Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Bun Yeoul Lee' _publ_contact_author_address ; Department of Molecular Science and Technology Ajou University Suwon 443-749 SOUTH KOREA ; _publ_contact_author_email BUNYEOUL@AJOU.AC.KR _publ_section_title ; o-Phenylene-Bridged Cp/Sulfonamido Titanium Complexes for Ethylene/1-Octene Copolymerization ; loop_ _publ_author_name 'Bun Yeoul Lee.' 'Taekki Bok.' 'Won-Sik Han.' 'Dae June Joe.' ; Sang Ook Kang ; 'Eun Jung Lee.' 'Choong Hoon Lee.' 'Chun Ji Wu.' data_27 _database_code_depnum_ccdc_archive 'CCDC 604506' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H31 N3 O2 S Ti' _chemical_formula_weight 473.48 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' 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 C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 31.743(3) _cell_length_b 11.5195(11) _cell_length_c 13.1968(12) _cell_angle_alpha 90.00 _cell_angle_beta 98.297(2) _cell_angle_gamma 90.00 _cell_volume 4775.1(8) _cell_formula_units_Z 8 _cell_measurement_temperature 233(2) _cell_measurement_reflns_used 7017 _cell_measurement_theta_min 2.3845 _cell_measurement_theta_max 27.9895 _exptl_crystal_description Block _exptl_crystal_colour Red _exptl_crystal_size_max 0.520 _exptl_crystal_size_mid 0.321 _exptl_crystal_size_min 0.101 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.317 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2000 _exptl_absorpt_coefficient_mu 0.471 _exptl_absorpt_correction_type 'multi scan' _exptl_absorpt_correction_T_min 0.7743 _exptl_absorpt_correction_T_max 0.9535 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 233(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD diffractometer' _diffrn_measurement_method \w-scans _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 24251 _diffrn_reflns_av_R_equivalents 0.0328 _diffrn_reflns_av_sigmaI/netI 0.0302 _diffrn_reflns_limit_h_min -41 _diffrn_reflns_limit_h_max 42 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.30 _diffrn_reflns_theta_max 28.39 _reflns_number_total 5993 _reflns_number_gt 4599 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1999)' _computing_cell_refinement 'SMART (Bruker, 1999)' _computing_data_reduction 'SAINT-Plus (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0512P)^2^+5.1994P] 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 SHELXL _refine_ls_extinction_coef 0.00008(8) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 5993 _refine_ls_number_parameters 288 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0566 _refine_ls_R_factor_gt 0.0376 _refine_ls_wR_factor_ref 0.1136 _refine_ls_wR_factor_gt 0.0953 _refine_ls_goodness_of_fit_ref 1.052 _refine_ls_restrained_S_all 1.052 _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 0.355976(10) 0.12520(3) 0.14336(2) 0.02558(10) Uani 1 1 d . . . S S 0.373073(16) 0.20418(4) -0.07937(3) 0.03104(12) Uani 1 1 d . . . O1 O 0.37516(5) 0.07979(13) -0.07086(11) 0.0401(3) Uani 1 1 d . . . O2 O 0.34752(5) 0.25256(14) -0.16835(10) 0.0430(4) Uani 1 1 d . . . N1 N 0.35859(5) 0.24944(13) 0.02700(11) 0.0273(3) Uani 1 1 d . . . N2 N 0.40180(5) 0.01505(15) 0.15406(13) 0.0354(4) Uani 1 1 d . . . N3 N 0.30743(5) 0.03811(15) 0.08832(14) 0.0360(4) Uani 1 1 d . . . C1 C 0.34040(7) 0.39995(17) 0.13706(15) 0.0345(4) Uani 1 1 d . . . C2 C 0.34844(6) 0.36956(15) 0.03864(14) 0.0278(4) Uani 1 1 d . . . C3 C 0.34578(6) 0.45652(18) -0.03590(16) 0.0353(4) Uani 1 1 d . . . H3 H 0.3512 0.4385 -0.1023 0.042 Uiso 1 1 calc R . . C4 C 0.33519(7) 0.56906(19) -0.01266(18) 0.0424(5) Uani 1 1 d . . . H4 H 0.3335 0.6265 -0.0637 0.051 Uiso 1 1 calc R . . C5 C 0.32703(8) 0.59841(18) 0.08367(19) 0.0447(5) Uani 1 1 d . . . H5 H 0.3199 0.6751 0.0986 0.054 Uiso 1 1 calc R . . C6 C 0.32948(8) 0.51320(18) 0.15830(17) 0.0437(5) Uani 1 1 d . . . H6 H 0.3237 0.5322 0.2242 0.052 Uiso 1 1 calc R . . C7 C 0.34670(7) 0.30711(17) 0.21509(14) 0.0361(5) Uani 1 1 d . . . C8 C 0.38804(8) 0.26934(18) 0.26141(15) 0.0393(5) Uani 1 1 d . . . C9 C 0.38164(8) 0.16946(19) 0.31899(15) 0.0423(5) Uani 1 1 d . . . H9 H 0.4032 0.1251 0.3572 0.051 Uiso 1 1 calc R . . C10 C 0.33773(8) 0.14727(19) 0.30981(16) 0.0437(5) Uani 1 1 d . . . H10 H 0.3252 0.0849 0.3403 0.052 Uiso 1 1 calc R . . C11 C 0.31544(8) 0.23341(19) 0.24754(16) 0.0404(5) Uani 1 1 d . . . C12 C 0.42890(9) 0.3271(2) 0.2474(2) 0.0552(7) Uani 1 1 d . . . H12A H 0.4523 0.2891 0.2902 0.083 Uiso 1 1 calc R . . H12B H 0.4279 0.4082 0.2668 0.083 Uiso 1 1 calc R . . H12C H 0.4331 0.3215 0.1762 0.083 Uiso 1 1 calc R . . C13 C 0.26803(8) 0.2443(2) 0.2201(2) 0.0597(7) Uani 1 1 d . . . H13A H 0.2572 0.2974 0.2673 0.090 Uiso 1 1 calc R . . H13B H 0.2550 0.1687 0.2245 0.090 Uiso 1 1 calc R . . H13C H 0.2613 0.2739 0.1508 0.090 Uiso 1 1 calc R . . C14 C 0.42581(6) 0.25491(17) -0.07755(15) 0.0318(4) Uani 1 1 d . . . C15 C 0.43475(7) 0.3473(2) -0.1374(2) 0.0469(6) Uani 1 1 d . . . H15 H 0.4130 0.3827 -0.1829 0.056 Uiso 1 1 calc R . . C16 C 0.47636(8) 0.3874(2) -0.1295(2) 0.0580(7) Uani 1 1 d . . . H16 H 0.4824 0.4510 -0.1697 0.070 Uiso 1 1 calc R . . C17 C 0.50904(7) 0.3367(2) -0.0644(2) 0.0453(5) Uani 1 1 d . . . C18 C 0.49960(8) 0.2423(2) -0.00737(19) 0.0478(6) Uani 1 1 d . . . H18 H 0.5216 0.2051 0.0360 0.057 Uiso 1 1 calc R . . C19 C 0.45833(7) 0.2014(2) -0.01277(17) 0.0447(5) Uani 1 1 d . . . H19 H 0.4524 0.1376 0.0273 0.054 Uiso 1 1 calc R . . C20 C 0.55406(8) 0.3828(3) -0.0567(3) 0.0637(8) Uani 1 1 d . . . H20A H 0.5651 0.3672 -0.1201 0.095 Uiso 1 1 calc R . . H20B H 0.5719 0.3449 -0.0004 0.095 Uiso 1 1 calc R . . H20C H 0.5540 0.4659 -0.0447 0.095 Uiso 1 1 calc R . . C21 C 0.44379(7) 0.0130(2) 0.2163(2) 0.0525(6) Uani 1 1 d . . . H21A H 0.4438 -0.0427 0.2714 0.079 Uiso 1 1 calc R . . H21B H 0.4504 0.0895 0.2448 0.079 Uiso 1 1 calc R . . H21C H 0.4650 -0.0093 0.1739 0.079 Uiso 1 1 calc R . . C22 C 0.39525(9) -0.0970(2) 0.1017(2) 0.0510(6) Uani 1 1 d . . . H22A H 0.4175 -0.1094 0.0597 0.077 Uiso 1 1 calc R . . H22B H 0.3678 -0.0973 0.0587 0.077 Uiso 1 1 calc R . . H22C H 0.3961 -0.1586 0.1521 0.077 Uiso 1 1 calc R . . C23 C 0.29191(9) -0.0568(2) 0.1459(2) 0.0597(7) Uani 1 1 d . . . H23A H 0.2666 -0.0319 0.1734 0.090 Uiso 1 1 calc R . . H23B H 0.3138 -0.0788 0.2017 0.090 Uiso 1 1 calc R . . H23C H 0.2850 -0.1228 0.1010 0.090 Uiso 1 1 calc R . . C24 C 0.27670(7) 0.0675(2) -0.00078(19) 0.0516(6) Uani 1 1 d . . . H24A H 0.2731 0.0019 -0.0473 0.077 Uiso 1 1 calc R . . H24B H 0.2869 0.1339 -0.0354 0.077 Uiso 1 1 calc R . . H24C H 0.2496 0.0865 0.0209 0.077 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 0.02820(18) 0.02258(16) 0.02596(17) 0.00114(12) 0.00394(12) -0.00029(12) S 0.0359(3) 0.0341(3) 0.0232(2) -0.00414(18) 0.00476(18) -0.0074(2) O1 0.0519(9) 0.0326(8) 0.0372(8) -0.0095(6) 0.0108(7) -0.0094(7) O2 0.0462(9) 0.0568(10) 0.0240(7) -0.0010(6) -0.0021(6) -0.0061(7) N1 0.0310(8) 0.0274(8) 0.0237(7) -0.0016(6) 0.0048(6) -0.0038(6) N2 0.0345(9) 0.0344(9) 0.0363(9) 0.0023(7) 0.0022(7) 0.0057(7) N3 0.0310(9) 0.0314(9) 0.0455(10) 0.0036(7) 0.0047(7) -0.0048(7) C1 0.0466(11) 0.0269(9) 0.0287(10) 0.0004(7) 0.0013(8) 0.0003(8) C2 0.0274(9) 0.0256(9) 0.0297(9) 0.0024(7) 0.0012(7) -0.0032(7) C3 0.0353(10) 0.0365(11) 0.0340(10) 0.0089(8) 0.0047(8) -0.0014(8) C4 0.0414(12) 0.0336(11) 0.0505(13) 0.0164(9) 0.0010(10) -0.0020(9) C5 0.0537(14) 0.0242(10) 0.0535(14) 0.0019(9) -0.0008(11) 0.0030(9) C6 0.0620(15) 0.0292(10) 0.0381(12) -0.0043(9) 0.0012(10) 0.0040(10) C7 0.0600(13) 0.0260(9) 0.0228(9) -0.0018(7) 0.0077(9) 0.0046(9) C8 0.0605(14) 0.0307(10) 0.0237(9) -0.0023(8) -0.0041(9) -0.0018(9) C9 0.0649(15) 0.0365(11) 0.0236(10) 0.0036(8) 0.0004(9) 0.0039(10) C10 0.0654(15) 0.0374(11) 0.0319(11) 0.0075(9) 0.0192(10) 0.0064(10) C11 0.0580(14) 0.0359(11) 0.0306(10) 0.0014(8) 0.0176(9) 0.0113(10) C12 0.0645(16) 0.0426(13) 0.0514(14) 0.0022(11) -0.0163(12) -0.0151(12) C13 0.0584(16) 0.0562(16) 0.0713(18) 0.0106(13) 0.0321(14) 0.0218(13) C14 0.0334(10) 0.0351(10) 0.0287(9) -0.0018(8) 0.0102(8) -0.0037(8) C15 0.0387(12) 0.0473(13) 0.0575(14) 0.0184(11) 0.0167(11) 0.0046(10) C16 0.0449(13) 0.0450(14) 0.090(2) 0.0237(13) 0.0300(14) 0.0023(11) C17 0.0374(12) 0.0434(12) 0.0587(14) -0.0071(11) 0.0194(10) -0.0035(10) C18 0.0384(12) 0.0612(15) 0.0435(13) 0.0038(11) 0.0045(10) -0.0009(11) C19 0.0413(12) 0.0530(14) 0.0398(12) 0.0124(10) 0.0059(9) -0.0036(10) C20 0.0410(14) 0.0631(17) 0.091(2) -0.0078(15) 0.0249(14) -0.0099(12) C21 0.0374(12) 0.0619(16) 0.0560(15) 0.0086(12) -0.0010(11) 0.0099(11) C22 0.0601(15) 0.0394(12) 0.0539(14) -0.0022(11) 0.0092(12) 0.0168(11) C23 0.0565(16) 0.0425(14) 0.0805(19) 0.0170(13) 0.0113(14) -0.0130(12) C24 0.0321(11) 0.0647(16) 0.0550(15) 0.0053(12) -0.0044(10) -0.0119(11) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti N3 1.8935(17) . ? Ti N2 1.9200(17) . ? Ti N1 2.1095(15) . ? Ti C7 2.3355(19) . ? Ti C10 2.365(2) . ? Ti C11 2.369(2) . ? Ti C9 2.398(2) . ? Ti C8 2.400(2) . ? S O1 1.4381(16) . ? S O2 1.4396(15) . ? S N1 1.6249(15) . ? S C14 1.770(2) . ? N1 C2 1.434(2) . ? N2 C21 1.461(3) . ? N2 C22 1.465(3) . ? N3 C24 1.455(3) . ? N3 C23 1.457(3) . ? C1 C6 1.389(3) . ? C1 C2 1.404(3) . ? C1 C7 1.478(3) . ? C2 C3 1.398(3) . ? C3 C4 1.385(3) . ? C3 H3 0.9400 . ? C4 C5 1.376(3) . ? C4 H4 0.9400 . ? C5 C6 1.385(3) . ? C5 H5 0.9400 . ? C6 H6 0.9400 . ? C7 C11 1.418(3) . ? C7 C8 1.433(3) . ? C8 C9 1.410(3) . ? C8 C12 1.493(3) . ? C9 C10 1.405(3) . ? C9 H9 0.9400 . ? C10 C11 1.412(3) . ? C10 H10 0.9400 . ? C11 C13 1.502(4) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C12 H12C 0.9700 . