# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Yong Tang' _publ_contact_author_email TANGY@MAIL.SIOC.AC.CN _publ_section_title ; Synthesis, Characterization, and Catalytic Behaviors of ?-Carbonylenamine-derived [O-NS]TiCl3 Complexes in Ethylene Homo- and Co-polymerization ; loop_ _publ_author_name 'Yong Tang' 'Xiu-Li Sun' 'Zheng Wang' 'Xiao-Hong Yang' # Attachment 'cd26113-4m.cif' data_cd26113 _database_code_depnum_ccdc_archive 'CCDC 734045' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H23 N O S' _chemical_formula_weight 373.49 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 '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)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 21.6646(19) _cell_length_b 8.0100(7) _cell_length_c 24.360(2) _cell_angle_alpha 90.00 _cell_angle_beta 106.432(2) _cell_angle_gamma 90.00 _cell_volume 4054.6(6) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1860 _cell_measurement_theta_min 4.449 _cell_measurement_theta_max 38.491 _exptl_crystal_description ? _exptl_crystal_colour yellow _exptl_crystal_size_max 0.369 _exptl_crystal_size_mid 0.278 _exptl_crystal_size_min 0.125 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.224 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1584 _exptl_absorpt_coefficient_mu 0.173 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.56879 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type '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 23753 _diffrn_reflns_av_R_equivalents 0.1314 _diffrn_reflns_av_sigmaI/netI 0.1843 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 1.74 _diffrn_reflns_theta_max 27.50 _reflns_number_total 9119 _reflns_number_gt 3129 _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^)+(0.0553P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 9119 _refine_ls_number_parameters 509 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.1590 _refine_ls_R_factor_gt 0.0654 _refine_ls_wR_factor_ref 0.1931 _refine_ls_wR_factor_gt 0.1749 _refine_ls_goodness_of_fit_ref 0.881 _refine_ls_restrained_S_all 0.881 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group S1 S 0.19156(5) 0.12519(16) 0.08425(5) 0.0777(4) Uani 1 1 d . . . S2 S 0.30647(5) 0.31690(14) 0.40787(5) 0.0692(4) Uani 1 1 d . . . O1 O 0.30205(13) 0.4582(4) 0.15826(12) 0.0738(8) Uani 1 1 d . . . O2 O 0.18268(13) -0.0232(4) 0.32921(12) 0.0771(9) Uani 1 1 d . . . N1 N 0.18439(17) 0.3902(4) 0.16113(15) 0.0584(9) Uani 1 1 d D . . N2 N 0.30263(17) 0.0433(4) 0.32886(15) 0.0570(9) Uani 1 1 d D . . C1 C 0.11875(17) 0.2184(5) 0.08698(17) 0.0547(10) Uani 1 1 d . . . C2 C 0.0587(2) 0.1731(5) 0.05139(18) 0.0720(12) Uani 1 1 d . . . H2 H 0.0557 0.0915 0.0236 0.086 Uiso 1 1 calc R . . C3 C 0.0037(2) 0.2488(6) 0.0571(2) 0.0822(14) Uani 1 1 d . . . H3 H -0.0364 0.2150 0.0343 0.099 Uiso 1 1 calc R . . C4 C 0.0081(2) 0.3714(7) 0.0957(2) 0.0914(16) Uani 1 1 d . . . H4 H -0.0290 0.4249 0.0984 0.110 Uiso 1 1 calc R . . C5 C 0.0669(2) 0.4191(6) 0.1314(2) 0.0812(14) Uani 1 1 d . . . H5 H 0.0692 0.5031 0.1583 0.097 Uiso 1 1 calc R . . C6 C 0.12224(18) 0.3419(5) 0.12719(17) 0.0550(10) Uani 1 1 d . . . C7 C 0.2059(2) 0.4250(5) 0.21763(18) 0.0564(11) Uani 1 1 d . . . C8 C 0.2683(2) 0.4711(5) 0.2413(2) 0.0584(11) Uani 1 1 d . . . C9 C 0.31507(19) 0.4867(4) 0.21093(18) 0.0550(10) Uani 1 1 d . . . C10 C 0.38156(19) 0.5393(4) 0.24141(17) 0.0516(10) Uani 1 1 d . . . C11 C 0.4093(2) 0.5195(5) 0.29956(19) 0.0660(12) Uani 1 1 d . . . H11 H 0.3854 0.4694 0.3213 0.079 Uiso 1 1 calc R . . C12 C 0.4710(2) 0.5715(6) 0.3262(2) 0.0789(14) Uani 1 1 d . . . H12 H 0.4882 0.5570 0.3655 0.095 Uiso 1 1 calc R . . C13 C 0.5068(2) 0.6443(6) 0.2950(2) 0.0809(14) Uani 1 1 d . . . H13 H 0.5487 0.6789 0.3127 0.097 Uiso 1 1 calc R . . C14 C 0.4801(2) 0.6663(6) 0.2365(2) 0.0815(14) Uani 1 1 d . . . H14 H 0.5040 0.7177 0.2149 0.098 Uiso 1 1 calc R . . C15 C 0.4193(2) 0.6131(5) 0.21054(19) 0.0672(12) Uani 1 1 d . . . H15 H 0.4025 0.6264 0.1712 0.081 Uiso 1 1 calc R . . C16 C 0.16149(19) 0.4040(5) 0.25467(17) 0.0753(13) Uani 1 1 d . . . H16A H 0.1379 0.5056 0.2545 0.113 Uiso 1 1 calc R . . H16B H 0.1863 0.3786 0.2931 0.113 Uiso 1 1 calc R . . H16C H 0.1320 0.3145 0.2400 0.113 Uiso 1 1 calc R . . C17 C 0.17356(17) 