factor_all 0.0800 _refine_ls_wR_factor_obs 0.0694 _refine_ls_goodness_of_fit_all 1.013 _refine_ls_goodness_of_fit_obs 1.064 _refine_ls_restrained_S_all 1.060 _refine_ls_restrained_S_obs 1.064 _refine_ls_shift/esd_max 0.008 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ta Ta 1.104249(7) 0.593616(7) 0.72969(2) 0.02573(8) Uani 1 d . . S1 S 1.13393(5) 0.58158(5) 0.89716(12) 0.0360(3) Uani 1 d . . S2 S 1.05858(5) 0.59563(5) 0.58228(13) 0.0391(4) Uani 1 d . . S3 S 1.04154(5) 0.61784(5) 0.80942(12) 0.0326(3) Uani 1 d . . S4 S 1.11604(5) 0.52031(5) 0.71578(13) 0.0362(3) Uani 1 d . . N N 1.1454(2) 0.6317(2) 0.6786(4) 0.0334(11) Uani 1 d . . C1 C 1.1846(2) 0.6174(3) 0.6344(6) 0.051(2) Uani 1 d . . H1A H 1.1856(2) 0.6251(3) 0.5630(6) 0.076 Uiso 1 d R . H1B H 1.1864(2) 0.5873(3) 0.6406(6) 0.076 Uiso 1 d R . H1C H 1.2077(2) 0.6302(3) 0.6702(6) 0.076 Uiso 1 d R . C2 C 1.1413(2) 0.6767(2) 0.6735(6) 0.049(2) Uani 1 d . . H2A H 1.1146(2) 0.6849(2) 0.7014(6) 0.073 Uiso 1 d R . H2B H 1.1432(2) 0.6856(2) 0.6031(6) 0.073 Uiso 1 d R . H2C H 1.1635(2) 0.6896(2) 0.7126(6) 0.073 Uiso 1 d R . C3 C 1.1863(2) 0.6007(2) 0.8938(5) 0.0317(13) Uani 1 d . . C4 C 1.2189(2) 0.5732(2) 0.8766(5) 0.0361(14) Uani 1 d . . C5 C 1.2594(2) 0.5891(2) 0.8769(6) 0.047(2) Uani 1 d . . H5A H 1.2820(2) 0.5713(2) 0.8637(6) 0.056 Uiso 1 calc R . C6 C 1.2665(2) 0.6309(3) 0.8963(6) 0.053(2) Uani 1 d . . H6A H 1.2939(2) 0.6412(3) 0.8968(6) 0.063 Uiso 1 calc R . C7 C 1.2336(2) 0.6575(2) 0.9151(6) 0.046(2) Uani 1 d . . H7A H 1.2389(2) 0.6858(2) 0.9284(6) 0.055 Uiso 1 calc R . C8 C 1.1928(2) 0.6430(2) 0.9147(5) 0.0364(14) Uani 1 d . . C9 C 1.2123(2) 0.5277(2) 0.8578(6) 0.048(2) Uani 1 d . . H9A H 1.1896(2) 0.5178(2) 0.9003(6) 0.072 Uiso 1 d R . H9B H 1.2375(2) 0.5126(2) 0.8744(6) 0.072 Uiso 1 d R . H9C H 1.2053(2) 0.5233(2) 0.7867(6) 0.072 Uiso 1 d R . C10 C 1.1581(2) 0.6726(2) 0.9392(6) 0.046(2) Uani 1 d . . H10A H 1.1382(2) 0.6728(2) 0.8836(6) 0.070 Uiso 1 d R . H10B H 1.1693(2) 0.7004(2) 0.9486(6) 0.070 Uiso 1 d R . H10C H 1.1443(2) 0.6637(2) 1.0012(6) 0.070 Uiso 1 d R . C11 C 1.0759(2) 0.6362(2) 0.4968(5) 0.0336(13) Uani 1 d . . C12 C 1.1044(2) 0.6269(2) 0.4214(6) 0.049(2) Uani 1 d . . C13 C 1.1169(3) 0.6584(3) 0.3565(7) 0.062(2) Uani 1 d . . H13A H 1.1362(3) 0.6525(3) 0.3046(7) 0.075 Uiso 1 calc R . C14 C 1.1016(3) 0.6981(3) 0.3663(7) 0.067(2) Uani 1 d . . H14A H 1.1113(3) 0.7195(3) 0.3235(7) 0.081 Uiso 1 calc R . C15 C 1.0718(3) 0.7064(2) 0.4393(6) 0.053(2) Uani 1 d . . H15A H 1.0605(3) 0.7333(2) 0.4438(6) 0.063 Uiso 1 calc R . C16 C 1.0583(2) 