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C13 H13C 0.9700 . ? C14 C15 1.379(3) . ? C14 C19 1.386(3) . ? C15 C16 1.389(3) . ? C15 H15 0.9400 . ? C16 C17 1.378(4) . ? C16 H16 0.9400 . ? C17 C18 1.380(3) . ? C17 C20 1.514(3) . ? C18 C19 1.385(3) . ? C18 H18 0.9400 . ? C19 H19 0.9400 . ? C20 H20A 0.9700 . ? C20 H20B 0.9700 . ? C20 H20C 0.9700 . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C21 H21C 0.9700 . ? C22 H22A 0.9700 . ? C22 H22B 0.9700 . ? C22 H22C 0.9700 . ? C23 H23A 0.9700 . ? C23 H23B 0.9700 . ? C23 H23C 0.9700 . ? C24 H24A 0.9700 . ? C24 H24B 0.9700 . ? C24 H24C 0.9700 . ? 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 N3 Ti N2 104.12(8) . . ? N3 Ti N1 101.27(7) . . ? N2 Ti N1 113.14(7) . . ? N3 Ti C7 119.19(8) . . ? N2 Ti C7 134.56(8) . . ? N1 Ti C7 72.95(6) . . ? N3 Ti C10 96.80(8) . . ? N2 Ti C10 106.69(8) . . ? N1 Ti C10 130.08(7) . . ? C7 Ti C10 57.65(7) . . ? N3 Ti C11 91.23(8) . . ? N2 Ti C11 140.75(8) . . ? N1 Ti C11 98.46(7) . . ? C7 Ti C11 35.09(8) . . ? C10 Ti C11 34.70(7) . . ? N3 Ti C9 128.87(8) . . ? N2 Ti C9 85.49(8) . . ? N1 Ti C9 121.05(7) . . ? C7 Ti C9 57.49(7) . . ? C10 Ti C9 34.30(8) . . ? C11 Ti C9 57.61(8) . . ? N3 Ti C8 149.40(8) . . ? N2 Ti C8 99.42(8) . . ? N1 Ti C8 86.88(6) . . ? C7 Ti C8 35.19(8) . . ? C10 Ti C8 57.35(8) . . ? C11 Ti C8 58.28(8) . . ? C9 Ti C8 34.17(7) . . ? O1 S O2 117.62(9) . . ? O1 S N1 105.54(8) . . ? O2 S N1 112.58(9) . . ? O1 S C14 107.16(9) . . ? O2 S C14 107.69(9) . . ? N1 S C14 105.51(9) . . ? C2 N1 S 119.88(12) . . ? C2 N1 Ti 122.93(12) . . ? S N1 Ti 117.19(8) . . ? C21 N2 C22 107.84(18) . . ? C21 N2 Ti 132.21(16) . . ? C22 N2 Ti 119.57(14) . . ? C24 N3 C23 111.01(18) . . ? C24 N3 Ti 126.87(15) . . ? C23 N3 Ti 120.99(16) . . ? C6 C1 C2 120.33(18) . . ? C6 C1 C7 123.48(19) . . ? C2 C1 C7 116.09(17) . . ? C3 C2 C1 118.16(18) . . ? C3 C2 N1 127.42(18) . . ? C1 C2 N1 114.42(16) . . ? C4 C3 C2 120.5(2) . . ? C4 C3 H3 119.8 . . ? C2 C3 H3 119.8 . . ? C5 C4 C3 121.3(2) . . ? C5 C4 H4 119.4 . . ? C3 C4 H4 119.4 . . ? C4 C5 C6 119.0(2) . . ? C4 C5 H5 120.5 . . ? C6 C5 H5 120.5 . . ? C5 C6 C1 120.8(2) . . ? C5 C6 H6 119.6 . . ? C1 C6 H6 119.6 . . ? C11 C7 C8 109.08(18) . . ? C11 C7 C1 127.8(2) . . ? C8 C7 C1 122.7(2) . . ? C11 C7 Ti 73.73(11) . . ? C8 C7 Ti 74.88(11) . . ? C1 C7 Ti 112.28(13) . . ? C9 C8 C7 106.5(2) . . ? C9 C8 C12 128.7(2) . . ? C7 C8 C12 124.78(19) . . ? C9 C8 Ti 72.82(12) . . ? C7 C8 Ti 69.93(11) . . ? C12 C8 Ti 121.50(16) . . ? C10 C9 C8 108.7(2) . . ? C10 C9 Ti 71.56(12) . . ? C8 C9 Ti 73.01(11) . . ? C10 C9 H9 125.7 . . ? C8 C9 H9 125.7 . . ? Ti C9 H9 121.5 . . ? C9 C10 C11 109.3(2) . . ? C9 C10 Ti 74.14(12) . . ? C11 C10 Ti 72.79(12) . . ? C9 C10 H10 125.4 . . ? C11 C10 H10 125.4 . . ? Ti C10 H10 119.4 . . ? C10 C11 C7 106.4(2) . . ? C10 C11 C13 126.9(2) . . ? C7 C11 C13 126.7(2) . . ? C10 C11 Ti 72.50(12) . . ? C7 C11 Ti 71.18(11) . . ? C13 C11 Ti 120.90(17) . . ? C8 C12 H12A 109.5 . . ? C8 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C8 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C11 C13 H13A 109.5 . . ? C11 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C11 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C15 C14 C19 120.0(2) . . ? C15 C14 S 121.29(17) . . ? C19 C14 S 118.70(16) . . ? C14 C15 C16 119.1(2) . . ? C14 C15 H15 120.5 . . ? C16 C15 H15 120.5 . . ? C17 C16 C15 121.9(2) . . ? C17 C16 H16 119.1 . . ? C15 C16 H16 119.1 . . ? C16 C17 C18 118.1(2) . . ? C16 C17 C20 120.8(2) . . ? C18 C17 C20 121.1(2) . . ? C17 C18 C19 121.2(2) . . ? C17 C18 H18 119.4 . . ? C19 C18 H18 119.4 . . ? C18 C19 C14 119.7(2) . . ? C18 C19 H19 120.2 . . ? C14 C19 H19 120.2 . . ? C17 C20 H20A 109.5 . . ? C17 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C17 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? N2 C21 H21A 109.5 . . ? N2 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? N2 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N2 C22 H22A 109.5 . . ? N2 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? N2 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? N3 C23 H23A 109.5 . . ? N3 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? N3 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? N3 C24 H24A 109.5 . . ? N3 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? N3 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 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 O1 S N1 C2 -172.47(14) . . . . ? O2 S N1 C2 -42.92(16) . . . . ? C14 S N1 C2 74.27(15) . . . . ? O1 S N1 Ti 7.81(12) . . . . ? O2 S N1 Ti 137.36(9) . . . . ? C14 S N1 Ti -105.45(10) . . . . ? N3 Ti N1 C2 108.64(14) . . . . ? N2 Ti N1 C2 -140.52(14) . . . . ? C7 Ti N1 C2 -8.68(14) . . . . ? C10 Ti N1 C2 -0.36(18) . . . . ? C11 Ti N1 C2 15.68(15) . . . . ? C9 Ti N1 C2 -41.46(16) . . . . ? C8 Ti N1 C2 -41.60(14) . . . . ? N3 Ti N1 S -71.65(10) . . . . ? N2 Ti N1 S 39.19(12) . . . . ? C7 Ti N1 S 171.03(11) . . . . ? C10 Ti N1 S 179.35(10) . . . . ? C11 Ti N1 S -164.61(10) . . . . ? C9 Ti N1 S 138.25(10) . . . . ? C8 Ti N1 S 138.11(10) . . . . ? N3 Ti N2 C21 -158.6(2) . . . . ? N1 Ti N2 C21 92.3(2) . . . . ? C7 Ti N2 C21 3.8(2) . . . . ? C10 Ti N2 C21 -56.9(2) . . . . ? C11 Ti N2 C21 -48.6(3) . . . . ? C9 Ti N2 C21 -29.6(2) . . . . ? C8 Ti N2 C21 1.7(2) . . . . ? N3 Ti N2 C22 13.42(18) . . . . ? N1 Ti N2 C22 -95.65(17) . . . . ? C7 Ti N2 C22 175.88(15) . . . . ? C10 Ti N2 C22 115.13(17) . . . . ? C11 Ti N2 C22 123.46(18) . . . . ? C9 Ti N2 C22 142.41(17) . . . . ? C8 Ti N2 C22 173.72(17) . . . . ? N2 Ti N3 C24 -128.16(19) . . . . ? N1 Ti N3 C24 -10.6(2) . . . . ? C7 Ti N3 C24 66.1(2) . . . . ? C10 Ti N3 C24 122.7(2) . . . . ? C11 Ti N3 C24 88.3(2) . . . . ? C9 Ti N3 C24 136.18(19) . . . . ? C8 Ti N3 C24 92.6(2) . . . . ? N2 Ti N3 C23 65.10(19) . . . . ? N1 Ti N3 C23 -177.30(18) . . . . ? C7 Ti N3 C23 -100.66(19) . . . . ? C10 Ti N3 C23 -44.07(19) . . . . ? C11 Ti N3 C23 -78.42(19) . . . . ? C9 Ti N3 C23 -30.6(2) . . . . ? C8 Ti N3 C23 -74.1(2) . . . . ? C6 C1 C2 C3 1.0(3) . . . . ? C7 C1 C2 C3 -175.64(19) . . . . ? C6 C1 C2 N1 -178.91(19) . . . . ? C7 C1 C2 N1 4.5(3) . . . . ? S N1 C2 C3 6.0(3) . . . . ? Ti N1 C2 C3 -174.33(15) . . . . ? S N1 C2 C1 -174.14(14) . . . . ? Ti N1 C2 C1 5.6(2) . . . . ? C1 C2 C3 C4 -0.4(3) . . . . ? N1 C2 C3 C4 179.45(18) . . . . ? C2 C3 C4 C5 0.0(3) . . . . ? C3 C4 C5 C6 -0.1(3) . . . . ? C4 C5 C6 C1 0.6(4) . . . . ? C2 C1 C6 C5 -1.1(4) . . . . ? C7 C1 C6 C5 175.3(2) . . . . ? C6 C1 C7 C11 86.3(3) . . . . ? C2 C1 C7 C11 -97.2(3) . . . . ? C6 C1 C7 C8 -101.6(3) . . . . ? C2 C1 C7 C8 74.9(3) . . . . ? C6 C1 C7 Ti 172.54(18) . . . . ? C2 C1 C7 Ti -10.9(2) . . . . ? N3 Ti C7 C11 41.17(15) . . . . ? N2 Ti C7 C11 -119.26(14) . . . . ? N1 Ti C7 C11 134.78(14) . . . . ? C10 Ti C7 C11 -37.69(13) . . . . ? C9 Ti C7 C11 -78.58(14) . . . . ? C8 Ti C7 C11 -115.57(18) . . . . ? N3 Ti C7 C8 156.74(12) . . . . ? N2 Ti C7 C8 -3.70(17) . . . . ? N1 Ti C7 C8 -109.65(13) . . . . ? C10 Ti C7 C8 77.88(13) . . . . ? C11 Ti C7 C8 115.57(18) . . . . ? C9 Ti C7 C8 36.98(12) . . . . ? N3 Ti C7 C1 -83.62(17) . . . . ? N2 Ti C7 C1 115.94(16) . . . . ? N1 Ti C7 C1 9.98(15) . . . . ? C10 Ti C7 C1 -162.5(2) . . . . ? C11 Ti C7 C1 -124.8(2) . . . . ? C9 Ti C7 C1 156.6(2) . . . . ? C8 Ti C7 C1 119.6(2) . . . . ? C11 C7 C8 C9 2.2(2) . . . . ? C1 C7 C8 C9 -171.20(18) . . . . ? Ti C7 C8 C9 -64.16(14) . . . . ? C11 C7 C8 C12 -178.5(2) . . . . ? C1 C7 C8 C12 8.0(3) . . . . ? Ti C7 C8 C12 115.1(2) . . . . ? C11 C7 C8 Ti 66.39(14) . . . . ? C1 C7 C8 Ti -107.05(18) . . . . ? N3 Ti C8 C9 72.8(2) . . . . ? N2 Ti C8 C9 -67.27(15) . . . . ? N1 Ti C8 C9 179.78(15) . . . . ? C7 Ti C8 C9 115.4(2) . . . . ? C10 Ti C8 C9 36.59(14) . . . . ? C11 Ti C8 C9 77.84(15) . . . . ? N3 Ti C8 C7 -42.6(2) . . . . ? N2 Ti C8 C7 177.33(12) . . . . ? N1 Ti C8 C7 64.38(12) . . . . ? C10 Ti C8 C7 -78.81(14) . . . . ? C11 Ti C8 C7 -37.56(12) . . . . ? C9 Ti C8 C7 -115.4(2) . . . . ? N3 Ti C8 C12 -161.86(17) . . . . ? N2 Ti C8 C12 58.10(18) . . . . ? N1 Ti C8 C12 -54.85(18) . . . . ? C7 Ti C8 C12 -119.2(2) . . . . ? C10 Ti C8 C12 162.0(2) . . . . ? C11 Ti C8 C12 -156.8(2) . . . . ? C9 Ti C8 C12 125.4(2) . . . . ? C7 C8 C9 C10 -0.9(2) . . . . ? C12 C8 C9 C10 180.0(2) . . . . ? Ti C8 C9 C10 -63.09(15) . . . . ? C7 C8 C9 Ti 62.23(13) . . . . ? C12 C8 C9 