0.0150(5) 0.01882(17) 0.0533(10) Uani 1 1 d . . . C18 C 0.16153(17) 0.0977(5) -0.03320(19) 0.0592(11) Uani 1 1 d . . . C19 C 0.1573(2) 0.0074(9) -0.0820(2) 0.0932(17) Uani 1 1 d . . . H19 H 0.1485 0.0609 -0.1172 0.112 Uiso 1 1 calc R . . C20 C 0.1661(2) -0.1628(10) -0.0784(3) 0.115(3) Uani 1 1 d . . . H20 H 0.1642 -0.2236 -0.1114 0.138 Uiso 1 1 calc R . . C21 C 0.1774(3) -0.2416(7) -0.0285(4) 0.104(2) Uani 1 1 d . . . H21 H 0.1830 -0.3568 -0.0275 0.125 Uiso 1 1 calc R . . C22 C 0.1810(2) -0.1594(6) 0.0217(2) 0.0795(14) Uani 1 1 d . . . C23 C 0.1532(2) 0.2859(6) -0.0368(2) 0.0947(16) Uani 1 1 d . . . H23A H 0.1619 0.3260 -0.0710 0.142 Uiso 1 1 calc R . . H23B H 0.1825 0.3368 -0.0040 0.142 Uiso 1 1 calc R . . H23C H 0.1098 0.3139 -0.0378 0.142 Uiso 1 1 calc R . . C24 C 0.1934(3) -0.2555(6) 0.0764(3) 0.135(2) Uani 1 1 d . . . H24A H 0.2250 -0.1983 0.1060 0.202 Uiso 1 1 calc R . . H24B H 0.2089 -0.3650 0.0712 0.202 Uiso 1 1 calc R . . H24C H 0.1541 -0.2650 0.0871 0.202 Uiso 1 1 calc R . . C25 C 0.37443(18) 0.2000(5) 0.40513(17) 0.0548(10) Uani 1 1 d . . . C26 C 0.4356(2) 0.2300(5) 0.44098(19) 0.0716(12) Uani 1 1 d . . . H26 H 0.4421 0.3136 0.4685 0.086 Uiso 1 1 calc R . . C27 C 0.4872(2) 0.1339(7) 0.4355(2) 0.0915(16) Uani 1 1 d . . . H27 H 0.5284 0.1537 0.4593 0.110 Uiso 1 1 calc R . . C28 C 0.4771(2) 0.0088(7) 0.3944(2) 0.0868(15) Uani 1 1 d . . . H28 H 0.5116 -0.0556 0.3909 0.104 Uiso 1 1 calc R . . C29 C 0.4172(2) -0.0196(5) 0.35930(18) 0.0669(12) Uani 1 1 d . . . H29 H 0.4108 -0.1042 0.3321 0.080 Uiso 1 1 calc R . . C30 C 0.36547(19) 0.0760(5) 0.36342(17) 0.0539(10) Uani 1 1 d . . . C31 C 0.2807(2) 0.0148(4) 0.27211(18) 0.0547(10) Uani 1 1 d . . . C32 C 0.2175(2) -0.0288(5) 0.2468(2) 0.0577(11) Uani 1 1 d . . . C33 C 0.1706(2) -0.0487(5) 0.27650(18) 0.0571(11) Uani 1 1 d . . . C34 C 0.10519(19) -0.1104(5) 0.24509(19) 0.0578(11) Uani 1 1 d . . . C35 C 0.0786(2) -0.0919(5) 0.18672(19) 0.0685(12) Uani 1 1 d . . . H35 H 0.1022 -0.0386 0.1654 0.082 Uiso 1 1 calc R . . C36 C 0.0179(2) -0.1508(6) 0.1595(2) 0.0818(14) Uani 1 1 d . . . H36 H 0.0007 -0.1364 0.1203 0.098 Uiso 1 1 calc R . . C37 C -0.0175(2) -0.2318(6) 0.1910(2) 0.0827(14) Uani 1 1 d . . . H37 H -0.0579 -0.2753 0.1727 0.099 Uiso 1 1 calc R . . C38 C 0.0070(2) -0.2473(6) 0.2484(2) 0.0805(14) Uani 1 1 d . . . H38 H -0.0169 -0.2999 0.2697 0.097 Uiso 1 1 calc R . . C39 C 0.0675(2) -0.1850(5) 0.2755(2) 0.0739(13) Uani 1 1 d . . . H39 H 0.0833 -0.1936 0.3151 0.089 Uiso 1 1 calc R . . C40 C 0.32673(19) 0.0334(5) 0.23656(17) 0.0722(12) Uani 1 1 d . . . H40A H 0.3569 0.1208 0.2522 0.108 Uiso 1 1 calc R . . H40B H 0.3032 0.0609 0.1979 0.108 Uiso 1 1 calc R . . H40C H 0.3495 -0.0696 0.2369 0.108 Uiso 1 1 calc R . . C42 C 0.33967(19) 0.5739(5) 0.48451(19) 0.0604(11) Uani 1 1 d . . . C43 C 0.35215(19) 0.6381(5) 0.5393(2) 0.0688(12) Uani 1 1 d . . . H43 H 0.3576 0.7527 0.5447 0.083 Uiso 1 1 calc R . . C44 C 0.3566(2) 0.5374(6) 0.58565(19) 0.0693(12) Uani 1 1 d . . . H44 H 0.3653 0.5842 0.6220 0.083 Uiso 1 1 calc R . . C45 C 0.34845(18) 0.3685(5) 0.57894(18) 0.0615(11) Uani 1 1 d . . . H45 H 0.3519 0.3008 0.6107 0.074 Uiso 1 1 calc R . . C46 C 0.33510(17) 0.2989(5) 0.52507(17) 0.0531(10) Uani 1 1 d . . . C41 C 0.33075(17) 0.4019(5) 0.47839(16) 0.0500(10) Uani 1 1 d . . . C47 C 0.3370(2) 0.6887(5) 0.4336(2) 0.0939(16) Uani 1 1 d . . . H47A H 0.3516 0.7982 0.4474 0.141 Uiso 1 1 calc R . . H47B H 0.2935 0.6952 0.4095 0.141 Uiso 1 1 calc R . . H47C H 0.3642 0.6447 0.4121 0.141 Uiso 1 1 calc R . . C48 C 0.3276(2) 0.1108(4) 0.52021(19) 0.0756(13) Uani 1 1 d . . . H48A H 0.3642 0.0635 0.5110 0.113 Uiso 1 1 calc R . . H48B H 0.2892 0.0837 0.4906 0.113 Uiso 1 1 calc R . . H48C H 0.3249 0.0659 0.5560 0.113 Uiso 1 1 calc R . . H1 H 0.2129(19) 0.404(6) 0.144(2) 0.12(2) Uiso 1 1 d D . . H2A H 0.2729(13) 0.046(4) 0.3443(14) 0.050(12) Uiso 1 1 d D . . H8 H 0.2799(16) 0.490(4) 0.2793(14) 0.052(11) Uiso 1 1 d . . . H32 H 0.2060(13) -0.045(3) 0.2072(13) 0.032(9) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 S1 0.0532(7) 0.1171(10) 0.0583(8) -0.0251(7) 0.0083(5) 0.0210(7) S2 0.0608(7) 0.0876(8) 0.0555(7) -0.0099(6) 0.0102(6) 0.0155(6) O1 0.0628(19) 0.111(2) 0.0504(19) -0.0041(17) 0.0202(15) -0.0100(16) O2 0.072(2) 