0.6761(2) 0.5058(6) 0.044(2) Uani 1 d . . C17 C 1.1217(3) 0.5832(3) 0.4057(7) 0.072(3) Uani 1 d . . H17A H 1.1388(3) 0.5756(3) 0.4638(7) 0.108 Uiso 1 d R . H17B H 1.1385(3) 0.5827(3) 0.3443(7) 0.108 Uiso 1 d R . H17C H 1.0989(3) 0.5636(3) 0.3991(7) 0.108 Uiso 1 d R . C18 C 1.0267(3) 0.6865(3) 0.5868(7) 0.057(2) Uani 1 d . . H18A H 1.0404(3) 0.6878(3) 0.6526(7) 0.085 Uiso 1 d R . H18B H 1.0053(3) 0.6651(3) 0.5882(7) 0.085 Uiso 1 d R . H18C H 1.0141(3) 0.7132(3) 0.5716(7) 0.085 Uiso 1 d R . C19 C 1.0422(2) 0.6191(2) 0.9458(5) 0.0335(13) Uani 1 d . . C20 C 1.0446(2) 0.6574(2) 0.9961(5) 0.042(2) Uani 1 d . . C21 C 1.0416(3) 0.6574(3) 1.1010(6) 0.057(2) Uani 1 d . . H21A H 1.0428(3) 0.6830(3) 1.1356(6) 0.068 Uiso 1 calc R . C22 C 1.0367(3) 0.6211(3) 1.1574(6) 0.061(2) Uani 1 d . . H22A H 1.0354(3) 0.6219(3) 1.2289(6) 0.074 Uiso 1 calc R . C23 C 1.0338(2) 0.5841(3) 1.1064(6) 0.049(2) Uani 1 d . . H23A H 1.0296(2) 0.5595(3) 1.1438(6) 0.059 Uiso 1 calc R . C24 C 1.0368(2) 0.5817(2) 1.0010(5) 0.039(2) Uani 1 d . . C25 C 1.0487(2) 0.6981(2) 0.9409(6) 0.051(2) Uani 1 d . . H25A H 1.0555(2) 0.6929(2) 0.8701(6) 0.076 Uiso 1 d R . H25B H 1.0705(2) 0.7145(2) 0.9721(6) 0.076 Uiso 1 d R . H25C H 1.0225(2) 0.7131(2) 0.9448(6) 0.076 Uiso 1 d R . C26 C 1.0339(2) 0.5408(2) 0.9487(6) 0.050(2) Uani 1 d . . H26A H 1.0610(2) 0.5334(2) 0.9212(6) 0.075 Uiso 1 d R . H26B H 1.0138(2) 0.5427(2) 0.8936(6) 0.075 Uiso 1 d R . H26C H 1.0250(2) 0.5197(2) 0.9969(6) 0.075 Uiso 1 d R . C27 C 1.0953(2) 0.4956(2) 0.6046(5) 0.0352(13) Uani 1 d . . C28 C 1.0529(2) 0.4842(2) 0.6031(6) 0.041(2) Uani 1 d . . C29 C 1.0384(3) 0.4631(2) 0.5182(7) 0.053(2) Uani 1 d . . H29A H 1.0102(3) 0.4553(2) 0.5149(7) 0.063 Uiso 1 calc R . C30 C 1.0647(3) 0.4534(3) 0.4384(7) 0.065(2) Uani 1 d . . H30A H 1.0542(3) 0.4396(3) 0.3808(7) 0.078 Uiso 1 calc R . C31 C 1.1056(3) 0.4636(3) 0.4423(7) 0.066(2) Uani 1 d . . H31A H 1.1230(3) 0.4563(3) 0.3875(7) 0.079 Uiso 1 calc R . C32 C 1.1228(2) 0.4848(2) 0.5259(6) 0.049(2) Uani 1 d . . C33 C 1.0243(2) 0.4932(2) 0.6898(6) 0.047(2) Uani 1 d . . H33A H 1.0208(2) 0.5231(2) 0.6966(6) 0.070 Uiso 1 d R . H33B H 1.0360(2) 0.4820(2) 0.7522(6) 0.070 Uiso 1 d R . H33C H 0.9974(2) 0.4804(2) 0.6770(6) 0.070 Uiso 1 d R . C34 C 1.1689(3) 0.4935(3) 0.5282(9) 0.073(3) Uani 1 d . . H34A H 1.1821(3) 0.4803(3) 0.4701(9) 0.109 Uiso 1 d R . H34B H 1.1808(3) 0.4824(3) 0.5906(9) 0.109 Uiso 1 d R . H34C H 1.1736(3) 0.5234(3) 0.5254(9) 0.109 Uiso 1 d 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 Ta 0.02470(12) 0.02465(12) 0.02785(11) 