Ti -116.9(2) . . . . ? N3 Ti C9 C10 -24.30(17) . . . . ? N2 Ti C9 C10 -128.82(13) . . . . ? N1 Ti C9 C10 116.81(13) . . . . ? C7 Ti C9 C10 78.95(14) . . . . ? C11 Ti C9 C10 37.09(13) . . . . ? C8 Ti C9 C10 117.1(2) . . . . ? N3 Ti C9 C8 -141.36(14) . . . . ? N2 Ti C9 C8 114.11(15) . . . . ? N1 Ti C9 C8 -0.26(17) . . . . ? C7 Ti C9 C8 -38.12(14) . . . . ? C10 Ti C9 C8 -117.1(2) . . . . ? C11 Ti C9 C8 -79.97(15) . . . . ? C8 C9 C10 C11 -0.8(3) . . . . ? Ti C9 C10 C11 -64.85(15) . . . . ? C8 C9 C10 Ti 64.03(15) . . . . ? N3 Ti C10 C9 161.17(13) . . . . ? N2 Ti C10 C9 54.18(14) . . . . ? N1 Ti C10 C9 -87.87(14) . . . . ? C7 Ti C10 C9 -78.44(14) . . . . ? C11 Ti C10 C9 -116.6(2) . . . . ? C8 Ti C10 C9 -36.44(13) . . . . ? N3 Ti C10 C11 -82.27(15) . . . . ? N2 Ti C10 C11 170.73(14) . . . . ? N1 Ti C10 C11 28.69(19) . . . . ? C7 Ti C10 C11 38.11(14) . . . . ? C9 Ti C10 C11 116.6(2) . . . . ? C8 Ti C10 C11 80.11(15) . . . . ? C9 C10 C11 C7 2.2(2) . . . . ? Ti C10 C11 C7 -63.54(14) . . . . ? C9 C10 C11 C13 -178.4(2) . . . . ? Ti C10 C11 C13 115.9(2) . . . . ? C9 C10 C11 Ti 65.72(16) . . . . ? C8 C7 C11 C10 -2.7(2) . . . . ? C1 C7 C11 C10 170.30(19) . . . . ? Ti C7 C11 C10 64.43(15) . . . . ? C8 C7 C11 C13 177.8(2) . . . . ? C1 C7 C11 C13 -9.1(4) . . . . ? Ti C7 C11 C13 -115.0(2) . . . . ? C8 C7 C11 Ti -67.15(14) . . . . ? C1 C7 C11 Ti 105.9(2) . . . . ? N3 Ti C11 C10 100.21(15) . . . . ? N2 Ti C11 C10 -14.1(2) . . . . ? N1 Ti C11 C10 -158.20(14) . . . . ? C7 Ti C11 C10 -114.9(2) . . . . ? C9 Ti C11 C10 -36.66(14) . . . . ? C8 Ti C11 C10 -77.21(15) . . . . ? N3 Ti C11 C7 -144.91(13) . . . . ? N2 Ti C11 C7 100.77(15) . . . . ? N1 Ti C11 C7 -43.32(13) . . . . ? C10 Ti C11 C7 114.9(2) . . . . ? C9 Ti C11 C7 78.22(14) . . . . ? C8 Ti C11 C7 37.67(12) . . . . ? N3 Ti C11 C13 -22.77(18) . . . . ? N2 Ti C11 C13 -137.09(17) . . . . ? N1 Ti C11 C13 78.82(18) . . . . ? C7 Ti C11 C13 122.1(2) . . . . ? C10 Ti C11 C13 -123.0(2) . . . . ? C9 Ti C11 C13 -159.6(2) . . . . ? C8 Ti C11 C13 159.8(2) . . . . ? O1 S C14 C15 142.73(19) . . . . ? O2 S C14 C15 15.3(2) . . . . ? N1 S C14 C15 -105.15(19) . . . . ? O1 S C14 C19 -38.63(19) . . . . ? O2 S C14 C19 -166.06(17) . . . . ? N1 S C14 C19 73.49(19) . . . . ? C19 C14 C15 C16 -1.7(4) . . . . ? S C14 C15 C16 176.9(2) . . . . ? C14 C15 C16 C17 0.7(4) . . . . ? C15 C16 C17 C18 1.1(4) . . . . ? C15 C16 C17 C20 -179.5(3) . . . . ? C16 C17 C18 C19 -1.8(4) . . . . ? C20 C17 C18 C19 178.7(2) . . . . ? C17 C18 C19 C14 0.9(4) . . . . ? C15 C14 C19 C18 1.0(4) . . . . ? S C14 C19 C18 -177.69(18) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 28.39 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.356 _refine_diff_density_min -0.325 _refine_diff_density_rms 0.058 #===END data_28 _database_code_depnum_ccdc_archive 'CCDC 604507' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C40 H36 Cl4 F4 N2 O5 S2 Ti2' _chemical_formula_weight 1002.43 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.927(5) _cell_length_b 13.917(8) _cell_length_c 18.663(10) _cell_angle_alpha 101.172(12) _cell_angle_beta 97.017(13) _cell_angle_gamma 102.053(13) _cell_volume 2192(2) _cell_formula_units_Z 2 _cell_measurement_temperature 233(2) _cell_measurement_reflns_used 741 _cell_measurement_theta_min 2.427 _cell_measurement_theta_max 14.034 _exptl_crystal_description Plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.519 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1020 _exptl_absorpt_coefficient_mu 0.765 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min 0.8985 _exptl_absorpt_correction_T_max 0.9563 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 233(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD diffractometer' _diffrn_measurement_method \w-scans _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 30361 _diffrn_reflns_av_R_equivalents 0.3568 _diffrn_reflns_av_sigmaI/netI 0.6265 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 1.13 _diffrn_reflns_theta_max 28.42 _reflns_number_total 10937 _reflns_number_gt 2371 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1999)' _computing_cell_refinement 'SMART (Bruker, 1999)' _computing_data_reduction 'SAINT-Plus (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0767P)^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 fixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.048(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 10937 _refine_ls_number_parameters 539 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.3708 _refine_ls_R_factor_gt 0.0924 _refine_ls_wR_factor_ref 0.3499 _refine_ls_wR_factor_gt 0.1957 _refine_ls_goodness_of_fit_ref 0.856 _refine_ls_restrained_S_all 0.856 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.1599(2) 0.21491(15) 0.22969(11) 0.0512(7) Uani 1 1 d . . . Ti2 Ti 0.5262(2) 0.27633(15) 0.17269(11) 0.0532(7) Uani 1 1 d . . . Cl1 Cl 0.1284(4) 0.3723(2) 0.24770(17) 0.0679(10) Uani 1 1 d . . . Cl2 Cl -0.0140(3) 0.1323(2) 0.12645(16) 0.0654(10) Uani 1 1 d . . . Cl3 Cl 0.5382(4) 0.4413(2) 0.19840(18) 0.0772(11) Uani 1 1 d . . . Cl4 Cl 0.7052(4) 0.2633(3) 0.26241(17) 0.0801(11) Uani 1 1 d . . . S1 S 0.3630(4) 0.1174(2) 0.51481(16) 0.0585(9) Uani 1 1 d . . . S2 S 0.3577(4) 0.1311(3) -0.15390(19) 0.0701(10) Uani 1 1 d . . . F1 F 0.6563(9) 0.5187(6) 0.4162(4) 0.096(2) Uani 1 1 d . . . F2 F 0.7572(8) 0.2470(6) 0.5095(4) 0.084(2) Uani 1 1 d . . . F3 F 0.0203(8) 0.4120(5) 0.0540(4) 0.082(2) Uani 1 1 d . . . F4 F -0.0481(8) 0.1291(6) -0.1356(4) 0.086(2) Uani 1 1 d . . . O1 O 0.2367(9) 0.1604(6) 0.4986(4) 0.070(2) Uani 1 1 d . . . O2 O 0.3387(9) 0.0132(6) 0.5166(4) 0.069(2) Uani 1 1 d . . . O3 O 0.4911(10) 0.2029(7) -0.1133(4) 0.077(3) Uani 1 1 d . . . O4 O 0.3680(12) 0.0350(6) -0.1941(5) 0.097(3) Uani 1 1 d . . . O10 O 0.3417(7) 0.2252(5) 0.1974(3) 0.0481(19) Uani 1 1 d . . . N1 N 0.4704(10) 0.1292(7) 0.4511(5) 0.058(3) Uani 1 1 d . . . H1 H 0.4983 0.0776 0.4270 0.069 Uiso 1 1 calc R . . N2 N 0.2414(10) 0.1035(7) -0.0957(5) 0.060(3) Uani 1 1 d . . . H2 H 0.2141 0.0417 -0.0908 0.073 Uiso 1 1 calc R . . C1 C 0.2508(13) 0.1093(9) 0.2996(6) 0.049(3) Uani 1 1 d . . . C2 C 0.2681(13) 0.2023(9) 0.3498(6) 0.049(3) Uani 1 1 d . . . C3 C 0.1218(13) 0.2241(9) 0.3566(6) 0.053(3) Uani 1 1 d . . . C4 C 0.0120(15) 0.1420(9) 0.3093(6) 0.060(3) Uani 1 1 d . . . H4 H -0.0961 0.1347 0.3004 0.072 Uiso 1 1 calc R . . C5 C 0.0923(16) 0.0736(9) 0.2779(6) 0.063(3) Uani 1 1 d . . . H5 H 0.0445 0.0107 0.2459 0.075 Uiso 1 1 calc R . . C6 C 0.3720(15) 0.0582(9) 0.2768(6) 0.071(4) Uani 1 1 d . . . H6A H 0.3966 0.0185 0.3120 0.107 Uiso 1 1 calc R . . H6B H 0.4646 0.1081 0.2753 0.107 Uiso 1 1 calc R . . H6C H 0.3344 0.0141 0.2280 0.107 Uiso 1 1 calc R . . C7 C 0.0874(13) 0.3084(9) 0.4078(7) 0.071(4) Uani 1 1 d . . . H7A H 0.1007 0.2976 0.4578 0.107 Uiso 1 1 calc R . . H7B H -0.0189 0.3121 0.3931 0.107 Uiso 1 1 calc R . . H7C H 0.1578 0.3711 0.4064 0.107 Uiso 1 1 calc R . . C8 C 0.4189(13) 0.2655(9) 0.3914(5) 0.048(3) Uani 1 1 d . . . C9 C 0.4710(15) 0.3664(10) 0.3868(6) 0.059(3) Uani 1 1 d . . . H9 H 0.4061 0.3955 0.3586 0.070 Uiso 1 1 calc R . . C10 C 0.6120(17) 0.4219(10) 0.4221(7) 0.069(4) Uani 1 1 d . . . C11 C 0.7107(15) 0.3854(11) 0.4641(7) 0.067(4) Uani 1 1 d . . . H11 H 0.8094 0.4247 0.4882 0.080 Uiso 1 1 calc R . . C12 C 0.6585(15) 0.2879(11) 0.4695(6) 0.066(4) Uani 1 1 d . . . C13 C 0.5177(14) 0.2270(9) 0.4357(6) 0.050(3) Uani 1 1 d . . . C14 C 0.4751(14) 0.1914(9) 0.5975(6) 0.055(3) Uani 1 1 d . . . C15 C 0.4642(15) 0.2873(10) 0.6225(8) 0.071(4) Uani 1 1 d . . . H15 H 0.3945 0.3145 0.5955 0.085 Uiso 1 1 calc R . . C16 C 0.5551(16) 0.3443(10) 0.6874(8) 0.076(4) Uani 1 1 d . . . H16 H 0.5475 0.4111 0.7042 0.091 Uiso 1 1 calc R . . C17 C 0.6571(15) 0.3064(10) 0.7285(7) 0.064(3) Uani 1 1 d . . . C18 C 0.6710(16) 0.2108(10) 0.7020(8) 0.084(4) Uani 1 1 d . . . H18 H 0.7423 0.1844 0.7289 0.100 Uiso 1 1 calc R . . C19 C 0.5823(17) 0.1527(10) 0.6366(8) 0.085(4) Uani 1 1 d . . . H19 H 0.5939 0.0872 0.6183 0.102 Uiso 1 1 calc R . . C20 C 0.7517(18) 0.3673(10) 0.8014(7) 0.094(5) Uani 1 1 d . . . H20A H 0.7881 0.4367 0.7979 0.141 Uiso 1 1 calc R . . H20B H 0.8402 0.3395 0.8134 0.141 Uiso 1 1 calc R . . H20C H 0.6880 0.3649 0.8398 0.141 Uiso 1 1 calc R . . C51 C 0.4478(14) 0.1413(8) 0.0650(6) 0.050(3) Uani 1 1 d . . . C52 C 0.4266(13) 0.2297(9) 0.0428(6) 0.055(3) Uani 1 1 d . . . C53 C 0.5734(13) 0.2991(9) 0.0537(6) 0.051(3) Uani 1 1 d . . . C54 C 0.6857(14) 0.2560(9) 0.0839(6) 0.058(3) Uani 1 1 d . . . H54 H 0.7928 0.2859 0.0965 0.070 Uiso 1 1 calc R . . C55 C 0.6121(14) 0.1592(9) 0.0925(6) 0.056(3) Uani 1 1 d . . . H55 H 0.6614 0.1146 0.1126 0.067 Uiso 1 1 calc R . . C56 C 0.3314(13) 0.0484(8) 0.0617(6) 0.063(3) Uani 1 1 d . . . H56A H 0.2343 0.0649 0.0713 0.094 Uiso 1 1 calc R . . H56B H 0.3677 0.0145 0.0987 0.094 Uiso 1 1 calc R . . H56C H 0.3152 0.0045 0.0128 0.094 Uiso 1 1 calc R . . C57 C 0.6064(14) 0.3978(9) 0.0297(7) 0.071(4) Uani 1 1 