0.108(2) 0.057(2) 0.0006(18) 0.0277(17) -0.0158(17) N1 0.051(2) 0.075(2) 0.053(2) -0.0063(19) 0.0201(19) -0.0028(19) N2 0.053(2) 0.073(2) 0.051(2) -0.0020(19) 0.025(2) -0.0042(19) C1 0.041(2) 0.068(3) 0.057(3) -0.005(2) 0.017(2) 0.002(2) C2 0.059(3) 0.096(3) 0.061(3) -0.019(3) 0.018(2) -0.003(3) C3 0.039(3) 0.116(4) 0.090(4) -0.020(3) 0.015(2) 0.000(3) C4 0.049(3) 0.129(4) 0.100(4) -0.017(4) 0.027(3) 0.019(3) C5 0.066(3) 0.094(4) 0.086(4) -0.020(3) 0.026(3) 0.016(3) C6 0.048(3) 0.066(3) 0.055(3) -0.003(2) 0.020(2) -0.001(2) C7 0.061(3) 0.057(3) 0.056(3) -0.002(2) 0.024(2) 0.003(2) C8 0.057(3) 0.063(3) 0.057(3) -0.013(2) 0.019(2) -0.001(2) C9 0.063(3) 0.050(2) 0.059(3) 0.000(2) 0.028(2) -0.002(2) C10 0.057(3) 0.043(2) 0.056(3) -0.004(2) 0.018(2) 0.003(2) C11 0.066(3) 0.067(3) 0.068(3) -0.006(3) 0.025(3) -0.001(2) C12 0.062(3) 0.095(4) 0.075(3) -0.012(3) 0.011(3) 0.009(3) C13 0.055(3) 0.085(3) 0.098(4) -0.017(3) 0.015(3) -0.001(3) C14 0.056(3) 0.081(3) 0.113(5) 0.008(3) 0.032(3) -0.008(3) C15 0.062(3) 0.069(3) 0.073(3) 0.007(2) 0.023(3) -0.001(2) C16 0.063(3) 0.112(4) 0.058(3) -0.003(3) 0.028(2) 0.004(3) C17 0.045(2) 0.059(3) 0.057(3) -0.008(2) 0.017(2) 0.003(2) C18 0.047(2) 0.070(3) 0.059(3) -0.004(3) 0.012(2) -0.006(2) C19 0.059(3) 0.168(6) 0.051(3) -0.018(4) 0.015(2) 0.011(3) C20 0.057(3) 0.143(7) 0.134(6) -0.094(5) 0.009(4) -0.003(4) C21 0.068(4) 0.065(4) 0.178(7) -0.040(5) 0.035(5) 0.000(3) C22 0.062(3) 0.063(3) 0.119(5) -0.006(3) 0.034(3) 0.003(2) C23 0.083(4) 0.094(4) 0.104(4) 0.029(3) 0.021(3) 0.005(3) C24 0.135(5) 0.094(4) 0.189(7) 0.069(4) 0.067(5) 0.026(4) C25 0.051(3) 0.065(3) 0.054(3) 0.004(2) 0.024(2) 0.003(2) C26 0.059(3) 0.088(3) 0.068(3) -0.010(3) 0.018(2) -0.005(3) C27 0.045(3) 0.147(5) 0.082(4) -0.001(4) 0.016(3) 0.000(3) C28 0.066(4) 0.113(4) 0.087(4) 0.005(3) 0.030(3) 0.026(3) C29 0.061(3) 0.070(3) 0.070(3) -0.002(2) 0.019(3) 0.012(2) C30 0.050(3) 0.063(3) 0.053(3) 0.005(2) 0.022(2) -0.002(2) C31 0.069(3) 0.044(2) 0.058(3) -0.001(2) 0.028(2) 0.001(2) C32 0.062(3) 0.064(3) 0.050(3) -0.005(2) 0.021(2) -0.007(2) C33 0.067(3) 0.056(2) 0.051(3) 0.002(2) 0.021(2) -0.003(2) C34 0.058(3) 0.052(2) 0.067(3) 0.006(2) 0.024(2) 0.004(2) C35 0.068(3) 0.076(3) 0.059(3) -0.002(3) 0.015(2) -0.008(3) C36 0.073(3) 0.093(4) 0.073(3) -0.003(3) 0.011(3) -0.006(3) C37 0.065(3) 0.077(3) 0.096(4) -0.004(3) 0.008(3) 0.002(3) C38 0.057(3) 0.085(3) 0.102(4) 0.017(3) 0.025(3) 0.000(3) C39 0.054(3) 0.089(3) 0.080(3) 0.022(3) 0.021(3) 0.005(3) C40 0.070(3) 0.098(3) 0.057(3) 0.001(2) 0.033(2) 0.003(2) C42 0.060(3) 0.062(3) 0.065(3) 0.008(2) 0.028(2) 0.001(2) C43 0.075(3) 0.055(3) 0.087(4) -0.013(3) 0.038(3) -0.012(2) C44 0.072(3) 0.081(3) 0.057(3) -0.013(3) 0.023(2) -0.012(3) C45 0.057(3) 0.071(3) 0.055(3) 0.000(2) 0.014(2) -0.006(2) C46 0.044(2) 0.057(3) 0.056(3) -0.002(2) 0.012(2) -0.0048(19) C41 0.052(2) 0.055(3) 0.045(2) -0.004(2) 0.0169(19) -0.0023(19) C47 0.128(4) 0.075(3) 0.095(4) 0.008(3) 0.058(3) -0.012(3) C48 0.080(3) 0.053(3) 0.091(4) 0.004(2) 0.020(3) -0.002(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 S1 C1 1.763(4) . ? S1 C17 1.766(4) . ? S2 C25 1.762(4) . ? S2 C41 1.783(4) . ? O1 C9 1.254(4) . ? O2 C33 1.253(4) . ? N1 C7 1.351(5) . ? N1 C6 1.420(5) . ? N1 H1 0.844(19) . ? N2 C31 1.348(5) . ? N2 C30 1.408(5) . ? N2 H2A 0.831(17) . ? C1 C6 1.379(5) . ? C1 C2 1.391(5) . ? C2 C3 1.380(5) . ? C2 H2 0.9300 . ? C3 C4 1.344(6) . ? C3 H3 0.9300 . ? C4 C5 1.377(6) . ? C4 H4 0.9300 . ? C5 C6 1.379(5) . ? C5 H5 0.9300 . ? C7 C8 1.362(5) . ? C7 C16 1.503(5) . ? C8 C9 1.419(5) . ? C8 H8 0.90(3) . ? C9 C10 1.483(5) . ? C10 C11 1.382(5) . ? C10 C15 1.389(5) . ? C11 C12 1.375(6) . ? C11 H11 0.9300 . ? C12 C13 1.363(6) . ? C12 H12 0.9300 . ? C13 C14 1.391(6) . ? C13 H13 0.9300 . ? C14 C15 1.359(5) . ? C14 H14 0.9300 . ? C15 H15 0.9300 . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C17 C18 1.388(5) . ? C17 C22 1.406(6) . ? C18 C19 1.372(6) . ? C18 C23 1.518(5) . ? C19 C20 1.376(7) . ? C19 H19 0.9300 . ? C20 C21 1.332(7) . ? C20 H20 0.9300 . ? C21 C22 1.369(7) . ? C21 H21 0.9300 . ? C22 C24 1.497(7) . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? C24 H24A 0.9600 . ? C24 H24B 0.9600 . ? C24 H24C 0.9600 . ? C25 C26 1.386(5) . ? C25 C30 1.395(5) . ? C26 C27 1.395(5) . ? C26 H26 0.9300 . ? C27 C28 1.389(6) . ? C27 H27 0.9300 . ? C28 C29 1.356(6) . ? C28 H28 0.9300 . ? C29 C30 1.384(5) . ? C29 H29 0.9300 . ? C31 C32 1.377(5) . ? C31 C40 1.502(5) . ? C32 C33 1.413(5) . ? C32 H32 0.94(3) . ? C33 C34 1.491(5) . ? C34 C35 1.383(5) . ? C34 C39 1.384(5) . ? C35 C36 1.378(5) . ? C35 H35 0.9300 . ? C36 C37 1.389(6) . ? C36 H36 0.9300 . ? C37 C38 1.354(6) . ? C37 H37 0.9300 . ? C38 C39 1.384(5) . ? C38 H38 0.9300 . ? C39 H39 0.9300 . ? C40 H40A 0.9600 . ? C40 H40B 0.9600 . ? C40 H40C 0.9600 . ? C42 C43 1.383(5) . ? C42 C41 1.393(5) . ? C42 C47 1.531(5) . ? C43 C44 1.369(5) . ? C43 H43 0.9300 . ? C44 C45 1.368(5) . ? C44 H44 0.9300 . ? C45 C46 1.379(5) . ? C45 H45 0.9300 . ? C46 C41 1.386(5) . ? C46 C48 1.517(5) . ? C47 H47A 0.9600 . ? C47 H47B 0.9600 . ? C47 H47C 0.9600 . ? C48 H48A 0.9600 . ? C48 H48B 0.9600 . ? C48 H48C 0.9600 . ? 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 C1 S1 C17 105.91(19) . . ? C25 S2 C41 102.56(19) . . ? C7 N1 C6 130.2(4) . . ? C7 N1 H1 113(4) . . ? C6 N1 H1 117(4) . . ? C31 N2 C30 130.2(3) . . ? C31 N2 H2A 112(3) . . ? C30 N2 H2A 118(3) . . ? C6 C1 C2 118.9(4) . . ? C6 C1 S1 117.4(3) . . ? C2 C1 S1 123.7(3) . . ? C3 C2 C1 120.3(4) . . ? C3 C2 H2 119.9 . . ? C1 C2 H2 119.9 . . ? C4 C3 C2 120.0(4) . . ? C4 C3 H3 120.0 . . ? C2 C3 H3 120.0 . . ? C3 C4 C5 121.0(4) . . ? C3 C4 H4 119.5 . . ? C5 C4 H4 119.5 . . ? C4 C5 C6 119.8(4) . . ? C4 C5 H5 120.1 . . ? C6 C5 H5 120.1 . . ? C1 C6 C5 120.1(4) . . ? C1 C6 N1 117.5(3) . . ? C5 C6 N1 122.4(4) . . ? N1 C7 C8 120.1(4) . . ? N1 C7 C16 119.6(4) . . ? C8 C7 C16 120.2(4) . . ? C7 C8 C9 124.9(4) . . ? C7 C8 H8 116(2) . . ? C9 C8 H8 119(2) . . ? O1 C9 C8 122.0(4) . . ? O1 C9 C10 118.0(3) . . ? C8 C9 C10 120.0(4) . . ? C11 C10 C15 116.9(4) . . ? C11 C10 C9 124.0(4) . . ? C15 C10 C9 119.1(4) . . ? C12 C11 C10 122.1(4) . . ? C12 C11 H11 118.9 . . ? C10 C11 H11 118.9 . . ? C13 C12 C11 119.8(5) . . ? C13 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C12 C13 C14 119.3(5) . . ? C12 C13 H13 120.4 . . ? C14 C13 H13 120.4 . . ? C15 C14 C13 120.3(4) . . ? C15 C14 H14 119.9 . . ? C13 C14 H14 119.9 . . ? C14 C15 C10 121.6(4) . . ? C14 C15 H15 119.2 . . ? C10 C15 H15 119.2 . . ? C7 C16 H16A 109.5 . . ? C7 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C7 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C18 C17 C22 120.5(4) . . ? C18 C17 S1 121.5(3) . . ? C22 C17 S1 117.3(4) . . ? C19 C18 C17 119.3(4) . . ? C19 C18 C23 119.7(5) . . ? C17 C18 C23 121.0(4) . . ? C18 C19 C20 119.6(5) . . ? C18 C19 H19 120.2 . . ? C20 C19 H19 120.2 . . ? C21 C20 C19 120.9(6) . . ? C21 C20 H20 119.6 . . ? C19 C20 H20 119.6 . . ? C20 C21 C22 122.4(6) . . ? C20 C21 H21 118.8 . . ? C22 C21 H21 118.8 . . ? C21 C22 C17 117.2(5) . . ? C21 C22 C24 119.8(5) . . ? C17 C22 C24 123.0(5) . . ? C18 C23 H23A 109.5 . . ? C18 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C18 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C26 C25 C30 119.6(4) . . ? C26 C25 S2 122.9(3) . . ? C30 C25 S2 117.4(3) . . ? C25 C26 C27 119.5(4) . . ? C25 C26 H26 120.2 . . ? C27 C26 H26 120.2 . . ? C28 C27 C26 120.0(4) . . ? C28 C27 H27 120.0 . . ? C26 C27 H27 120.0 . . ? C29 C28 C27 120.1(4) . . ? C29 C28 H28 119.9 . . ? C27 C28 H28 119.9 . . ? C28 C29 C30 120.8(4) . . ? C28 C29 H29 119.6 . . ? C30 C29 H29 119.6 . . ? C29 C30 C25 119.8(4) . . ? C29 C30 N2 121.4(4) . . ? C25 C30 N2 118.7(3) . . ? N2 C31 C32 121.3(4) . . ? N2 C31 C40 118.4(4) . . ? C32 C31 C40 120.3(4) . . ? C31 C32 C33 124.6(4) . . ? C31 C32 H32 116.0(18) . . ? C33 C32 H32 119.5(18) . . ? O2 C33 C32 122.3(4) . . ? O2 C33 C34 118.2(4) . . ? C32 C33 C34 119.5(4) . . ? C35 C34 C39 117.4(4) . . ? C35 C34 C33 123.4(4) . . ? C39 C34 C33 119.1(4) . . ? C36 C35 C34 121.4(4) . . ? C36 C35 H35 119.3 . . ? C34 C35 H35 119.3 . . ? C35 C36 C37 119.7(5) . . ? C35 C36 H36 120.2 . . ? C37 C36 H36 120.2 . . ? C38 C37 C36 119.8(5) . . ? C38 C37 H37 120.1 . . ? C36 C37 H37 120.1 . . ? C37 C38 C39 120.1(4) . . ? C37 C38 H38 120.0 . . ? C39 C38 H38 120.0 . . ? C38 C39 C34 121.5(5) . . ? C38 C39 H39 119.2 . . ? C34 C39 H39 119.2 . . ? C31 C40 H40A 109.5 . . ? C31 C40 H40B 109.5 . . ? H40A C40 H40B 109.5 . . ? C31 C40 H40C 