0.00083(9) -0.00145(9) -0.00365(9) S1 0.0290(7) 0.0487(9) 0.0305(8) 0.0054(7) -0.0049(6) -0.0088(6) S2 0.0431(9) 0.0380(8) 0.0363(9) 0.0045(7) -0.0103(7) -0.0121(7) S3 0.0273(7) 0.0384(8) 0.0319(7) 0.0043(6) -0.0007(6) 0.0008(6) S4 0.0378(8) 0.0268(7) 0.0440(9) -0.0008(6) -0.0102(7) -0.0002(6) N 0.029(2) 0.039(3) 0.032(3) 0.002(2) -0.004(2) -0.008(2) C1 0.035(4) 0.059(5) 0.058(5) 0.003(4) 0.012(3) -0.001(3) C2 0.057(4) 0.030(3) 0.060(5) 0.010(3) -0.006(4) -0.011(3) C3 0.030(3) 0.040(3) 0.025(3) -0.001(2) -0.005(2) -0.004(2) C4 0.037(3) 0.035(3) 0.036(3) 0.004(3) -0.008(3) -0.001(3) C5 0.035(3) 0.058(4) 0.048(4) 0.010(3) -0.003(3) 0.005(3) C6 0.036(4) 0.066(5) 0.055(5) 0.009(4) -0.004(3) -0.018(3) C7 0.045(4) 0.044(4) 0.048(4) -0.003(3) -0.008(3) -0.013(3) C8 0.036(3) 0.044(4) 0.029(3) 0.002(3) -0.005(3) -0.006(3) C9 0.047(4) 0.038(4) 0.058(5) 0.000(3) -0.011(3) 0.003(3) C10 0.049(4) 0.042(4) 0.048(4) -0.015(3) -0.015(3) 0.008(3) C11 0.041(3) 0.031(3) 0.029(3) 0.005(2) -0.013(3) -0.008(2) C12 0.053(4) 0.053(4) 0.041(4) 0.001(3) 0.003(3) -0.002(3) C13 0.058(5) 0.082(6) 0.047(5) 0.015(4) 0.010(4) 0.000(4) C14 0.090(7) 0.059(5) 0.052(5) 0.024(4) -0.010(5) -0.009(5) C15 0.068(5) 0.036(4) 0.054(5) 0.011(3) -0.013(4) -0.007(3) C16 0.044(4) 0.046(4) 0.042(4) 0.007(3) -0.011(3) 0.002(3) C17 0.089(7) 0.078(6) 0.049(5) -0.004(5) 0.010(5) 0.029(5) C18 0.057(5) 0.054(4) 0.060(5) -0.007(4) -0.004(4) 0.014(4) C19 0.028(3) 0.038(3) 0.034(3) 0.001(3) 0.002(2) -0.001(2) C20 0.035(3) 0.052(4) 0.039(4) -0.005(3) 0.000(3) 0.003(3) C21 0.059(5) 0.063(5) 0.049(5) -0.014(4) -0.005(4) 0.016(4) C22 0.056(5) 0.091(7) 0.037(4) 0.005(4) 0.009(4) 0.026(4) C23 0.037(4) 0.067(5) 0.043(4) 0.020(4) 0.011(3) 0.012(3) C24 0.022(3) 0.053(4) 0.043(4) 0.009(3) 0.003(3) 0.001(2) C25 0.054(4) 0.042(4) 0.057(5) -0.005(3) -0.001(4) 0.000(3) C26 0.049(4) 0.050(4) 0.052(5) 0.018(3) -0.002(3) -0.011(3) C27 0.041(3) 0.027(3) 0.037(3) -0.004(3) -0.008(3) 0.000(3) C28 0.050(4) 0.028(3) 0.046(4) -0.002(3) -0.010(3) -0.002(3) C29 0.064(5) 0.039(4) 0.055(4) -0.007(4) -0.021(4) 0.004(3) C30 0.094(7) 0.048(4) 0.053(5) -0.020(4) -0.029(5) 0.013(4) C31 0.081(6) 0.060(5) 0.058(5) -0.019(4) 0.000(5) 0.019(5) C32 0.058(4) 0.033(3) 0.055(4) -0.005(3) -0.007(4) 0.010(3) C33 0.043(4) 0.048(4) 0.049(4) 0.000(3) -0.009(3) -0.010(3) C34 0.051(5) 0.076(6) 0.091(7) -0.017(6) 0.018(5) 0.007(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 Ta N 1.921(5) . ? Ta S4 2.389(2) . ? Ta S3 2.398(2) . ? Ta S1 2.427(2) . ? Ta S2 2.428(2) . ? S1 C3 1.788(6) . ? S2 C11 1.807(6) . ? S3 C19 