d . . . H57A H 0.7029 0.4410 0.0587 0.106 Uiso 1 1 calc R . . H57B H 0.5221 0.4307 0.0373 0.106 Uiso 1 1 calc R . . H57C H 0.6154 0.3852 -0.0224 0.106 Uiso 1 1 calc R . . C58 C 0.2744(14) 0.2453(9) 0.0118(6) 0.052(3) Uani 1 1 d . . . C59 C 0.2190(13) 0.3250(9) 0.0471(7) 0.057(3) Uani 1 1 d . . . H59 H 0.2806 0.3718 0.0889 0.069 Uiso 1 1 calc R . . C60 C 0.0729(16) 0.3351(10) 0.0205(8) 0.066(4) Uani 1 1 d . . . C61 C -0.0203(15) 0.2687(11) -0.0413(7) 0.073(4) Uani 1 1 d . . . H61 H -0.1205 0.2744 -0.0590 0.087 Uiso 1 1 calc R . . C62 C 0.0433(15) 0.1935(10) -0.0753(7) 0.063(3) Uani 1 1 d . . . C63 C 0.1842(15) 0.1809(8) -0.0527(7) 0.054(3) Uani 1 1 d . . . C64 C 0.2613(14) 0.1917(10) -0.2143(6) 0.061(3) Uani 1 1 d . . . C65 C 0.2611(15) 0.2883(11) -0.1884(7) 0.077(4) Uani 1 1 d . . . H65 H 0.3131 0.3225 -0.1405 0.093 Uiso 1 1 calc R . . C66 C 0.1814(15) 0.3387(13) -0.2341(10) 0.102(6) Uani 1 1 d . . . H66 H 0.1813 0.4067 -0.2164 0.123 Uiso 1 1 calc R . . C67 C 0.1062(18) 0.2896(19) -0.3025(11) 0.110(6) Uani 1 1 d . . . C68 C 0.1095(18) 0.1918(17) -0.3273(8) 0.097(6) Uani 1 1 d . . . H68 H 0.0581 0.1583 -0.3755 0.117 Uiso 1 1 calc R . . C69 C 0.1839(19) 0.1394(12) -0.2855(9) 0.104(6) Uani 1 1 d . . . H69 H 0.1831 0.0714 -0.3038 0.125 Uiso 1 1 calc R . . C70 C 0.0275(18) 0.3454(17) -0.3517(10) 0.174(10) Uani 1 1 d . . . H70A H 0.0233 0.3138 -0.4033 0.261 Uiso 1 1 calc R . . H70B H 0.0859 0.4151 -0.3416 0.261 Uiso 1 1 calc R . . H70C H -0.0773 0.3432 -0.3419 0.261 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 Ti1 0.0518(13) 0.0591(14) 0.0429(13) 0.0134(10) 0.0064(10) 0.0130(11) Ti2 0.0547(14) 0.0578(15) 0.0476(13) 0.0093(11) 0.0109(10) 0.0154(11) Cl1 0.076(2) 0.067(2) 0.070(2) 0.0229(17) 0.0187(17) 0.0292(18) Cl2 0.0555(19) 0.080(2) 0.0552(19) 0.0172(17) -0.0013(15) 0.0084(17) Cl3 0.090(2) 0.053(2) 0.081(2) -0.0016(18) 0.026(2) 0.0097(18) Cl4 0.060(2) 0.119(3) 0.059(2) 0.012(2) 0.0047(17) 0.027(2) S1 0.068(2) 0.064(2) 0.0466(19) 0.0161(16) 0.0087(16) 0.0209(18) S2 0.081(3) 0.074(3) 0.059(2) 0.0150(19) 0.025(2) 0.019(2) F1 0.091(6) 0.063(5) 0.113(7) 0.010(5) -0.006(5) -0.003(4) F2 0.069(5) 0.104(6) 0.075(5) 0.024(4) -0.009(4) 0.022(4) F3 0.088(5) 0.082(5) 0.079(5) 0.009(4) 0.005(4) 0.042(4) F4 0.072(5) 0.104(6) 0.071(5) 0.007(5) 0.003(4) 0.015(4) O1 0.073(6) 0.097(6) 0.058(5) 0.034(5) 0.024(4) 0.036(5) O2 0.091(6) 0.055(5) 0.064(5) 0.018(4) 0.014(5) 0.022(5) O3 0.065(6) 0.112(7) 0.058(6) 0.027(5) 0.024(5) 0.017(6) O4 0.151(9) 0.063(6) 0.089(7) 0.000(5) 0.058(6) 0.044(6) O10 0.045(4) 0.061(5) 0.039(4) 0.019(4) 0.010(3) 0.006(4) N1 0.072(7) 0.054(7) 0.049(6) 0.007(5) 0.016(5) 0.021(5) N2 0.080(7) 0.062(7) 0.055(6) 0.025(5) 0.031(5) 0.028(6) C1 0.050(8) 0.062(8) 0.039(7) 0.011(6) 0.012(6) 0.015(7) C2 0.049(8) 0.061(8) 0.033(6) 0.009(6) 0.003(6) 0.008(6) C3 0.051(8) 0.053(8) 0.053(8) 0.010(6) 0.000(6) 0.011(7) C4 0.061(8) 0.074(9) 0.055(8) 0.022(7) 0.017(7) 0.024(8) C5 0.081(10) 0.057(8) 0.047(8) 0.014(6) 0.009(7) 0.006(8) C6 0.102(10) 0.066(9) 0.051(8) 0.013(6) 0.000(7) 0.037(8) C7 0.067(9) 0.098(10) 0.065(8) 0.024(8) 0.017(7) 0.045(8) C8 0.065(8) 0.056(8) 0.028(6) 0.002(6) 0.021(6) 0.025(7) C9 0.063(9) 0.071(10) 0.052(8) 0.013(7) 0.014(7) 0.036(8) C10 0.077(10) 0.056(9) 0.065(9) 0.007(7) 0.001(8) 0.008(8) C11 0.064(9) 0.066(10) 0.060(9) 0.005(7) -0.004(7) 0.009(8) C12 0.065(9) 0.081(10) 0.044(8) 0.004(7) -0.011(7) 0.020(8) C13 0.056(8) 0.054(8) 0.040(7) 0.001(6) 0.002(6) 0.025(7) C14 0.081(9) 0.058(8) 0.034(7) 0.017(6) 0.021(6) 0.024(7) C15 0.078(10) 0.078(10) 0.075(10) 0.030(8) 0.028(8) 0.039(8) C16 0.096(11) 0.075(10) 0.068(10) 0.013(8) 0.022(9) 0.040(9) C17 0.087(10) 0.055(9) 0.043(8) 0.000(7) 0.017(7) 0.007(8) C18 0.105(11) 0.053(9) 0.079(10) 0.012(8) -0.020(9) 0.011(8) C19 0.109(12) 0.049(8) 0.088(11) 0.006(8) -0.008(9) 0.022(8) C20 0.136(13) 0.074(10) 0.075(11) 0.018(8) 0.022(10) 0.027(10) C51 0.078(9) 0.042(7) 0.036(6) 0.007(5) 0.022(6) 0.022(7) C52 0.045(7) 0.071(9) 0.050(7) 0.010(6) 0.008(6) 0.022(7) C53 0.050(8) 0.054(8) 0.045(7) 0.005(6) 0.014(6) 0.008(7) C54 0.059(8) 0.067(9) 0.053(8) 0.004(7) 0.008(6) 0.034(7) C55 0.061(8) 0.064(9) 0.049(7) 0.011(6) 0.019(6) 0.024(7) C56 0.084(9) 0.048(8) 0.049(7) -0.001(6) -0.002(7) 0.018(7) C57 0.077(9) 0.074(9) 0.065(9) 0.019(7) 0.016(7) 0.021(7) C58 0.074(9) 0.056(8) 0.033(7) 0.023(6) 0.017(6) 0.010(7) C59 0.056(8) 0.061(8) 0.063(8) 0.024(7) 0.019(7) 0.020(7) C60 0.076(10) 0.058(9) 0.073(9) 0.015(8) 0.020(8) 0.036(8) C61 0.065(9) 0.093(11) 0.066(9) 0.029(8) 0.014(8) 0.022(9) C62 0.057(9) 0.066(9) 0.056(8) 0.002(7) -0.008(7) 0.015(7) C63 0.069(9) 0.051(8) 0.053(8) 0.026(7) 0.023(7) 0.020(7) C64 0.070(9) 0.064(9) 0.044(8) 0.012(7) 0.008(6) 0.001(7) C65 0.086(10) 0.076(11) 0.062(9) 0.026(8) -0.006(8) 0.004(8) C66 0.049(9) 0.131(14) 0.131(15) 0.084(13) -0.001(9) -0.010(9) C67 0.058(10) 0.17(2) 0.108(16) 0.078(15) 0.004(10) -0.009(13) C68 0.083(11) 0.148(18) 0.049(10) 0.045(12) -0.001(8) -0.012(13) C69 0.116(13) 0.097(12) 0.068(11) 0.016(10) 0.023(10) -0.046(11) C70 0.078(11) 0.32(3) 0.169(19) 0.18(2) 0.009(12) 0.033(15) _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 Ti1 O10 1.786(7) . ? Ti1 Cl1 2.233(4) . ? Ti1 Cl2 2.260(4) . ? Ti1 C5 2.317(12) . ? Ti1 C4 2.341(11) . ? Ti1 C1 2.346(11) . ? Ti1 C2 2.384(10) . ? Ti1 C3 2.417(12) . ? Ti2 O10 1.804(7) . ? Ti2 Cl3 2.230(4) . ? Ti2 Cl4 2.231(4) . ? Ti2 C55 2.312(11) . ? Ti2 C54 2.328(11) . ? Ti2 C53 2.378(11) . ? Ti2 C51 2.389(10) . ? Ti2 C52 2.390(11) . ? S1 O1 1.410(8) . ? S1 O2 1.429(8) . ? S1 N1 1.628(9) . ? S1 C14 1.739(11) . ? S2 O3 1.407(9) . ? S2 O4 1.428(8) . ? S2 N2 1.635(9) . ? S2 C64 1.777(13) . ? F1 C10 1.353(14) . ? F2 C12 1.368(13) . ? F3 C60 1.334(12) . ? F4 C62 1.348(12) . ? N1 C13 1.433(13) . ? N1 H1 0.8700 . ? N2 C63 1.436(13) . ? N2 H2 0.8700 . ? C1 C5 1.379(15) . ? C1 C2 1.410(14) . ? C1 C6 1.475(15) . ? C2 C3 1.415(14) . ? C2 C8 1.475(14) . ? C3 C4 1.405(15) . ? C3 C7 1.475(15) . ? C4 C5 1.391(15) . ? C4 H4 0.9400 . ? C5 H5 0.9400 . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C6 H6C 0.9700 . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C7 H7C 0.9700 . ? C8 C13 1.392(14) . ? C8 C9 1.407(15) . ? C9 C10 1.345(16) . ? C9 H9 0.9400 . ? C10 C11 1.350(16) . ? C11 C12 1.367(16) . ? C11 H11 0.9400 . ? C12 C13 1.360(15) . ? C14 C15 1.353(15) . ? C14 C19 1.390(16) . ? C15 C16 1.368(16) . ? C15 H15 0.9400 . ? C16 C17 1.372(16) . ? C16 H16 0.9400 . ? C17 C18 1.363(16) . ? C17 C20 1.502(16) . ? C18 C19 1.374(17) . ? C18 H18 0.9400 . ? C19 H19 0.9400 . ? C20 H20A 0.9700 . ? C20 H20B 0.9700 . ? C20 H20C 0.9700 . ? C51 C52 1.412(14) . ? C51 C55 1.446(15) . ? C51 C56 1.465(14) . ? C52 C53 1.422(14) . ? C52 C58 1.486(15) . ? C53 C54 1.387(14) . ? C53 C57 1.509(15) . ? C54 C55 1.419(15) . ? C54 H54 0.9400 . ? C55 H55 0.9400 . ? C56 H56A 0.9700 . ? C56 H56B 0.9700 . ? C56 H56C 0.9700 . ? C57 H57A 0.9700 . ? C57 H57B 0.9700 . ? C57 H57C 0.9700 . ? C58 C59 1.391(15) . ? C58 C63 1.394(15) . ? C59 C60 1.383(15) . ? C59 H59 0.9400 . ? C60 C61 1.382(16) . ? C61 C62 1.378(16) . ? C61 H61 0.9400 . ? C62 C63 1.335(15) . ? C64 C65 1.339(15) . ? C64 C69 1.401(17) . ? C65 C66 1.420(17) . ? C65 H65 0.9400 . ? C66 C67 1.35(2) . ? C66 H66 0.9400 . ? C67 C68 1.36(2) . ? C67 C70 1.51(2) . ? C68 C69 1.37(2) . ? C68 H68 0.9400 . ? C69 H69 0.9400 . ? C70 H70A 0.9700 . ? C70 H70B 0.9700 . ? C70 H70C 0.9700 . ? 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 O10 Ti1 Cl1 103.3(2) . . ? O10 Ti1 Cl2 102.9(2) . . ? Cl1 Ti1 Cl2 103.71(14) . . ? O10 Ti1 C5 112.7(4) . . ? Cl1 Ti1 C5 138.5(3) . . ? Cl2 Ti1 C5 88.1(3) . . ? O10 Ti1 C4 143.2(4) . . ? Cl1 Ti1 C4 104.0(3) . . ? Cl2 Ti1 C4 94.0(3) . . ? C5 Ti1 C4 34.8(4) . . ? O10 Ti1 C1 84.7(3) . . ? Cl1 Ti1 C1 138.3(3) . . ? Cl2 Ti1 C1 114.4(3) . . ? C5 Ti1 C1 34.4(4) . . ? C4 Ti1 C1 58.5(4) . . ? O10 Ti1 C2 93.2(3) . . ? Cl1 Ti1 C2 103.6(3) . . ? Cl2 Ti1 C2 144.0(3) . . ? C5 Ti1 C2 55.9(4) . . ? C4 Ti1 C2 56.7(4) . . ? C1 Ti1 C2 34.7(3) . . ? O10 Ti1 C3 126.0(3) . . ? Cl1 Ti1 C3 85.6(3) . . ? Cl2 Ti1 C3 126.9(3) . . ? C5 Ti1 C3 56.9(4) . . ? C4 Ti1 C3 34.3(4) . . ? C1 Ti1 C3 58.5(4) . . ? C2 Ti1 C3 34.3(3) . . ? O10 Ti2 Cl3 102.0(2) . . ? O10 Ti2 Cl4 105.3(2) . . ? Cl3 Ti2 Cl4 102.14(15) . . ? O10 Ti2 C55 113.2(4) . . ? Cl3 Ti2 C55 139.5(3) . . ? Cl4 Ti2 C55 87.8(3) . . ? O10 Ti2 C54 144.3(4) . . ? Cl3 Ti2 C54 104.1(3) . . ? Cl4 Ti2 C54 92.6(3) . . ? C55 Ti2 C54 35.6(4) . . ? O10 Ti2 C53 126.9(4) . . ? Cl3 Ti2 C53 85.0(3) . . ? Cl4 Ti2 C53 124.8(3) . . ? C55 Ti2 C53 58.2(4) . . ? C54 Ti2 C53 34.3(3) . . ? O10 Ti2 C51 85.5(4) . . ? Cl3 Ti2 C51 136.1(3) . . ? Cl4 Ti2 C51 117.6(3) . . ? C55 Ti2 C51 35.8(4) . . ? C54 Ti2 C51 58.8(4) . . ? C53 Ti2 C51 57.9(4) . . ? O10 Ti2 C52 93.5(3) . . ? Cl3 Ti2 C52 101.8(3) . . ? Cl4 Ti2 C52 145.6(3) . . ? C55 Ti2 C52 58.2(4) . . ? C54 Ti2 C52 57.6(4) . . ? C53 Ti2 C52 34.7(4) . . ? C51 Ti2 C52 34.4(3) . . ? O1 S1 O2 121.1(5) . . ? O1 S1 N1 