109.5 . . ? H40A C40 H40C 109.5 . . ? H40B C40 H40C 109.5 . . ? C43 C42 C41 117.0(4) . . ? C43 C42 C47 120.6(4) . . ? C41 C42 C47 122.3(4) . . ? C44 C43 C42 121.7(4) . . ? C44 C43 H43 119.1 . . ? C42 C43 H43 119.1 . . ? C45 C44 C43 120.5(4) . . ? C45 C44 H44 119.8 . . ? C43 C44 H44 119.8 . . ? C44 C45 C46 119.9(4) . . ? C44 C45 H45 120.0 . . ? C46 C45 H45 120.0 . . ? C45 C46 C41 119.2(4) . . ? C45 C46 C48 117.7(4) . . ? C41 C46 C48 123.1(4) . . ? C46 C41 C42 121.7(4) . . ? C46 C41 S2 119.7(3) . . ? C42 C41 S2 118.3(3) . . ? C42 C47 H47A 109.5 . . ? C42 C47 H47B 109.5 . . ? H47A C47 H47B 109.5 . . ? C42 C47 H47C 109.5 . . ? H47A C47 H47C 109.5 . . ? H47B C47 H47C 109.5 . . ? C46 C48 H48A 109.5 . . ? C46 C48 H48B 109.5 . . ? H48A C48 H48B 109.5 . . ? C46 C48 H48C 109.5 . . ? H48A C48 H48C 109.5 . . ? H48B C48 H48C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C17 S1 C1 C6 -165.6(3) . . . . ? C17 S1 C1 C2 14.9(4) . . . . ? C6 C1 C2 C3 -1.2(6) . . . . ? S1 C1 C2 C3 178.3(3) . . . . ? C1 C2 C3 C4 2.7(7) . . . . ? C2 C3 C4 C5 -2.5(8) . . . . ? C3 C4 C5 C6 0.9(8) . . . . ? C2 C1 C6 C5 -0.4(6) . . . . ? S1 C1 C6 C5 -179.9(3) . . . . ? C2 C1 C6 N1 -177.3(4) . . . . ? S1 C1 C6 N1 3.2(5) . . . . ? C4 C5 C6 C1 0.6(7) . . . . ? C4 C5 C6 N1 177.3(4) . . . . ? C7 N1 C6 C1 -138.5(4) . . . . ? C7 N1 C6 C5 44.7(6) . . . . ? C6 N1 C7 C8 -179.4(4) . . . . ? C6 N1 C7 C16 3.8(6) . . . . ? N1 C7 C8 C9 0.0(6) . . . . ? C16 C7 C8 C9 176.9(4) . . . . ? C7 C8 C9 O1 -0.1(6) . . . . ? C7 C8 C9 C10 179.5(4) . . . . ? O1 C9 C10 C11 -156.6(4) . . . . ? C8 C9 C10 C11 23.8(6) . . . . ? O1 C9 C10 C15 23.4(5) . . . . ? C8 C9 C10 C15 -156.3(4) . . . . ? C15 C10 C11 C12 0.7(6) . . . . ? C9 C10 C11 C12 -179.4(4) . . . . ? C10 C11 C12 C13 -0.4(6) . . . . ? C11 C12 C13 C14 0.6(7) . . . . ? C12 C13 C14 C15 -1.1(7) . . . . ? C13 C14 C15 C10 1.5(7) . . . . ? C11 C10 C15 C14 -1.3(6) . . . . ? C9 C10 C15 C14 178.8(4) . . . . ? C1 S1 C17 C18 72.3(3) . . . . ? C1 S1 C17 C22 -116.8(3) . . . . ? C22 C17 C18 C19 -0.3(6) . . . . ? S1 C17 C18 C19 170.4(3) . . . . ? C22 C17 C18 C23 179.8(4) . . . . ? S1 C17 C18 C23 -9.5(5) . . . . ? C17 C18 C19 C20 -1.2(6) . . . . ? C23 C18 C19 C20 178.7(4) . . . . ? C18 C19 C20 C21 1.4(8) . . . . ? C19 C20 C21 C22 -0.2(9) . . . . ? C20 C21 C22 C17 -1.2(8) . . . . ? C20 C21 C22 C24 179.6(5) . . . . ? C18 C17 C22 C21 1.5(6) . . . . ? S1 C17 C22 C21 -169.6(3) . . . . ? C18 C17 C22 C24 -179.3(4) . . . . ? S1 C17 C22 C24 9.6(6) . . . . ? C41 S2 C25 C26 -21.8(4) . . . . ? C41 S2 C25 C30 160.3(3) . . . . ? C30 C25 C26 C27 -1.0(6) . . . . ? S2 C25 C26 C27 -178.8(3) . . . . ? C25 C26 C27 C28 -0.2(7) . . . . ? C26 C27 C28 C29 0.4(7) . . . . ? C27 C28 C29 C30 0.6(7) . . . . ? C28 C29 C30 C25 -1.8(6) . . . . ? C28 C29 C30 N2 -177.4(4) . . . . ? C26 C25 C30 C29 2.0(6) . . . . ? S2 C25 C30 C29 179.9(3) . . . . ? C26 C25 C30 N2 177.7(4) . . . . ? S2 C25 C30 N2 -4.4(5) . . . . ? C31 N2 C30 C29 -46.9(6) . . . . ? C31 N2 C30 C25 137.5(4) . . . . ? C30 N2 C31 C32 174.5(4) . . . . ? C30 N2 C31 C40 -6.2(6) . . . . ? N2 C31 C32 C33 -0.4(6) . . . . ? C40 C31 C32 C33 -179.8(4) . . . . ? C31 C32 C33 O2 2.1(6) . . . . ? C31 C32 C33 C34 -174.8(4) . . . . ? O2 C33 C34 C35 158.0(4) . . . . ? C32 C33 C34 C35 -25.1(6) . . . . ? O2 C33 C34 C39 -19.7(6) . . . . ? C32 C33 C34 C39 157.3(4) . . . . ? C39 C34 C35 C36 -2.3(6) . . . . ? C33 C34 C35 C36 -179.9(4) . . . . ? C34 C35 C36 C37 -0.5(7) . . . . ? C35 C36 C37 C38 2.2(7) . . . . ? C36 C37 C38 C39 -1.1(7) . . . . ? C37 C38 C39 C34 -1.9(7) . . . . ? C35 C34 C39 C38 3.5(6) . . . . ? C33 C34 C39 C38 -178.8(4) . . . . ? C41 C42 C43 C44 1.0(6) . . . . ? C47 C42 C43 C44 -178.1(4) . . . . ? C42 C43 C44 C45 -0.3(6) . . . . ? C43 C44 C45 C46 -0.5(6) . . . . ? C44 C45 C46 C41 0.6(6) . . . . ? C44 C45 C46 C48 179.0(3) . . . . ? C45 C46 C41 C42 0.1(5) . . . . ? C48 C46 C41 C42 -178.1(3) . . . . ? C45 C46 C41 S2 -174.4(3) . . . . ? C48 C46 C41 S2 7.3(5) . . . . ? C43 C42 C41 C46 -0.9(6) . . . . ? C47 C42 C41 C46 178.2(4) . . . . ? C43 C42 C41 S2 173.7(3) . . . . ? C47 C42 C41 S2 -7.2(5) . . . . ? C25 S2 C41 C46 -72.4(3) . . . . ? C25 S2 C41 C42 112.9(3) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H1 O1 0.844(19) 1.91(4) 2.627(4) 141(5) . N2 H2A