1.791(7) . ? S4 C27 1.789(6) . ? N C2 1.450(8) . ? N C1 1.458(8) . ? C3 C4 1.387(9) . ? C3 C8 1.400(9) . ? C4 C5 1.397(9) . ? C4 C9 1.496(9) . ? C5 C6 1.384(11) . ? C6 C7 1.378(11) . ? C7 C8 1.389(9) . ? C8 C10 1.499(9) . ? C11 C12 1.380(10) . ? C11 C16 1.403(9) . ? C12 C13 1.380(11) . ? C12 C17 1.521(11) . ? C13 C14 1.372(13) . ? C14 C15 1.378(13) . ? C15 C16 1.377(10) . ? C16 C18 1.507(11) . ? C19 C20 1.397(9) . ? C19 C24 1.412(9) . ? C20 C21 1.379(11) . ? C20 C25 1.500(10) . ? C21 C22 1.389(13) . ? C22 C23 1.364(13) . ? C23 C24 1.389(10) . ? C24 C26 1.483(11) . ? C27 C32 1.402(11) . ? C27 C28 1.408(9) . ? C28 C29 1.384(10) . ? C28 C33 1.492(10) . ? C29 C30 1.383(13) . ? C30 C31 1.353(14) . ? C31 C32 1.404(12) . ? C32 C34 1.506(11) . ? 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 N Ta S4 119.4(2) . . ? N Ta S3 121.6(2) . . ? S4 Ta S3 119.04(6) . . ? N Ta S1 98.5(2) . . ? S4 Ta S1 81.40(6) . . ? S3 Ta S1 89.17(6) . . ? N Ta S2 96.9(2) . . ? S4 Ta S2 93.49(6) . . ? S3 Ta S2 80.37(6) . . ? S1 Ta S2 164.37(5) . . ? C3 S1 Ta 106.9(2) . . ? C11 S2 Ta 109.2(2) . . ? C19 S3 Ta 115.7(2) . . ? C27 S4 Ta 116.1(2) . . ? C2 N C1 111.9(6) . . ? C2 N Ta 125.9(5) . . ? C1 N Ta 122.1(5) . . ? C4 C3 C8 122.3(6) . . ? C4 C3 S1 119.6(5) . . ? C8 C3 S1 118.0(5) . . ? C3 C4 C5 118.0(6) . . ? C3 C4 C9 122.7(6) . . ? C5 C4 C9 119.3(6) . . ? C6 C5 C4 120.5(7) . . ? C7 C6 C5 120.4(7) . . ? C6 C7 C8 121.0(7) . . ? C7 C8 C3 117.8(6) . . ? C7 C8 C10 119.3(6) . . ? C3 C8 C10 122.9(6) . . ? C12 C11 C16 121.6(6) . . ? C12 C11 S2 119.5(5) . . ? C16 C11 S2 118.8(5) . . ? C11 C12 C13 118.4(7) . . ? C11 C12 C17 122.6(7) . . ? C13 C12 C17 118.9(8) . . ? C14 C13 C12 121.2(8) . . ? C13 C14 C15 119.5(8) . . ? C16 C15 C14 121.5(8) . . ? C15 C16 C11 117.7(7) . . ? C15 C16 C18 120.2(7) . . ? C11 C16 C18 122.2(7) . . ? C20 C19 C24 120.8(6) . . ? C20 C19 S3 119.5(5) . . ? C24 C19 S3 119.5(5) . . ? C21 C20 C19 117.9(7) . . ? C21 C20 C25 119.2(7) . . ? C19 C20 C25 122.8(6) . . ? C20 C21 C22 122.7(8) . . ? C23 C22 C21 118.3(8) . . ? C22 C23 C24 122.2(7) . . ? C23 C24 C19 118.1(7) . . ? C23 C24 C26 120.4(7) . . ? C19 C24 C26 121.4(6) . . ? C32 C27 C28 122.2(6) . . ? C32 C27 S4 118.5(5) . . ? C28 C27 S4 119.0(5) . . ? C29 C28 C27 117.7(7) . . ? C29 C28 C33 120.0(7) . . ? C27 C28 C33 122.3(6) . . ? C30 C29 C28 120.9(8) . . ? C31 C30 C29 120.7(8) . . ? C30 C31 C32 121.8(9) . . ? C27 C32 C31 116.6(7) . . ? C27 C32 C34 123.9(7) . . ? C31 C32 C34 119.4(8) . . ? _refine_diff_density_max 0.537 _refine_diff_density_min -0.498 _refine_diff_density_rms 0.103