107.3(5) . . ? O2 S1 N1 103.9(5) . . ? O1 S1 C14 107.3(6) . . ? O2 S1 C14 109.9(5) . . ? N1 S1 C14 106.3(5) . . ? O3 S2 O4 121.2(6) . . ? O3 S2 N2 107.7(5) . . ? O4 S2 N2 103.9(5) . . ? O3 S2 C64 107.0(6) . . ? O4 S2 C64 109.7(6) . . ? N2 S2 C64 106.6(5) . . ? Ti1 O10 Ti2 162.3(4) . . ? C13 N1 S1 118.2(7) . . ? C13 N1 H1 120.9 . . ? S1 N1 H1 120.9 . . ? C63 N2 S2 120.3(7) . . ? C63 N2 H2 119.9 . . ? S2 N2 H2 119.9 . . ? C5 C1 C2 104.4(10) . . ? C5 C1 C6 126.8(11) . . ? C2 C1 C6 128.8(11) . . ? C5 C1 Ti1 71.6(7) . . ? C2 C1 Ti1 74.1(6) . . ? C6 C1 Ti1 120.4(7) . . ? C1 C2 C3 110.9(10) . . ? C1 C2 C8 123.8(10) . . ? C3 C2 C8 125.2(10) . . ? C1 C2 Ti1 71.2(6) . . ? C3 C2 Ti1 74.1(6) . . ? C8 C2 Ti1 123.6(7) . . ? C4 C3 C2 105.4(10) . . ? C4 C3 C7 126.2(11) . . ? C2 C3 C7 128.2(11) . . ? C4 C3 Ti1 69.9(6) . . ? C2 C3 Ti1 71.6(6) . . ? C7 C3 Ti1 127.6(8) . . ? C5 C4 C3 107.7(11) . . ? C5 C4 Ti1 71.7(7) . . ? C3 C4 Ti1 75.8(7) . . ? C5 C4 H4 126.2 . . ? C3 C4 H4 126.2 . . ? Ti1 C4 H4 118.3 . . ? C1 C5 C4 111.6(11) . . ? C1 C5 Ti1 74.0(7) . . ? C4 C5 Ti1 73.6(7) . . ? C1 C5 H5 124.2 . . ? C4 C5 H5 124.2 . . ? Ti1 C5 H5 119.8 . . ? C1 C6 H6A 109.5 . . ? C1 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C1 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? C3 C7 H7A 109.5 . . ? C3 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C3 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C13 C8 C9 117.1(11) . . ? C13 C8 C2 121.3(11) . . ? C9 C8 C2 121.6(11) . . ? C10 C9 C8 121.1(12) . . ? C10 C9 H9 119.4 . . ? C8 C9 H9 119.4 . . ? C9 C10 C11 122.7(13) . . ? C9 C10 F1 118.8(13) . . ? C11 C10 F1 118.4(13) . . ? C10 C11 C12 115.9(12) . . ? C10 C11 H11 122.0 . . ? C12 C11 H11 122.0 . . ? C13 C12 C11 124.9(12) . . ? C13 C12 F2 117.3(12) . . ? C11 C12 F2 117.8(12) . . ? C12 C13 C8 118.2(12) . . ? C12 C13 N1 119.6(11) . . ? C8 C13 N1 122.0(11) . . ? C15 C14 C19 119.8(12) . . ? C15 C14 S1 120.9(10) . . ? C19 C14 S1 119.2(10) . . ? C14 C15 C16 119.8(12) . . ? C14 C15 H15 120.1 . . ? C16 C15 H15 120.1 . . ? C15 C16 C17 121.5(12) . . ? C15 C16 H16 119.3 . . ? C17 C16 H16 119.3 . . ? C18 C17 C16 118.6(12) . . ? C18 C17 C20 119.8(13) . . ? C16 C17 C20 121.6(12) . . ? C17 C18 C19 120.9(13) . . ? C17 C18 H18 119.6 . . ? C19 C18 H18 119.6 . . ? C18 C19 C14 119.4(12) . . ? C18 C19 H19 120.3 . . ? C14 C19 H19 120.3 . . ? C17 C20 H20A 109.5 . . ? C17 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C17 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C52 C51 C55 106.2(10) . . ? C52 C51 C56 128.7(11) . . ? C55 C51 C56 125.1(11) . . ? C52 C51 Ti2 72.9(6) . . ? C55 C51 Ti2 69.2(6) . . ? C56 C51 Ti2 122.8(7) . . ? C51 C52 C53 109.1(10) . . ? C51 C52 C58 124.7(11) . . ? C53 C52 C58 126.2(11) . . ? C51 C52 Ti2 72.8(6) . . ? C53 C52 Ti2 72.2(6) . . ? C58 C52 Ti2 122.1(7) . . ? C54 C53 C52 108.1(11) . . ? C54 C53 C57 125.0(11) . . ? C52 C53 C57 126.6(11) . . ? C54 C53 Ti2 70.9(7) . . ? C52 C53 Ti2 73.1(6) . . ? C57 C53 Ti2 126.5(7) . . ? C53 C54 C55 108.7(11) . . ? C53 C54 Ti2 74.8(6) . . ? C55 C54 Ti2 71.6(7) . . ? C53 C54 H54 125.6 . . ? C55 C54 H54 125.6 . . ? Ti2 C54 H54 119.7 . . ? C54 C55 C51 107.8(10) . . ? C54 C55 Ti2 72.8(6) . . ? C51 C55 Ti2 75.0(6) . . ? C54 C55 H55 126.1 . . ? C51 C55 H55 126.1 . . ? Ti2 C55 H55 118.1 . . ? C51 C56 H56A 109.5 . . ? C51 C56 H56B 109.5 . . ? H56A C56 H56B 109.5 . . ? C51 C56 H56C 109.5 . . ? H56A C56 H56C 109.5 . . ? H56B C56 H56C 109.5 . . ? C53 C57 H57A 109.5 . . ? C53 C57 H57B 109.5 . . ? H57A C57 H57B 109.5 . . ? C53 C57 H57C 109.5 . . ? H57A C57 H57C 109.5 . . ? H57B C57 H57C 109.5 . . ? C59 C58 C63 118.7(11) . . ? C59 C58 C52 120.2(11) . . ? C63 C58 C52 121.1(11) . . ? C60 C59 C58 119.7(12) . . ? C60 C59 H59 120.2 . . ? C58 C59 H59 120.2 . . ? F3 C60 C61 118.3(12) . . ? F3 C60 C59 119.7(12) . . ? C61 C60 C59 121.9(12) . . ? C62 C61 C60 115.6(12) . . ? C62 C61 H61 122.2 . . ? C60 C61 H61 122.2 . . ? C63 C62 F4 119.6(12) . . ? C63 C62 C61 125.1(12) . . ? F4 C62 C61 115.3(11) . . ? C62 C63 C58 118.9(11) . . ? C62 C63 N2 119.8(12) . . ? C58 C63 N2 121.3(11) . . ? C65 C64 C69 121.2(14) . . ? C65 C64 S2 117.5(10) . . ? C69 C64 S2 121.3(12) . . ? C64 C65 C66 119.3(14) . . ? C64 C65 H65 120.3 . . ? C66 C65 H65 120.3 . . ? C67 C66 C65 120.3(18) . . ? C67 C66 H66 119.8 . . ? C65 C66 H66 119.8 . . ? C66 C67 C68 118.9(18) . . ? C66 C67 C70 120(2) . . ? C68 C67 C70 121(2) . . ? C67 C68 C69 123.2(17) . . ? C67 C68 H68 118.4 . . ? C69 C68 H68 118.4 . . ? C68 C69 C64 117.1(16) . . ? C68 C69 H69 121.5 . . ? C64 C69 H69 121.5 . . ? C67 C70 H70A 109.5 . . ? C67 C70 H70B 109.5 . . ? H70A C70 H70B 109.5 . . ? C67 C70 H70C 109.5 . . ? H70A C70 H70C 109.5 . . ? H70B C70 H70C 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 Cl1 Ti1 O10 Ti2 8.3(13) . . . . ? Cl2 Ti1 O10 Ti2 116.0(13) . . . . ? C5 Ti1 O10 Ti2 -150.6(13) . . . . ? C4 Ti1 O10 Ti2 -128.8(13) . . . . ? C1 Ti1 O10 Ti2 -130.2(13) . . . . ? C2 Ti1 O10 Ti2 -96.5(13) . . . . ? C3 Ti1 O10 Ti2 -85.9(14) . . . . ? Cl3 Ti2 O10 Ti1 -2.0(13) . . . . ? Cl4 Ti2 O10 Ti1 104.3(13) . . . . ? C55 Ti2 O10 Ti1 -161.5(12) . . . . ? C54 Ti2 O10 Ti1 -138.3(12) . . . . ? C53 Ti2 O10 Ti1 -94.8(13) . . . . ? C51 Ti2 O10 Ti1 -138.3(13) . . . . ? C52 Ti2 O10 Ti1 -104.8(13) . . . . ? O1 S1 N1 C13 51.2(9) . . . . ? O2 S1 N1 C13 -179.4(8) . . . . ? C14 S1 N1 C13 -63.5(9) . . . . ? O3 S2 N2 C63 59.5(10) . . . . ? O4 S2 N2 C63 -170.8(9) . . . . ? C64 S2 N2 C63 -54.9(10) . . . . ? O10 Ti1 C1 C5 -145.2(7) . . . . ? Cl1 Ti1 C1 C5 110.7(7) . . . . ? Cl2 Ti1 C1 C5 -43.4(7) . . . . ? C4 Ti1 C1 C5 35.8(7) . . . . ? C2 Ti1 C1 C5 111.5(10) . . . . ? C3 Ti1 C1 C5 76.3(7) . . . . ? O10 Ti1 C1 C2 103.4(7) . . . . ? Cl1 Ti1 C1 C2 -0.8(9) . . . . ? Cl2 Ti1 C1 C2 -154.9(6) . . . . ? C5 Ti1 C1 C2 -111.5(10) . . . . ? C4 Ti1 C1 C2 -75.7(7) . . . . ? C3 Ti1 C1 C2 -35.2(6) . . . . ? O10 Ti1 C1 C6 -22.7(9) . . . . ? Cl1 Ti1 C1 C6 -126.8(8) . . . . ? Cl2 Ti1 C1 C6 79.1(9) . . . . ? C5 Ti1 C1 C6 122.5(13) . . . . ? C4 Ti1 C1 C6 158.3(11) . . . . ? C2 Ti1 C1 C6 -126.1(12) . . . . ? C3 Ti1 C1 C6 -161.3(11) . . . . ? C5 C1 C2 C3 -1.8(13) . . . . ? C6 C1 C2 C3 -179.6(11) . . . . ? Ti1 C1 C2 C3 63.9(8) . . . . ? C5 C1 C2 C8 175.9(10) . . . . ? C6 C1 C2 C8 -1.9(18) . . . . ? Ti1 C1 C2 C8 -118.4(10) . . . . ? C5 C1 C2 Ti1 -65.7(8) . . . . ? C6 C1 C2 Ti1 116.5(12) . . . . ? O10 Ti1 C2 C1 -76.0(7) . . . . ? Cl1 Ti1 C2 C1 179.5(6) . . . . ? Cl2 Ti1 C2 C1 41.1(9) . . . . ? C5 Ti1 C2 C1 39.4(6) . . . . ? C4 Ti1 C2 C1 81.5(7) . . . . ? C3 Ti1 C2 C1 119.3(9) . . . . ? O10 Ti1 C2 C3 164.8(7) . . . . ? Cl1 Ti1 C2 C3 60.2(7) . . . . ? Cl2 Ti1 C2 C3 -78.2(8) . . . . ? C5 Ti1 C2 C3 -79.8(7) . . . . ? C4 Ti1 C2 C3 -37.8(6) . . . . ? C1 Ti1 C2 C3 -119.3(9) . . . . ? O10 Ti1 C2 C8 42.7(9) . . . . ? Cl1 Ti1 C2 C8 -61.8(9) . . . . ? Cl2 Ti1 C2 C8 159.7(6) . . . . ? C5 Ti1 C2 C8 158.1(11) . . . . ? C4 Ti1 C2 C8 -159.8(11) . . . . ? C1 Ti1 C2 C8 118.7(12) . . . . ? C3 Ti1 C2 C8 -122.1(12) . . . . ? C1 C2 C3 C4 0.0(13) . . . . ? C8 C2 C3 C4 -177.6(10) . . . . ? Ti1 C2 C3 C4 62.2(8) . . . . ? C1 C2 C3 C7 174.0(11) . . . . ? C8 C2 C3 C7 -3.6(19) . . . . ? Ti1 C2 C3 C7 -123.8(12) . . . . ? C1 C2 C3 Ti1 -62.1(8) . . . . ? C8 C2 C3 Ti1 120.2(11) . . . . ? O10 Ti1 C3 C4 -133.7(7) . . . . ? Cl1 Ti1 C3 C4 123.0(7) . . . . ? Cl2 Ti1 C3 C4 19.2(8) . . . . ? C5 Ti1 C3 C4 -38.3(7) . . . . ? C1 Ti1 C3 C4 -79.2(7) . . . . ? C2 Ti1 C3 C4 -114.8(10) . . . . ? O10 Ti1 C3 C2 -18.9(8) . . . . ? Cl1 Ti1 C3 C2 -122.2(6) . . . . ? Cl2 Ti1 C3 C2 133.9(6) . . . . ? C5 Ti1 C3 C2 76.5(7) . . . . ? C4 Ti1 C3 C2 114.8(10) . . . . ? C1 Ti1 C3 C2 35.6(6) . . . . ? O10 Ti1 C3 C7 105.5(10) . . . . ? Cl1 Ti1 C3 C7 2.2(10) . . . . ? Cl2 Ti1 C3 C7 -101.6(10) . . . . ? C5 Ti1 C3 C7 -159.1(12) . . . . ? C4 Ti1 C3 C7 -120.8(13) . . . . ? C1 Ti1 C3 C7 160.0(12) . . . . ? C2 Ti1 C3 C7 124.4(13) . . . . ? C2 C3 C4 C5 1.8(12) . . . . ? C7 C3 C4 C5 -172.4(11) . . . . ? Ti1 C3 C4 C5 65.1(8) . . . . ? C2 C3 C4 Ti1 -63.3(8) . . . . ? C7 C3 C4 Ti1 122.6(12) . . . . ? O10 Ti1 C4 C5 -37.0(11) . . . . ? Cl1 Ti1 C4 C5 -174.0(7) . . . . ? Cl2 Ti1 C4 C5 80.8(7) . . . . ? C1 Ti1 C4 C5 -35.4(7) . . . . ? C2 Ti1 C4 C5 -76.7(7) . . . . ? C3 Ti1 C4 C5 -114.4(10) . . . . ? O10 Ti1 C4 C3 77.5(9) . . . . ? Cl1 Ti1 C4 C3 -59.5(7) . . . . ? Cl2 Ti1 C4 C3 -164.7(6) . . . . ? C5 Ti1 C4 C3 114.4(10) . . . . ? C1 Ti1 C4 C3 79.0(7) . . . . ? C2 Ti1 C4 C3 37.7(6) . . . . ? C2 C1 C5 C4 3.0(13) . . . . ? C6 C1 C5 C4 -179.2(11) . . . . ? Ti1 C1 C5 C4 -64.5(9) . . . . ? C2 C1 C5 Ti1 67.5(7) . . . . ? C6 C1 C5 Ti1 -114.6(11) . . . . ? C3 C4 C5 C1 -3.1(14) . . . . ? Ti1 C4 C5 C1 64.8(9) . . . . ? C3 C4 C5 Ti1 -67.8(8) . . . . ? O10 Ti1 C5 C1 38.1(8) . . . . ? Cl1 Ti1 C5 C1 -110.1(7) . . . . ? Cl2 Ti1 C5 C1 141.2(7) . . . . ? C4 Ti1 C5 C1 -119.0(10) . . . . ? C2 Ti1 C5 C1 -39.8(6) . . . . ? C3 Ti1 C5 C1 -81.2(7) . . . . ? O10 Ti1 C5 C4 157.0(7) . . . . ? Cl1 Ti1 C5 C4 8.8(10) . . . . ? Cl2 Ti1 C5 C4 -99.8(7) . . . . ? C1 Ti1 C5 C4 119.0(10) . . . . ? C2 Ti1 C5 C4 79.2(7) . . . . ? C3 Ti1 C5 C4 37.8(7) . . . . ? C1 C2 C8 C13 -54.9(15) . . . . ? C3 C2 C8 C13 122.4(12) . . . . ? Ti1 C2 C8 C13 -143.7(8) . . . . ? C1 C2 C8 C9 123.5(12) . . . . ? C3 C2 C8 C9 -59.2(15) . . . . ? Ti1 C2 C8 C9 34.7(13) . . . . ? C13 C8 C9 C10 1.8(16) . . . . ? C2 C8 C9 C10 -176.7(11) . . . . ? C8 C9 C10 C11 -0.7(19) . . . . ? C8 C9 C10 F1 -179.7(10) . . . . ? C9 C10 C11 C12 -0.5(19) . . . . ? F1 C10 C11 C12 178.5(11) . . . . ? C10 C11 C12 C13 1(2) . . . . ? C10 C11 C12 F2 177.7(11) . . . . ? C11 C12 C13 C8 0.7(18) . . . . ? F2 C12 C13 C8 -176.6(9) . . . . ? C11 C12 C13 N1 -174.3(11) . . . . ? F2 C12 C13 N1 8.5(16) . . . . ? C9 C8 C13 C12 -1.8(15) . . . . ? C2 C8 C13 C12 176.7(10) . . . . ? C9 C8 C13 N1 173.0(9) . . . . ? C2 C8 C13 N1 -8.5(15) . . . . ? S1 N1 C13 C12 95.0(11) . . . . ? S1 N1 C13 C8 -79.8(11) . . . . ? O1 S1 C14 C15 -19.9(11) . . . . ? O2 S1 C14 C15 -153.4(9) . . . . ? N1 S1 C14 C15 94.8(10) . . . . ? O1 S1 C14 C19 163.1(10) . . . . ? O2 S1 C14 C19 29.5(12) . . . . ? N1 S1 C14 C19 -82.3(11) . . . . ? C19 C14 C15 C16 -2.2(18) . . . . ? S1 C14 C15 C16 -179.2(10) . . . . ? C14 C15 C16 C17 -1(2) . . . . ? C15 C16 C17 C18 2(2) . . . . ? C15 C16 C17 C20 -177.2(12) . . . . ? C16 C17 C18 C19 -2(2) . . . . ? C20 C17 C18 C19 178.0(13) . . . . ? C17 C18 C19 C14 -1(2) . . . . ? C15 C14 C19 C18 3(2) . . . . ? S1 C14 C19 C18 -179.9(10) . . . . ? O10 Ti2 C51 C52 102.9(7) . . . . ? Cl3 Ti2 C51 C52 0.3(9) . . . . ? Cl4 Ti2 C51 C52 -152.2(6) . . . . ? C55 Ti2 C51 C52 -115.4(10) . . . . ? C54 Ti2 C51 C52 -77.1(7) . . . . ? C53 Ti2 C51 C52 -36.7(6) . . . . ? O10 Ti2 C51 C55 -141.7(7) . . . . ? Cl3 Ti2 C51 C55 115.7(7) . . . . ? Cl4 Ti2 C51 C55 -36.8(7) . . . . ? C54 Ti2 C51 C55 38.3(6) . . . . ? C53 Ti2 C51 C55 78.8(7) . . . . ? C52 Ti2 C51 C55 115.4(10) . . . . ? O10 Ti2 C51 C56 -22.6(9) . . . . ? Cl3 Ti2 C51 C56 -125.2(8) . . . . ? Cl4 Ti2 C51 C56 82.3(9) . . . . ? C55 Ti2 C51 C56 119.1(12) . . . . ? C54 Ti2 C51 C56 157.4(11) . . . . ? C53 Ti2 C51 C56 -162.1(11) . . . . ? C52 Ti2 C51 C56 -125.4(13) . . . . ? C55 C51 C52 C53 2.0(12) . . . . ? C56 C51 C52 C53 -177.8(10) . . . . ? Ti2 C51 C52 C53 63.5(8) . . . . ? C55 C51 C52 C58 -179.1(10) . . . . ? C56 C51 C52 C58 1.1(18) . . . . ? Ti2 C51 C52 C58 -117.6(11) . . . . ? C55 C51 C52 Ti2 -61.6(7) . . . . ? C56 C51 C52 Ti2 118.6(11) . . . . ? O10 Ti2 C52 C51 -76.8(7) . . . . ? Cl3 Ti2 C52 C51 -179.8(6) . . . . ? Cl4 Ti2 C52 C51 47.0(10) . . . . ? C55 Ti2 C52 C51 38.5(6) . . . . ? C54 Ti2 C52 C51 80.8(7) . . . . ? C53 Ti2 C52 C51 117.3(9) . . . . ? O10 Ti2 C52 C53 165.9(7) . . . . ? Cl3 Ti2 C52 C53 62.9(6) . . . . ? Cl4 Ti2 C52 C53 -70.3(9) . . . . ? C55 Ti2 C52 C53 -78.9(7) . . . . ? C54 Ti2 C52 C53 -36.5(6) . . . . ? C51 Ti2 C52 C53 -117.3(9) . . . . ? O10 Ti2 C52 C58 43.8(9) . . . . ? Cl3 Ti2 C52 C58 -59.2(9) . . . . ? Cl4 Ti2 C52 C58 167.6(6) . . . . ? C55 Ti2 C52 C58 159.1(11) . . . . ? C54 Ti2 C52 C58 -158.6(11) . . . . ? C53 Ti2 C52 C58 -122.1(13) . . . . ? C51 Ti2 C52 C58 120.6(13) . . . . ? C51 C52 C53 C54 -1.2(12) . . . . ? C58 C52 C53 C54 179.9(10) . . . . ? Ti2 C52 C53 C54 62.6(8) . . . . ? C51 C52 C53 C57 172.8(10) . . . . ? C58 C52 C53 C57 -6.1(18) . . . . ? Ti2 C52 C53 C57 -123.3(11) . . . . ? C51 C52 C53 Ti2 -63.9(8) . . . . ? C58 C52 C53 Ti2 117.2(11) . . . . ? O10 Ti2 C53 C54 -134.5(7) . . . . ? Cl3 Ti2 C53 C54 124.3(7) . . . . ? Cl4 Ti2 C53 C54 22.9(8) . . . . ? C55 Ti2 C53 C54 -37.9(7) . . . . ? C51 Ti2 C53 C54 -80.4(7) . . . . ? C52 Ti2 C53 C54 -116.7(10) . . . . ? O10 Ti2 C53 C52 -17.8(8) . . . . ? Cl3 Ti2 C53 C52 -119.0(6) . . . . ? Cl4 Ti2 C53 C52 139.7(6) . . . . ? C55 Ti2 C53 C52 78.8(7) . . . . ? C54 Ti2 C53 C52 116.7(10) . . . . ? C51 Ti2 C53 C52 36.3(6) . . . . ? O10 Ti2 C53 C57 105.6(10) . . . . ? Cl3 Ti2 C53 C57 4.4(9) . . . . ? Cl4 Ti2 C53 C57 -96.9(10) . . . . ? C55 Ti2 C53 C57 -157.8(11) . . . . ? C54 Ti2 C53 C57 -119.9(13) . . . . ? C51 Ti2 C53 C57 159.7(11) . . . . ? C52 Ti2 C53 C57 123.4(13) . . . . ? C52 C53 C54 C55 0.0(12) . . . . ? C57 C53 C54 C55 -174.2(10) . . . . ? Ti2 C53 C54 C55 64.0(8) . . . . ? C52 C53 C54 Ti2 -64.1(8) . . . . ? C57 C53 C54 Ti2 121.8(10) . . . . ? O10 Ti2 C54 C53 77.7(9) . . . . ? Cl3 Ti2 C54 C53 -58.1(7) . . . . ? Cl4 Ti2 C54 C53 -161.3(7) . . . . ? C55 Ti2 C54 C53 116.2(10) . . . . ? C51 Ti2 C54 C53 77.7(7) . . . . ? C52 Ti2 C54 C53 37.0(6) . . . . ? O10 Ti2 C54 C55 -38.5(10) . . . . ? Cl3 Ti2 C54 C55 -174.3(6) . . . . ? Cl4 Ti2 C54 C55 82.5(7) . . . . ? C53 Ti2 C54 C55 -116.2(10) . . . . ? C51 Ti2 C54 C55 -38.5(6) . . . . ? C52 Ti2 C54 C55 -79.2(7) . . . . ? C53 C54 C55 C51 1.3(12) . . . . ? Ti2 C54 C55 C51 67.4(7) . . . . ? C53 C54 C55 Ti2 -66.2(8) . . . . ? C52 C51 C55 C54 -2.0(12) . . . . ? C56 C51 C55 C54 177.9(10) . . . . ? Ti2 C51 C55 C54 -66.0(7) . . . . ? C52 C51 C55 Ti2 64.0(7) . . . . ? C56 C51 C55 Ti2 -116.2(10) . . . . ? O10 Ti2 C55 C54 156.7(6) . . . . ? Cl3 Ti2 C55 C54 8.6(9) . . . . ? Cl4 Ti2 C55 C54 -97.6(7) . . . . ? C53 Ti2 C55 C54 36.5(6) . . . . ? C51 Ti2 C55 C54 114.5(10) . . . . ? C52 Ti2 C55 C54 77.6(7) . . . . ? O10 Ti2 C55 C51 42.2(7) . . . . ? Cl3 Ti2 C55 C51 -105.9(7) . . . . ? Cl4 Ti2 C55 C51 147.9(6) . . . . ? C54 Ti2 C55 C51 -114.5(10) . . . . ? C53 Ti2 C55 C51 -78.0(7) . . . . ? C52 Ti2 C55 C51 -36.9(6) . . . . ? C51 C52 C58 C59 120.8(12) . . . . ? C53 C52 C58 C59 -60.4(15) . . . . ? Ti2 C52 C58 C59 30.3(14) . . . . ? C51 C52 C58 C63 -59.0(15) . . . . ? C53 C52 C58 C63 119.7(12) . . . . ? Ti2 C52 C58 C63 -149.6(8) . . . . ? C63 C58 C59 C60 4.0(16) . . . . ? C52 C58 C59 C60 -175.9(10) . . . . ? C58 C59 C60 F3 -179.4(10) . . . . ? C58 C59 C60 C61 -0.9(18) . . . . ? F3 C60 C61 C62 177.2(11) . . . . ? C59 C60 C61 C62 -1.3(19) . . . . ? C60 C61 C62 C63 0(2) . . . . ? C60 C61 C62 F4 -179.9(11) . . . . ? F4 C62 C63 C58 -177.0(10) . . . . ? C61 C62 C63 C58 2.7(19) . . . . ? F4 C62 C63 N2 4.4(17) . . . . ? C61 C62 C63 N2 -175.9(11) . . . . ? C59 C58 C63 C62 -4.8(16) . . . . ? C52 C58 C63 C62 175.1(11) . . . . ? C59 C58 C63 N2 173.8(9) . . . . ? C52 C58 C63 N2 -6.4(16) . . . . ? S2 N2 C63 C62 97.6(12) . . . . ? S2 N2 C63 C58 -81.0(12) . . . . ? O3 S2 C64 C65 -37.6(12) . . . . ? O4 S2 C64 C65 -170.7(10) . . . . ? N2 S2 C64 C65 77.4(11) . . . . ? O3 S2 C64 C69 144.5(10) . . . . ? O4 S2 C64 C69 11.4(12) . . . . ? N2 S2 C64 C69 -100.5(11) . . . . ? C69 C64 C65 C66 0(2) . . . . ? S2 C64 C65 C66 -178.1(9) . . . . ? C64 C65 C66 C67 0(2) . . . . ? C65 C66 C67 C68 -1(2) . . . . ? C65 C66 C67 C70 -177.5(13) . . . . ? C66 C67 C68 C69 1(3) . . . . ? C70 C67 C68 C69 177.7(14) . . . . ? C67 C68 C69 C64 -1(2) . . . . ? C65 C64 C69 C68 0(2) . . . . ? S2 C64 C69 C68 178.3(11) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 28.42 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.759 _refine_diff_density_min -0.592 _refine_diff_density_rms 0.161 #===END data_24 _database_code_depnum_ccdc_archive 'CCDC 604508' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C21 H21 Cl2 N O2 S Ti' _chemical_formula_weight 470.25 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' Cl Cl 0.1484 0.1585 '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' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P212121 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 11.194(4) _cell_length_b 9.734(3) _cell_length_c 19.677(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2144.2(13) _cell_formula_units_Z 4 _cell_measurement_temperature 233(2) _cell_measurement_reflns_used 2355 _cell_measurement_theta_min 2.334 _cell_measurement_theta_max 20.305 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.457 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 968 _exptl_absorpt_coefficient_mu 0.762 _exptl_absorpt_correction_type 'multi scan' _exptl_absorpt_correction_T_min 0.8942 _exptl_absorpt_correction_T_max 0.9924 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 233(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD diffractometer' _diffrn_measurement_method \w-scans _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 21910 _diffrn_reflns_av_R_equivalents 0.1051 _diffrn_reflns_av_sigmaI/netI 0.1510 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 28.44 _reflns_number_total 5347 _reflns_number_gt 2905 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1999)' _computing_cell_refinement 'SMART (Bruker, 1999)' _computing_data_reduction 'SAINT-Plus (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0000P)^2^+2.6543P] 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 SHELXL _refine_ls_extinction_coef 0.0114(19) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _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 5347 _refine_ls_number_parameters 258 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1561 _refine_ls_R_factor_gt 0.0639 _refine_ls_wR_factor_ref 0.2004 _refine_ls_wR_factor_gt 0.1429 _refine_ls_goodness_of_fit_ref 