O2 0.831(17) 1.96(3) 2.655(4) 140(3) . _diffrn_measured_fraction_theta_max 0.980 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.980 _refine_diff_density_max 0.192 _refine_diff_density_min -0.196 _refine_diff_density_rms 0.054 # Attachment 'cd26190-5b.cif' data_cd26190 _database_code_depnum_ccdc_archive 'CCDC 734047' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H22 Cl3 N O S Ti' _chemical_formula_weight 478.70 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' Ti Ti 0.2776 0.4457 '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)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.0434(10) _cell_length_b 11.2130(15) _cell_length_c 28.939(4) _cell_angle_alpha 90.00 _cell_angle_beta 96.423(3) _cell_angle_gamma 90.00 _cell_volume 2271.2(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2184 _cell_measurement_theta_min 4.607 _cell_measurement_theta_max 44.988 _exptl_crystal_description prismatic _exptl_crystal_colour red _exptl_crystal_size_max 0.486 _exptl_crystal_size_mid 0.092 _exptl_crystal_size_min 0.070 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.400 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 984 _exptl_absorpt_coefficient_mu 0.832 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.8817 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type '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 13122 _diffrn_reflns_av_R_equivalents 0.0548 _diffrn_reflns_av_sigmaI/netI 0.0811 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_limit_l_max 36 _diffrn_reflns_theta_min 1.95 _diffrn_reflns_theta_max 27.00 _reflns_number_total 4923 _reflns_number_gt 3177 _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^)+(0.0291P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4923 _refine_ls_number_parameters 246 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0846 _refine_ls_R_factor_gt 0.0503 _refine_ls_wR_factor_ref 0.0928 _refine_ls_wR_factor_gt 0.0842 _refine_ls_goodness_of_fit_ref 0.921 _refine_ls_restrained_S_all 0.921 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti Ti 0.87544(8) 0.19827(5) 0.890387(18) 0.03254(16) Uani 1 1 d . . . Cl1 Cl 1.10232(12) 0.31730(7) 0.86302(3) 0.0466(2) Uani 1 1 d . . . Cl2 Cl 0.70988(13) 0.35574(8) 0.91482(3) 0.0553(3) Uani 1 1 d . . . Cl3 Cl 0.71102(12) 0.05915(7) 0.93054(3) 0.0469(2) Uani 1 1 d . . . S1 S 1.09363(12) 0.17980(7) 0.97045(3) 0.0370(2) Uani 1 1 d . . . O1 O 0.7403(3) 0.15820(16) 0.83498(7) 0.0385(5) Uani 1 1 d . . . N1 N 1.0493(3) 0.0478(2) 0.87676(8) 0.0327(6) Uani 1 1 d . . . C1 C 1.2124(5) 0.0448(2) 0.95539(10) 0.0405(8) Uani 1 1 d . . . H1A H 1.3366 0.0398 0.9735 0.049 Uiso 1 1 calc R . . H1B H 1.1379 -0.0237 0.9631 0.049 Uiso 1 1 calc R . . C2 C 1.2922(5) 0.2865(3) 0.97782(11) 0.0441(8) Uani 1 1 d . . . H2 H 1.3547 0.2893 0.9492 0.053 Uiso 1 1 calc R . . C3 C 1.4379(5) 0.2514(3) 1.01842(12) 0.0644(11) Uani 1 1 d . . . H3A H 1.5345 0.3120 1.0232 0.097 Uiso 1 1 calc R . . H3B H 1.4960 0.1769 1.0117 0.097 Uiso 1 1 calc R . . H3C H 1.3752 0.2433 1.0460 0.097 Uiso 1 1 calc R . . C4 C 1.2036(6) 0.4072(3) 0.98578(14) 0.0777(13) Uani 1 1 d . . . H4A H 1.1501 0.4065 1.0149 0.117 Uiso 1 1 calc R . . H4B H 1.1048 0.4237 0.9610 0.117 Uiso 1 1 calc R . . H4C H 1.3001 0.4679 0.9865 0.117 Uiso 1 1 calc R . . C5 C 1.0607(6) -0.2418(3) 0.88469(13) 0.0665(12) Uani 1 1 d . . . H5 H 0.9696 -0.2272 0.9049 0.080 Uiso 1 1 calc R . . C6 C 1.2373(4) 0.0417(3) 0.90428(10) 0.0384(8) Uani 1 1 d . . . H6A H 1.3152 0.1086 0.8966 0.046 Uiso 1 1 calc R . . H6B H 1.3018 -0.0313 0.8971 0.046 Uiso 1 1 calc R . . C7 C 0.9870(5) -0.0430(3) 0.85092(10) 0.0361(8) Uani 1 1 d . . . C8 C 0.8117(5) -0.0402(3) 0.82088(10) 0.0418(8) Uani 1 1 d . . . H8 H 0.7721 -0.1107 0.8059 0.050 Uiso 1 1 calc R . . C9 C 0.6986(5) 0.0565(3) 0.81244(10) 0.0354(8) Uani 1 1 d . . . C10 C 1.1599(8) -0.3481(3) 0.88741(15) 0.0831(15) Uani 1 1 d . . . H10 H 1.1333 -0.4050 0.9092 0.100 Uiso 1 1 calc R . . C11 C 1.2945(7) -0.3707(4) 0.85913(17) 0.0787(14) Uani 1 1 d . . . H11 H 1.3625 -0.4419 0.8615 0.094 Uiso 1 1 calc R . . C12 C 1.3290(6) -0.2880(4) 0.82725(17) 0.0852(15) Uani 1 1 d . . . H12 H 1.4226 -0.3024 0.8077 0.102 Uiso 1 1 calc R . . C13 C 1.2268(6) -0.1818(3) 0.82315(14) 0.0696(13) Uani 1 1 d . . . H13 H 1.2485 -0.1268 0.8003 0.083 Uiso 1 1 calc R . . C14 C 1.0951(5) -0.1589(3) 0.85284(11) 0.0373(8) Uani 1 1 d . . . C15 C 0.5232(5) 0.0590(3) 0.77908(10) 0.0384(8) Uani 1 1 d . . . C16 C 0.4957(5) -0.0208(3) 0.74188(11) 0.0493(9) Uani 1 1 d . . . H16 H 0.5920 -0.0744 0.7368 0.059 Uiso 1 1 calc R . . C17 C 0.3282(6) -0.0210(4) 0.71276(13) 0.0670(12) Uani 1 1 d . . . H17 H 0.3116 -0.0744 0.6881 0.080 Uiso 1 1 calc R . . C18 C 0.1840(6) 0.0581(4) 0.72001(14) 0.0726(12) Uani 1 1 d . . . H18 H 0.0700 0.0578 0.7004 0.087 Uiso 1 1 calc R . . C19 C 0.2104(6) 0.1375(3) 0.75649(14) 0.0641(11) Uani 1 1 d . . . H19 H 0.1140 0.1912 0.7614 0.077 Uiso 1 1 calc R . . C20 C 0.3787(5) 0.1381(3) 0.78581(11) 0.0463(9) Uani 1 1 d . . . H20 H 0.3950 0.1922 0.8103 0.056 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 Ti 0.0307(4) 0.0325(3) 0.0333(3) 0.0000(2) -0.0014(3) 0.0018(3) Cl1 0.0488(6) 0.0405(5) 0.0510(5) 0.0052(4) 0.0073(4) -0.0051(4) Cl2 0.0554(6) 0.0506(5) 0.0605(6) -0.0072(4) 0.0094(5) 0.0165(4) Cl3 0.0324(5) 0.0573(6) 0.0504(5) 0.0092(4) 0.0025(4) -0.0072(4) S1 0.0331(5) 0.0426(5) 0.0345(4) 0.0004(4) 0.0008(4) -0.0015(4) O1 0.0431(14) 0.0331(12) 0.0375(12) -0.0019(10) -0.0044(10) 0.0034(10) N1 0.0296(16) 0.0331(15) 0.0348(14) -0.0002(11) 0.0010(12) 0.0018(11) C1 0.037(2) 0.0343(18) 0.049(2) 0.0073(15) -0.0026(16) 0.0031(15) C2 0.042(2) 0.044(2) 0.045(2) -0.0060(16) -0.0008(17) -0.0099(16) C3 0.050(3) 0.066(3) 0.072(3) -0.003(2) -0.018(2) -0.008(2) C4 0.088(4) 0.045(2) 0.091(3) -0.007(2) -0.026(3) -0.005(2) C5 0.086(3) 0.056(3) 0.062(3) 0.013(2) 0.026(2) 0.016(2) C6 0.032(2) 0.0378(19) 0.044(2) -0.0024(15) -0.0019(16) 0.0043(15) C7 0.037(2) 0.0334(18) 0.0393(18) 0.0006(15) 0.0083(16) -0.0016(15) C8 0.044(2) 0.0341(19) 0.046(2) -0.0085(15) -0.0021(17) -0.0042(16) C9 0.039(2) 0.0349(18) 0.0324(17) -0.0023(14) 0.0033(15) -0.0061(15) C10 0.126(5) 0.048(3) 0.074(3) 0.025(2) 0.007(3) 0.015(3) C11 0.076(4) 0.044(3) 0.112(4) -0.013(3) -0.011(3) 0.018(2) C12 0.076(4) 0.054(3) 0.132(4) -0.016(3) 0.040(3) 0.011(2) C13 0.086(3) 0.042(2) 0.088(3) 0.002(2) 0.041(3) 0.004(2) C14 0.039(2) 0.0312(18) 0.0408(19) -0.0033(15) -0.0003(16) 0.0008(15) C15 0.039(2) 0.0402(19) 0.0342(18) 0.0022(15) -0.0022(15) -0.0058(16) C16 0.050(2) 0.053(2) 0.044(2) -0.0042(17) 0.0001(18) -0.0074(18) C17 0.074(3) 0.072(3) 0.050(2) -0.005(2) -0.014(2) -0.022(2) C18 0.056(3) 0.095(3) 0.059(3) 0.006(2) -0.028(2) -0.014(3) C19 0.047(3) 0.071(3) 0.070(3) 0.008(2) -0.012(2) 0.005(2) C20 0.049(2) 0.046(2) 0.042(2) 0.0043(16) -0.0046(18) 0.0015(18) _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 O1 1.827(2) . ? Ti N1 2.148(2) . ? Ti Cl2 2.2720(10) . ? Ti Cl1 2.2902(10) . ? Ti Cl3 2.3293(9) . ? Ti S1 2.6413(10) . ? S1 C1 1.806(3) . ? S1 C2 1.835(3) . ? O1 C9 1.330(3) . ? N1 C7 1.309(4) . ? N1 C6 1.468(4) . ? C1 C6 1.509(4) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C2 C4 1.518(4) . ? C2 C3 1.523(4) . ? C2 H2 0.9800 . ? C3 H3A 0.9600 . ? C3 H3B 0.9600 . ? C3 H3C 0.9600 . ? C4 H4A 0.9600 . ? C4 H4B 0.9600 . ? C4 H4C 0.9600 . ? C5 C14 1.350(4) . ? C5 C10 1.379(5) . ? C5 H5 0.9300 . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C8 1.429(4) . ? C7 C14 1.504(4) . ? C8 C9 1.351(4) . ? C8 H8 0.9300 . ? C9 C15 1.481(4) . ? C10 C11 1.344(5) . ? C10 H10 0.9300 . ? C11 C12 1.349(5) . ? C11 H11 0.9300 . ? C12 C13 1.390(5) . ? C12 H12 0.9300 . ? C13 C14 1.357(4) . ? C13 H13 0.9300 . ? C15 C20 1.381(4) . ? C15 C16 1.397(4) . ? C16 C17 1.371(5) . ? C16 H16 0.9300 . ? C17 C18 1.382(5) . ? C17 H17 0.9300 . ? C18 C19 1.378(5) . ? C18 H18 0.9300 . ? C19 C20 1.378(5) . ? C19 H19 0.9300 . ? C20 H20 0.9300 . ? 