1.050 _refine_ls_restrained_S_all 1.050 _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 0.74987(10) 0.52893(11) 0.76030(5) 0.0398(3) Uani 1 1 d . . . S S 0.65310(16) 0.34140(17) 0.65998(8) 0.0452(4) Uani 1 1 d . . . O1 O 0.6325(4) 0.3280(5) 0.7331(2) 0.0483(11) Uani 1 1 d . . . O2 O 0.6997(4) 0.2270(5) 0.6233(2) 0.0566(13) Uani 1 1 d . . . N N 0.7399(5) 0.4727(5) 0.6625(2) 0.0447(12) Uani 1 1 d . . . Cl1 Cl 0.84332(17) 0.37155(18) 0.82698(9) 0.0569(5) Uani 1 1 d . . . Cl2 Cl 0.57621(16) 0.57730(18) 0.81529(9) 0.0516(5) Uani 1 1 d . . . C1 C 0.8608(6) 0.6834(6) 0.6931(3) 0.0399(14) Uani 1 1 d . . . C2 C 0.9416(6) 0.6342(6) 0.7435(3) 0.0459(16) Uani 1 1 d . . . C3 C 0.8957(7) 0.6829(7) 0.8075(3) 0.0497(17) Uani 1 1 d . . . C4 C 0.7916(7) 0.7561(7) 0.7955(4) 0.0518(18) Uani 1 1 d . . . H4 H 0.7442 0.7980 0.8290 0.062 Uiso 1 1 calc R . . C5 C 0.7679(6) 0.7580(6) 0.7250(3) 0.0459(16) Uani 1 1 d . . . C6 C 1.0502(6) 0.5520(7) 0.7310(4) 0.0571(19) Uani 1 1 d . . . H6A H 1.0446 0.5086 0.6868 0.086 Uiso 1 1 calc R . . H6B H 1.0576 0.4820 0.7658 0.086 Uiso 1 1 calc R . . H6C H 1.1197 0.6114 0.7322 0.086 Uiso 1 1 calc R . . C7 C 0.9571(8) 0.6666(9) 0.8754(4) 0.070(2) Uani 1 1 d . . . H7A H 0.8990 0.6771 0.9116 0.105 Uiso 1 1 calc R . . H7B H 1.0187 0.7361 0.8800 0.105 Uiso 1 1 calc R . . H7C H 0.9930 0.5761 0.8781 0.105 Uiso 1 1 calc R . . C8 C 0.6639(7) 0.8297(8) 0.6914(4) 0.0602(19) Uani 1 1 d . . . H8A H 0.5990 0.8391 0.7237 0.090 Uiso 1 1 calc R . . H8B H 0.6371 0.7761 0.6527 0.090 Uiso 1 1 calc R . . H8C H 0.6888 0.9200 0.6761 0.090 Uiso 1 1 calc R . . C9 C 0.8634(6) 0.6494(7) 0.6196(3) 0.0411(15) Uani 1 1 d . . . C10 C 0.7942(6) 0.5321(7) 0.6037(3) 0.0422(15) Uani 1 1 d . . . C11 C 0.7845(7) 0.4874(8) 0.5369(3) 0.0587(19) Uani 1 1 d . . . H11 H 0.7380 0.4101 0.5259 0.070 Uiso 1 1 calc R . . C12 C 0.8458(8) 0.5608(9) 0.4863(4) 0.064(2) Uani 1 1 d . . . H12 H 0.8403 0.5313 0.4409 0.077 Uiso 1 1 calc R . . C13 C 0.9125(7) 0.6727(9) 0.5012(4) 0.060(2) Uani 1 1 d . . . H13 H 0.9527 0.7203 0.4665 0.073 Uiso 1 1 calc R . . C14 C 0.9214(7) 0.7173(8) 0.5688(3) 0.0489(16) Uani 1 1 d . . . H14 H 0.9678 0.7949 0.5792 0.059 Uiso 1 1 calc R . . C15 C 0.5208(6) 0.3963(7) 0.6186(3) 0.0479(17) Uani 1 1 d . . . C16 C 0.4800(7) 0.3295(8) 0.5611(4) 0.0541(18) Uani 1 1 d . . . H16 H 0.5229 0.2544 0.5436 0.065 Uiso 1 1 calc R . . C17 C 0.3781(6) 0.3717(8) 0.5296(4) 0.057(2) Uani 1 1 d . . . H17 H 0.3514 0.3249 0.4907 0.068 Uiso 1 1 calc R . . C18 C 0.3123(6) 0.4836(8) 0.5543(4) 0.0560(19) Uani 1 1 d . . . C19 C 0.3539(6) 0.5499(7) 0.6126(4) 0.0532(17) Uani 1 1 d . . . H19 H 0.3110 0.6248 0.6303 0.064 Uiso 1 1 calc R . . C20 C 0.4575(6) 0.5072(7) 0.6450(3) 0.0490(17) Uani 1 1 d . . . H20 H 0.4846 0.5526 0.6842 0.059 Uiso 1 1 calc R . . C21 C 0.1996(7) 0.5311(10) 0.5195(5) 0.078(3) Uani 1 1 d . . . H21A H 0.1319 0.4800 0.5371 0.118 Uiso 1 1 calc R . . H21B H 0.2064 0.5154 0.4710 0.118 Uiso 1 1 calc R . . H21C H 0.1879 0.6283 0.5280 0.118 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 0.0448(6) 0.0379(6) 0.0369(6) 0.0003(5) -0.0008(6) 0.0007(5) S 0.0475(9) 0.0437(9) 0.0443(9) -0.0085(7) -0.0004(8) -0.0010(8) O1 0.055(3) 0.049(3) 0.041(2) 0.000(2) 0.003(2) 0.001(2) O2 0.060(3) 0.049(3) 0.061(3) -0.019(2) 0.002(3) 0.003(2) N 0.053(3) 0.040(3) 0.041(3) -0.003(2) -0.001(3) -0.015(3) Cl1 0.0580(11) 0.0522(10) 0.0605(11) 0.0158(8) -0.0070(9) 0.0042(9) Cl2 0.0528(10) 0.0546(10) 0.0472(10) -0.0052(8) 0.0036(8) 0.0032(8) C1 0.047(4) 0.034(3) 0.038(3) -0.006(3) -0.002(3) -0.005(3) C2 0.052(4) 0.041(4) 0.045(4) 0.001(3) 0.002(3) -0.007(3) C3 0.060(4) 0.051(4) 0.038(4) 0.000(3) -0.010(3) -0.009(4) C4 0.069(5) 0.041(4) 0.045(4) -0.009(3) -0.002(3) -0.003(3) C5 0.057(4) 0.035(3) 0.046(4) -0.001(3) -0.005(3) -0.001(3) C6 0.048(4) 0.056(5) 0.067(5) 0.011(4) -0.003(4) 0.002(3) C7 0.078(6) 0.077(6) 0.056(5) 0.008(4) -0.016(4) -0.014(5) C8 0.063(5) 0.057(4) 0.061(5) 0.010(4) 0.003(4) 0.014(4) C9 0.043(4) 0.045(4) 0.035(3) 0.005(3) 0.002(3) 0.004(3) C10 0.044(3) 0.048(4) 0.035(3) -0.005(3) -0.002(3) 0.006(3) C11 0.066(5) 0.071(5) 0.040(4) -0.009(4) -0.003(3) -0.004(4) C12 0.069(5) 0.085(6) 0.038(4) -0.003(4) 0.002(4) 0.010(5) C13 0.065(5) 0.071(5) 0.046(4) 0.006(4) 0.010(4) 0.003(5) C14 0.049(4) 0.053(4) 0.045(4) 0.006(3) 0.001(3) -0.005(3) C15 0.047(4) 0.052(4) 0.045(4) -0.007(3) 0.000(3) -0.003(3) C16 0.059(5) 0.053(4) 0.051(4) -0.011(4) 0.002(3) -0.003(4) C17 0.046(4) 0.074(5) 0.050(4) -0.008(4) -0.002(3) -0.012(4) C18 0.049(4) 0.062(4) 0.057(4) 0.013(4) -0.002(3) -0.004(4) C19 0.045(4) 0.054(4) 0.061(4) 0.006(3) -0.002(3) 0.001(4) C20 0.056(4) 0.048(4) 0.043(4) -0.005(3) -0.004(3) -0.005(3) C21 0.057(5) 0.096(7) 0.082(6) 0.011(5) -0.023(4) 0.001(5) _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 2.005(5) . ? Ti Cl1 2.272(2) . ? Ti Cl2 2.274(2) . ? Ti C5 2.344(6) . ? Ti C1 2.356(6) . ? Ti C4 2.364(7) . ? Ti C2 2.401(7) . ? Ti C3 2.403(7) . ? Ti O1 2.416(5) . ? Ti S 2.899(2) . ? S O2 1.426(5) . ? S O1 1.462(5) . ? S N 1.606(5) . ? S C15 1.772(7) . ? N C10 1.429(8) . ? C1 C5 1.415(9) . ? C1 C2 1.425(9) . ? C1 C9 1.484(8) . ? C2 C3 1.439(9) . ? C2 C6 1.476(9) . ? C3 C4 1.386(10) . ? C3 C7 1.511(10) . ? C4 C5 1.412(9) . ? C4 H4 0.9400 . ? C5 C8 1.510(9) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C6 H6C 0.9700 . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C7 H7C 0.9700 . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C8 H8C 0.9700 . ? C9 C14 1.362(9) . ? C9 C10 1.415(9) . ? C10 C11 1.388(9) . ? C11 C12 1.405(11) . ? C11 H11 0.9400 . ? C12 C13 1.353(11) . ? C12 H12 0.9400 . ? C13 C14 1.404(10) . ? C13 H13 0.9400 . ? C14 H14 0.9400 . ? C15 C16 1.383(9) . ? C15 C20 1.392(9) . ? C16 C17 1.361(10) . ? C16 H16 0.9400 . ? C17 C18 1.402(11) . ? C17 H17 0.9400 . ? C18 C19 1.397(10) . ? C18 C21 1.508(10) . ? C19 C20 1.386(9) . ? C19 H19 0.9400 . ? C20 H20 0.9400 . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C21 H21C 0.9700 . ? 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 Cl1 113.33(17) . . ? N Ti Cl2 117.76(17) . . ? Cl1 Ti Cl2 104.98(8) . . ? N Ti C5 88.9(2) . . ? Cl1 Ti C5 140.59(19) . . ? Cl2 Ti C5 91.01(19) . . ? N Ti C1 70.4(2) . . ? Cl1 Ti C1 120.77(17) . . ? Cl2 Ti C1 125.83(17) . . ? C5 Ti C1 35.0(2) . . ? N Ti C4 123.2(2) . . ? Cl1 Ti C4 111.75(19) . . ? Cl2 Ti C4 80.6(2) . . ? C5 Ti C4 34.9(2) . . ? C1 Ti C4 57.5(2) . . ? N Ti C2 92.0(2) . . ? Cl1 Ti C2 87.45(18) . . ? Cl2 Ti C2 137.83(17) . . ? C5 Ti C2 58.4(2) . . ? C1 Ti C2 34.8(2) . . ? C4 Ti C2 57.6(2) . . ? N Ti C3 125.4(2) . . ? Cl1 Ti C3 83.38(18) . . ? Cl2 Ti C3 105.53(19) . . ? C5 Ti C3 57.5(2) . . ? C1 Ti C3 57.3(2) . . ? C4 Ti C3 33.8(2) . . ? C2 Ti C3 34.9(2) . . ? N Ti O1 62.32(18) . . ? Cl1 Ti O1 80.37(13) . . ? Cl2 Ti O1 78.94(12) . . ? C5 Ti O1 138.7(2) . . ? C1 Ti O1 132.75(18) . . ? C4 Ti O1 158.4(2) . . ? C2 Ti O1 143.23(19) . . ? C3 Ti O1 163.8(2) . . ? N Ti S 32.13(15) . . ? Cl1 Ti S 98.09(8) . . ? Cl2 Ti S 97.76(7) . . ? C5 Ti S 115.45(17) . . ? C1 Ti S 102.53(15) . . ? C4 Ti S 149.60(18) . . ? C2 Ti S 120.62(17) . . ? C3 Ti S 155.49(19) . . ? O1 Ti S 30.23(11) . . ? O2 S O1 119.1(3) . . ? O2 S N 114.6(3) . . ? O1 S N 97.9(3) . . ? O2 S C15 108.0(3) . . ? O1 S C15 110.3(3) . . ? N S C15 106.2(3) . . ? O2 S Ti 134.4(2) . . ? O1 S Ti 56.32(19) . . ? N S Ti 41.60(18) . . ? C15 S Ti 115.8(2) . . ? S O1 Ti 93.5(2) . . ? C10 N S 123.7(4) . . ? C10 N Ti 130.0(4) . . ? S N Ti 106.3(3) . . ? C5 C1 C2 109.3(6) . . ? C5 C1 C9 124.1(6) . . ? C2 C1 C9 126.2(6) . . ? C5 C1 Ti 72.0(4) . . ? C2 C1 Ti 74.3(4) . . ? C9 C1 Ti 114.5(4) . . ? C1 C2 C3 105.7(6) . . ? C1 C2 C6 126.1(6) . . ? C3 C2 C6 128.2(6) . . ? C1 C2 Ti 70.9(4) . . ? C3 C2 Ti 72.6(4) . . ? C6 C2 Ti 121.9(4) . . ? C4 C3 C2 108.7(6) . . ? C4 C3 C7 125.9(7) . . ? C2 C3 C7 125.2(7) . . ? C4 C3 Ti 71.6(4) . . ? C2 C3 Ti 72.5(4) . . ? C7 C3 Ti 125.8(5) . . ? C3 C4 C5 109.4(6) . . ? C3 C4 Ti 74.6(4) . . ? C5 C4 Ti 71.8(4) . . ? C3 C4 H4 125.3 . . ? C5 C4 H4 125.3 . . ? Ti C4 H4 120.0 . . ? C4 C5 C1 106.9(6) . . ? C4 C5 C8 125.5(7) . . ? C1 C5 C8 127.5(6) . . ? C4 C5 Ti 73.3(4) . . ? C1 C5 Ti 72.9(4) . . ? C8 C5 Ti 120.2(5) . . ? C2 C6 H6A 109.5 . . ? C2 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C2 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? C3 C7 H7A 109.5 . . ? C3 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C3 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C5 C8 H8A 109.5 . . ? C5 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C5 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C14 C9 C10 119.3(6) . . ? C14 C9 C1 128.0(6) . . ? C10 C9 C1 112.7(5) . . ? C11 C10 C9 120.4(6) . . ? C11 C10 N 127.3(6) . . ? C9 C10 N 112.3(5) . . ? C10 C11 C12 118.3(7) . . ? C10 C11 H11 120.9 . . ? C12 C11 H11 120.9 . . ? C13 C12 C11 121.7(7) . . ? C13 C12 H12 119.2 . . ? C11 C12 H12 119.2 . . ? C12 C13 C14 119.6(7) . . ? C12 C13 H13 120.2 . . ? C14 C13 H13 120.2 . . ? C9 C14 C13 120.8(7) . . ? C9 C14 H14 119.6 . . ? C13 C14 H14 119.6 . . ? C16 C15 C20 120.1(7) . . ? C16 C15 S 120.7(6) . . ? C20 C15 S 119.2(5) . . ? C17 C16 C15 120.5(7) . . ? C17 C16 H16 119.8 . . ? C15 C16 H16 119.8 . . ? C16 C17 C18 121.2(7) . . ? C16 C17 H17 119.4 . . ? C18 C17 H17 119.4 . . ? C19 C18 C17 117.9(7) . . ? C19 C18 C21 120.7(7) . . ? C17 C18 C21 121.4(8) . . ? C20 C19 C18 121.2(7) . . ? C20 C19 H19 119.4 . . ? C18 C19 H19 119.4 . . ? C19 C20 C15 119.2(6) . . ? C19 C20 H20 120.4 . . ? C15 C20 H20 120.4 . . ? C18 C21 H21A 109.5 . . ? C18 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C18 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 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 N Ti S O2 76.9(4) . . . . ? Cl1 Ti S O2 -44.8(3) . . . . ? Cl2 Ti S O2 -151.3(3) . . . . ? C5 Ti S O2 113.9(4) . . . . ? C1 Ti S O2 79.3(4) . . . . ? C4 Ti S O2 124.2(5) . . . . ? C2 Ti S O2 47.0(4) . . . . ? C3 Ti S O2 46.9(6) . . . . ? O1 Ti S O2 -99.5(4) . . . . ? N Ti S O1 176.3(4) . . . . ? Cl1 Ti S O1 54.6(2) . . . . ? Cl2 Ti S O1 -51.8(2) . . . . ? C5 Ti S O1 -146.7(3) . . . . ? C1 Ti S O1 178.7(3) . . . . ? C4 Ti S O1 -136.4(4) . . . . ? C2 Ti S O1 146.4(3) . . . . ? C3 Ti S O1 146.4(5) . . . . ? Cl1 Ti S N -121.7(3) . . . . ? Cl2 Ti S N 131.8(3) . . . . ? C5 Ti S N 37.0(4) . . . . ? C1 Ti S N 2.4(4) . . . . ? C4 Ti S N 47.3(5) . . . . ? C2 Ti S N -29.9(4) . . . . ? C3 Ti S N -30.0(5) . . . . ? O1 Ti S N -176.3(4) . . . . ? N Ti S C15 -85.6(4) . . . . ? Cl1 Ti S C15 152.7(3) . . . . ? Cl2 Ti S C15 46.3(3) . . . . ? C5 Ti S C15 -48.6(3) . . . . ? C1 Ti S C15 -83.2(3) . . . . ? C4 Ti S C15 -38.3(5) . . . . ? C2 Ti S C15 -115.5(3) . . . . ? C3 Ti S C15 -115.5(5) . . . . ? O1 Ti S C15 98.1(3) . . . . ? O2 S O1 Ti 126.3(3) . . . . ? N S O1 Ti 2.5(3) . . . . ? C15 S O1 Ti -108.1(3) . . . . ? N Ti O1 S -2.2(2) . . . . ? Cl1 Ti O1 S -125.1(2) . . . . ? Cl2 Ti O1 S 127.5(2) . . . . ? C5 Ti O1 S 48.7(4) . . . . ? C1 Ti O1 S -1.7(4) . . . . ? C4 Ti O1 S 108.6(5) . . . . ? C2 Ti O1 S -52.7(4) . . . . ? C3 Ti O1 S -124.8(7) . . . . ? O2 S N C10 50.7(6) . . . . ? O1 S N C10 177.7(5) . . . . ? C15 S N C10 -68.4(6) . . . . ? Ti S N C10 -179.2(7) . . . . ? O2 S N Ti -130.1(3) . . . . ? O1 S N Ti -3.1(3) . . . . ? C15 S N Ti 110.8(3) . . . . ? Cl1 Ti N C10 -114.3(5) . . . . ? Cl2 Ti N C10 122.6(5) . . . . ? C5 Ti N C10 32.1(6) . . . . ? C1 Ti N C10 1.6(5) . . . . ? C4 Ti N C10 25.6(7) . . . . ? C2 Ti N C10 -26.3(6) . . . . ? C3 Ti N C10 -15.6(7) . . . . ? O1 Ti N C10 -178.7(6) . . . . ? S Ti N C10 179.2(8) . . . . ? Cl1 Ti N S 66.5(3) . . . . ? Cl2 Ti N S -56.5(3) . . . . ? C5 Ti N S -147.1(3) . . . . ? C1 Ti N S -177.5(4) . . . . ? C4 Ti N S -153.6(3) . . . . ? C2 Ti N S 154.6(3) . . . . ? C3 Ti N S 165.3(3) . . . . ? O1 Ti N S 2.1(2) . . . . ? N Ti C1 C5 118.1(4) . . . . ? Cl1 Ti C1 C5 -135.8(3) . . . . ? Cl2 Ti C1 C5 7.4(4) . . . . ? C4 Ti C1 C5 -38.2(4) . . . . ? C2 Ti C1 C5 -116.9(5) . . . . ? C3 Ti C1 C5 -78.6(4) . . . . ? O1 Ti C1 C5 117.6(4) . . . . ? S Ti C1 C5 116.7(3) . . . . ? N Ti C1 C2 -125.1(4) . . . . ? Cl1 Ti C1 C2 -19.0(4) . . . . ? Cl2 Ti C1 C2 124.2(3) . . . . ? C5 Ti C1 C2 116.9(5) . . . . ? C4 Ti C1 C2 78.6(4) . . . . ? C3 Ti C1 C2 38.3(4) . . . . ? O1 Ti C1 C2 -125.5(4) . . . . ? S Ti C1 C2 -126.4(3) . . . . ? N Ti C1 C9 -2.0(4) . . . . ? Cl1 Ti C1 C9 104.1(4) . . . . ? Cl2 Ti C1 C9 -112.6(4) . . . . ? C5 Ti C1 C9 -120.0(6) . . . . ? C4 Ti C1 C9 -158.2(6) . . . . ? C2 Ti C1 C9 123.1(6) . . . . ? C3 Ti C1 C9 161.4(6) . . . . ? O1 Ti C1 C9 -2.4(6) . . . . ? S Ti C1 C9 -3.3(5) . . . . ? C5 C1 C2 C3 -0.8(7) . . . . ? C9 C1 C2 C3 -173.9(6) . . . . ? Ti C1 C2 C3 -64.8(4) . . . . ? C5 C1 C2 C6 -180.0(6) . . . . ? C9 C1 C2 C6 6.9(11) . . . . ? Ti C1 C2 C6 116.0(6) . . . . ? C5 C1 C2 Ti 64.0(4) . . . . ? C9 C1 C2 Ti -109.1(6) . . . . ? N Ti C2 C1 50.5(4) . . . . ? Cl1 Ti C2 C1 163.8(4) . . . . ? Cl2 Ti C2 C1 -86.6(4) . . . . ? C5 Ti C2 C1 -37.0(4) . . . . ? C4 Ti C2 C1 -78.4(4) . . . . ? C3 Ti C2 C1 -114.2(5) . . . . ? O1 Ti C2 C1 93.6(4) . . . . ? S Ti C2 C1 65.9(4) . . . . ? N Ti C2 C3 164.7(4) . . . . ? Cl1 Ti C2 C3 -82.1(4) . . . . ? Cl2 Ti C2 C3 27.6(5) . . . . ? C5 Ti C2 C3 77.2(4) . . . . ? C1 Ti C2 C3 114.2(5) . . . . ? C4 Ti C2 C3 35.8(4) . . . . ? O1 Ti C2 C3 -152.2(4) . . . . ? S Ti C2 C3 -180.0(3) . . . . ? N Ti C2 C6 -70.7(6) . . . . ? Cl1 Ti C2 C6 42.6(6) . . . . ? Cl2 Ti C2 C6 152.2(5) . . . . ? C5 Ti C2 C6 -158.1(7) . . . . ? C1 Ti C2 C6 -121.2(7) . . . . ? C4 Ti C2 C6 160.5(7) . . . . ? C3 Ti C2 C6 124.7(7) . . . . ? O1 Ti C2 C6 -27.6(7) . . . . ? S Ti C2 C6 -55.3(6) . . . . ? C1 C2 C3 C4 0.8(7) . . . . ? C6 C2 C3 C4 179.9(6) . . . . ? Ti C2 C3 C4 -62.8(5) . . . . ? C1 C2 C3 C7 -174.5(7) . . . . ? C6 C2 C3 C7 4.7(11) . . . . ? Ti C2 C3 C7 121.9(7) . . . . ? C1 C2 C3 Ti 63.6(4) . . . . ? C6 C2 C3 Ti -117.2(7) . . . . ? N Ti C3 C4 98.4(5) . . . . ? Cl1 Ti C3 C4 -147.6(4) . . . . ? Cl2 Ti C3 C4 -43.8(4) . . . . ? C5 Ti C3 C4 37.2(4) . . . . ? C1 Ti C3 C4 79.1(4) . . . . ? C2 Ti C3 C4 117.4(6) . . . . ? O1 Ti C3 C4 -147.8(7) . . . . ? S Ti C3 C4 117.4(5) . . . . ? N Ti C3 C2 -18.9(5) . . . . ? Cl1 Ti C3 C2 95.1(4) . . . . ? Cl2 Ti C3 C2 -161.2(3) . . . . ? C5 Ti C3 C2 -80.1(4) . . . . ? C1 Ti C3 C2 -38.3(4) . . . . ? C4 Ti C3 C2 -117.4(6) . . . . ? O1 Ti C3 C2 94.8(8) . . . . ? S Ti C3 C2 0.1(7) . . . . ? N Ti C3 C7 -140.1(6) . . . . ? Cl1 Ti C3 C7 -26.1(7) . . . . ? Cl2 Ti C3 C7 77.7(7) . . . . ? C5 Ti C3 C7 158.7(8) . . . . ? C1 Ti C3 C7 -159.4(8) . . . . ? C4 Ti C3 C7 121.5(9) . . . . ? C2 Ti C3 C7 -121.1(8) . . . . ? O1 Ti C3 C7 -26.3(12) . . . . ? S Ti C3 C7 -121.1(6) . . . . ? C2 C3 C4 C5 -0.5(8) . . . . ? C7 C3 C4 C5 174.8(7) . . . . ? Ti C3 C4 C5 -63.9(5) . . . . ? C2 C3 C4 Ti 63.4(5) . . . . ? C7 C3 C4 Ti -121.4(7) . . . . ? N Ti C4 C3 -105.5(4) . . . . ? Cl1 Ti C4 C3 35.0(4) . . . . ? Cl2 Ti C4 C3 137.4(4) . . . . ? C5 Ti C4 C3 -116.9(6) . . . . ? C1 Ti C4 C3 -78.5(4) . . . . ? C2 Ti C4 C3 -37.0(4) . . . . ? O1 Ti C4 C3 156.2(5) . . . . ? S Ti C4 C3 -133.3(4) . . . . ? N Ti C4 C5 11.4(5) . . . . ? Cl1 Ti C4 C5 151.9(4) . . . . ? Cl2 Ti C4 C5 -105.7(4) . . . . ? C1 Ti C4 C5 38.4(4) . . . . ? C2 Ti C4 C5 79.9(5) . . . . ? C3 Ti C4 C5 116.9(6) . . . . ? O1 Ti C4 C5 -86.9(7) . . . . ? S Ti C4 C5 -16.4(7) . . . . ? C3 C4 C5 C1 0.0(8) . . . . ? Ti C4 C5 C1 -65.7(4) . . . . ? C3 C4 C5 C8 -178.7(6) . . . . ? Ti C4 C5 C8 115.6(7) . . . . ? C3 C4 C5 Ti 65.7(5) . . . . ? C2 C1 C5 C4 0.5(7) . . . . ? C9 C1 C5 C4 173.8(6) . . . . ? Ti C1 C5 C4 66.0(5) . . . . ? C2 C1 C5 C8 179.2(7) . . . . ? C9 C1 C5 C8 -7.5(10) . . . . ? Ti C1 C5 C8 -115.3(7) . . . . ? C2 C1 C5 Ti -65.5(4) . . . . ? C9 C1 C5 Ti 107.8(6) . . . . ? N Ti C5 C4 -170.4(5) . . . . ? Cl1 Ti C5 C4 -43.6(6) . . . . ? Cl2 Ti C5 C4 71.8(4) . . . . ? C1 Ti C5 C4 -114.2(6) . . . . ? C2 Ti C5 C4 -77.4(5) . . . . ? C3 Ti C5 C4 -36.0(4) . . . . ? O1 Ti C5 C4 146.1(4) . . . . ? S Ti C5 C4 170.9(4) . . . . ? N Ti C5 C1 -56.3(4) . . . . ? Cl1 Ti C5 C1 70.6(4) . . . . ? Cl2 Ti C5 C1 -174.0(3) . . . . ? C4 Ti C5 C1 114.2(6) . . . . ? C2 Ti C5 C1 36.8(4) . . . . ? C3 Ti C5 C1 78.1(4) . . . . ? O1 Ti C5 C1 -99.7(4) . . . . ? S Ti C5 C1 -74.9(4) . . . . ? N Ti C5 C8 67.7(5) . . . . ? Cl1 Ti C5 C8 -165.4(4) . . . . ? Cl2 Ti C5 C8 -50.0(5) . . . . ? C1 Ti C5 C8 124.0(7) . . . . ? C4 Ti C5 C8 -121.8(8) . . . . ? C2 Ti C5 C8 160.7(6) . . . . ? C3 Ti C5 C8 -157.9(6) . . . . ? O1 Ti C5 C8 24.3(7) . . . . ? S Ti C5 C8 49.0(6) . . . . ? C5 C1 C9 C14 97.1(9) . . . . ? C2 C1 C9 C14 -90.7(9) . . . . ? Ti C1 C9 C14 -178.7(6) . . . . ? C5 C1 C9 C10 -82.0(8) . . . . ? C2 C1 C9 C10 90.2(8) . . . . ? Ti C1 C9 C10 2.2(7) . . . . ? C14 C9 C10 C11 -0.6(10) . . . . ? C1 C9 C10 C11 178.5(6) . . . . ? C14 C9 C10 N 179.8(6) . . . . ? C1 C9 C10 N -1.1(8) . . . . ? S N C10 C11 -1.5(10) . . . . ? Ti N C10 C11 179.5(6) . . . . ? S N C10 C9 178.1(4) . . . . ? Ti N C10 C9 -0.9(8) . . . . ? C9 C10 C11 C12 0.6(10) . . . . ? N C10 C11 C12 -179.8(7) . . . . ? C10 C11 C12 C13 -0.4(12) . . . . ? C11 C12 C13 C14 0.1(12) . . . . ? C10 C9 C14 C13 0.4(10) . . . . ? C1 C9 C14 C13 -178.7(7) . . . . ? C12 C13 C14 C9 -0.1(12) . . . . ? O2 S C15 C16 0.2(7) . . . . ? O1 S C15 C16 -131.4(6) . . . . ? N S C15 C16 123.6(6) . . . . ? Ti S C15 C16 167.1(5) . . . . ? O2 S C15 C20 179.7(5) . . . . ? O1 S C15 C20 48.0(6) . . . . ? N S C15 C20 -57.0(6) . . . . ? Ti S C15 C20 -13.4(6) . . . . ? C20 C15 C16 C17 0.3(11) . . . . ? S C15 C16 C17 179.7(6) . . . . ? C15 C16 C17 C18 0.2(11) . . . . ? C16 C17 C18 C19 -0.6(11) . . . . ? C16 C17 C18 C21 179.8(7) . . . . ? C17 C18 C19 C20 0.5(11) . . . . ? C21 C18 C19 C20 -179.9(7) . . . . ? C18 C19 C20 C15 0.0(10) . . . . ? C16 C15 C20 C19 -0.4(10) . . . . ? S C15 C20 C19 -179.9(5) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 28.44 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.641 _refine_diff_density_min -0.453 _refine_diff_density_rms 0.129 #===END