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 O1 Ti N1 84.12(9) . . ? O1 Ti Cl2 103.24(7) . . ? N1 Ti Cl2 172.31(7) . . ? O1 Ti Cl1 98.92(7) . . ? N1 Ti Cl1 87.72(7) . . ? Cl2 Ti Cl1 93.26(4) . . ? O1 Ti Cl3 91.93(7) . . ? N1 Ti Cl3 83.74(7) . . ? Cl2 Ti Cl3 93.68(4) . . ? Cl1 Ti Cl3 165.43(4) . . ? O1 Ti S1 161.00(7) . . ? N1 Ti S1 79.14(7) . . ? Cl2 Ti S1 93.24(3) . . ? Cl1 Ti S1 89.37(3) . . ? Cl3 Ti S1 77.46(3) . . ? C1 S1 C2 101.97(15) . . ? C1 S1 Ti 95.38(11) . . ? C2 S1 Ti 114.32(11) . . ? C9 O1 Ti 134.91(19) . . ? C7 N1 C6 119.9(3) . . ? C7 N1 Ti 123.6(2) . . ? C6 N1 Ti 115.79(18) . . ? C6 C1 S1 111.3(2) . . ? C6 C1 H1A 109.4 . . ? S1 C1 H1A 109.4 . . ? C6 C1 H1B 109.4 . . ? S1 C1 H1B 109.4 . . ? H1A C1 H1B 108.0 . . ? C4 C2 C3 111.5(3) . . ? C4 C2 S1 106.2(2) . . ? C3 C2 S1 111.1(2) . . ? C4 C2 H2 109.3 . . ? C3 C2 H2 109.3 . . ? S1 C2 H2 109.3 . . ? C2 C3 H3A 109.5 . . ? C2 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? C2 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? C2 C4 H4A 109.5 . . ? C2 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C2 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C14 C5 C10 120.4(4) . . ? C14 C5 H5 119.8 . . ? C10 C5 H5 119.8 . . ? N1 C6 C1 109.5(2) . . ? N1 C6 H6A 109.8 . . ? C1 C6 H6A 109.8 . . ? N1 C6 H6B 109.8 . . ? C1 C6 H6B 109.8 . . ? H6A C6 H6B 108.2 . . ? N1 C7 C8 122.8(3) . . ? N1 C7 C14 121.0(3) . . ? C8 C7 C14 116.2(3) . . ? C9 C8 C7 125.4(3) . . ? C9 C8 H8 117.3 . . ? C7 C8 H8 117.3 . . ? O1 C9 C8 120.4(3) . . ? O1 C9 C15 115.2(3) . . ? C8 C9 C15 124.4(3) . . ? C11 C10 C5 121.1(4) . . ? C11 C10 H10 119.5 . . ? C5 C10 H10 119.5 . . ? C10 C11 C12 118.7(4) . . ? C10 C11 H11 120.7 . . ? C12 C11 H11 120.7 . . ? C11 C12 C13 121.1(4) . . ? C11 C12 H12 119.5 . . ? C13 C12 H12 119.5 . . ? C14 C13 C12 119.5(4) . . ? C14 C13 H13 120.3 . . ? C12 C13 H13 120.3 . . ? C5 C14 C13 119.3(3) . . ? C5 C14 C7 119.4(3) . . ? C13 C14 C7 121.3(3) . . ? C20 C15 C16 118.7(3) . . ? C20 C15 C9 119.7(3) . . ? C16 C15 C9 121.6(3) . . ? C17 C16 C15 120.7(4) . . ? C17 C16 H16 119.7 . . ? C15 C16 H16 119.7 . . ? C16 C17 C18 120.1(4) . . ? C16 C17 H17 119.9 . . ? C18 C17 H17 119.9 . . ? C19 C18 C17 119.5(4) . . ? C19 C18 H18 120.2 . . ? C17 C18 H18 120.2 . . ? C18 C19 C20 120.5(4) . . ? C18 C19 H19 119.7 . . ? C20 C19 H19 119.7 . . ? C19 C20 C15 120.4(3) . . ? C19 C20 H20 119.8 . . ? C15 C20 H20 119.8 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O1 Ti S1 C1 23.7(2) . . . . ? N1 Ti S1 C1 -4.87(12) . . . . ? Cl2 Ti S1 C1 174.10(11) . . . . ? Cl1 Ti S1 C1 -92.66(11) . . . . ? Cl3 Ti S1 C1 81.05(11) . . . . ? O1 Ti S1 C2 129.5(2) . . . . ? N1 Ti S1 C2 100.87(13) . . . . ? Cl2 Ti S1 C2 -80.16(12) . . . . ? Cl1 Ti S1 C2 13.07(12) . . . . ? Cl3 Ti S1 C2 -173.21(12) . . . . ? N1 Ti O1 C9 32.8(3) . . . . ? Cl2 Ti O1 C9 -144.9(3) . . . . ? Cl1 Ti O1 C9 119.5(3) . . . . ? Cl3 Ti O1 C9 -50.7(3) . . . . ? S1 Ti O1 C9 4.6(4) . . . . ? O1 Ti N1 C7 -26.0(2) . . . . ? Cl2 Ti N1 C7 137.3(5) . . . . ? Cl1 Ti N1 C7 -125.2(2) . . . . ? Cl3 Ti N1 C7 66.6(2) . . . . ? S1 Ti N1 C7 145.0(2) . . . . ? O1 Ti N1 C6 163.53(19) . . . . ? Cl2 Ti N1 C6 -33.2(7) . . . . ? Cl1 Ti N1 C6 64.32(18) . . . . ? Cl3 Ti N1 C6 -103.86(18) . . . . ? S1 Ti N1 C6 -25.48(18) . . . . ? C2 S1 C1 C6 -82.6(2) . . . . ? Ti S1 C1 C6 33.7(2) . . . . ? C1 S1 C2 C4 174.3(2) . . . . ? Ti S1 C2 C4 72.7(2) . . . . ? C1 S1 C2 C3 -64.3(3) . . . . ? Ti S1 C2 C3 -165.9(2) . . . . ? C7 N1 C6 C1 -114.8(3) . . . . ? Ti N1 C6 C1 56.0(3) . . . . ? S1 C1 C6 N1 -59.7(3) . . . . ? C6 N1 C7 C8 -175.6(3) . . . . ? Ti N1 C7 C8 14.3(4) . . . . ? C6 N1 C7 C14 6.7(4) . . . . ? Ti N1 C7 C14 -163.4(2) . . . . ? N1 C7 C8 C9 5.7(5) . . . . ? C14 C7 C8 C9 -176.5(3) . . . . ? Ti O1 C9 C8 -24.2(4) . . . . ? Ti O1 C9 C15 155.2(2) . . . . ? C7 C8 C9 O1 -4.3(5) . . . . ? C7 C8 C9 C15 176.3(3) . . . . ? C14 C5 C10 C11 1.1(7) . . . . ? C5 C10 C11 C12 -1.1(7) . . . . ? C10 C11 C12 C13 -0.6(7) . . . . ? C11 C12 C13 C14 2.4(7) . . . . ? C10 C5 C14 C13 0.8(6) . . . . ? C10 C5 C14 C7 -179.2(4) . . . . ? C12 C13 C14 C5 -2.5(6) . . . . ? C12 C13 C14 C7 177.5(4) . . . . ? N1 C7 C14 C5 87.5(4) . . . . ? C8 C7 C14 C5 -90.4(4) . . . . ? N1 C7 C14 C13 -92.5(4) . . . . ? C8 C7 C14 C13 89.7(4) . . . . ? O1 C9 C15 C20 -26.3(4) . . . . ? C8 C9 C15 C20 153.1(3) . . . . ? O1 C9 C15 C16 156.8(3) . . . . ? C8 C9 C15 C16 -23.8(5) . . . . ? C20 C15 C16 C17 -0.3(5) . . . . ? C9 C15 C16 C17 176.7(3) . . . . ? C15 C16 C17 C18 -0.1(5) . . . . ? C16 C17 C18 C19 0.4(6) . . . . ? C17 C18 C19 C20 -0.3(6) . . . . ? C18 C19 C20 C15 -0.1(5) . . . . ? C16 C15 C20 C19 0.4(5) . . . . ? C9 C15 C20 C19 -176.7(3) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.00 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.349 _refine_diff_density_min -0.350 _refine_diff_density_rms 0.066