# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_name 'Jingyu Liu' _publ_contact_author_email ljy@ciac.jl.cn loop_ _publ_author_name 'Jingyu Liu' 'Ping Tao' 'Xiaoyan Tang' 'Baixiang Li' 'Yuesheng Li' data_2a _database_code_depnum_ccdc_archive 'CCDC 848391' #TrackingRef '- R.2a 2e 2f 4a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C17 H13 Cl3 F3 N O2 Ti' _chemical_formula_weight 474.53 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' 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)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 13.9210(10) _cell_length_b 8.7218(6) _cell_length_c 16.0158(12) _cell_angle_alpha 90.00 _cell_angle_beta 99.7500(10) _cell_angle_gamma 90.00 _cell_volume 1916.5(2) _cell_formula_units_Z 4 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.645 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 952 _exptl_absorpt_coefficient_mu 0.905 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7729 _exptl_absorpt_correction_T_max 0.9311 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 185(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11844 _diffrn_reflns_av_R_equivalents 0.0189 _diffrn_reflns_av_sigmaI/netI 0.0200 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.79 _diffrn_reflns_theta_max 26.03 _reflns_number_total 3775 _reflns_number_gt 3244 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0455P)^2^+0.7344P] 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 3775 _refine_ls_number_parameters 245 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0379 _refine_ls_R_factor_gt 0.0311 _refine_ls_wR_factor_ref 0.0837 _refine_ls_wR_factor_gt 0.0791 _refine_ls_goodness_of_fit_ref 1.039 _refine_ls_restrained_S_all 1.039 _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 Ti1 Ti 0.48688(2) 0.18891(4) 0.28249(2) 0.02710(11) Uani 1 1 d . . . Cl3 Cl 0.39756(4) 0.40953(7) 0.26486(3) 0.04527(16) Uani 1 1 d . . . Cl2 Cl 0.35548(4) 0.03531(8) 0.25468(4) 0.05129(17) Uani 1 1 d . . . Cl1 Cl 0.58847(4) -0.01419(6) 0.32918(3) 0.04064(14) Uani 1 1 d . . . O1 O 0.52753(9) 0.21243(15) 0.17912(8) 0.0293(3) Uani 1 1 d . . . O2 O 0.47867(9) 0.22273(17) 0.41362(8) 0.0343(3) Uani 1 1 d . . . F1 F 0.79962(10) 0.53567(17) 0.33730(9) 0.0544(4) Uani 1 1 d . . . F2 F 0.69578(12) 0.68853(15) 0.26744(9) 0.0580(4) Uani 1 1 d . . . C2 C 0.62298(14) 0.4340(2) 0.19482(12) 0.0303(4) Uani 1 1 d . . . H2 H 0.6459 0.5189 0.1666 0.036 Uiso 1 1 calc R . . F3 F 0.67967(12) 0.62283(17) 0.39267(9) 0.0592(4) Uani 1 1 d . . . N1 N 0.60906(11) 0.33121(19) 0.33185(9) 0.0282(3) Uani 1 1 d . . . C1 C 0.57431(13) 0.3213(2) 0.14509(12) 0.0282(4) Uani 1 1 d . . . C3 C 0.64209(14) 0.4353(2) 0.28405(12) 0.0307(4) Uani 1 1 d . . . C6 C 0.56734(15) 0.2581(2) 0.46466(12) 0.0343(4) Uani 1 1 d . . . C12 C 0.51225(17) 0.2056(3) 0.00479(13) 0.0416(5) Uani 1 1 d . . . H12 H 0.4708 0.1419 0.0312 0.050 Uiso 1 1 calc R . . C4 C 0.70497(18) 0.5712(3) 0.32144(14) 0.0430(5) Uani 1 1 d . . . C11 C 0.57339(14) 0.3102(2) 0.05330(12) 0.0299(4) Uani 1 1 d . . . C14 C 0.57048(18) 0.2850(3) -0.12076(14) 0.0471(6) Uani 1 1 d . . . H14 H 0.5690 0.2774 -0.1801 0.056 Uiso 1 1 calc R . . C16 C 0.63423(15) 0.4011(3) 0.01292(13) 0.0377(5) Uani 1 1 d . . . H16 H 0.6772 0.4723 0.0449 0.045 Uiso 1 1 calc R . . C5 C 0.63914(15) 0.3124(2) 0.42079(12) 0.0349(5) Uani 1 1 d . . . C10 C 0.73339(17) 0.3264(3) 0.46503(14) 0.0519(6) Uani 1 1 d . . . H10 H 0.7851 0.3526 0.4359 0.062 Uiso 1 1 calc R . . C15 C 0.63211(18) 0.3880(3) -0.07331(14) 0.0460(6) Uani 1 1 d . . . H15 H 0.6736 0.4506 -0.1002 0.055 Uiso 1 1 calc R . . C13 C 0.51114(19) 0.1933(3) -0.08148(14) 0.0509(6) Uani 1 1 d . . . H13 H 0.4692 0.1212 -0.1138 0.061 Uiso 1 1 calc R . . C9 C 0.75189(19) 0.3020(4) 0.55163(15) 0.0654(8) Uani 1 1 d . . . H9 H 0.8163 0.3142 0.5818 0.078 Uiso 1 1 calc R . . C8 C 0.67815(19) 0.2600(4) 0.59477(15) 0.0600(7) Uani 1 1 d . . . H8 H 0.6913 0.2486 0.6546 0.072 Uiso 1 1 calc R . . C17 C 0.39033(16) 0.2456(4) 0.44939(16) 0.0545(7) Uani 1 1 d . . . H17A H 0.3858 0.1662 0.4918 0.082 Uiso 1 1 calc R . . H17B H 0.3334 0.2394 0.4042 0.082 Uiso 1 1 calc R . . H17C H 0.3923 0.3468 0.4762 0.082 Uiso 1 1 calc R . . C7 C 0.58495(18) 0.2346(3) 0.55078(14) 0.0476(6) Uani 1 1 d . . . H7 H 0.5343 0.2017 0.5795 0.057 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 0.02402(18) 0.0340(2) 0.02369(18) 0.00510(14) 0.00509(13) -0.00174(13) Cl3 0.0393(3) 0.0533(4) 0.0457(3) 0.0154(3) 0.0142(2) 0.0177(2) Cl2 0.0393(3) 0.0663(4) 0.0461(3) 0.0083(3) 0.0010(2) -0.0232(3) Cl1 0.0463(3) 0.0368(3) 0.0414(3) 0.0115(2) 0.0146(2) 0.0089(2) O1 0.0295(7) 0.0342(8) 0.0246(6) 0.0037(5) 0.0056(5) -0.0025(6) O2 0.0289(7) 0.0492(9) 0.0269(7) 0.0021(6) 0.0110(5) -0.0028(6) F1 0.0446(8) 0.0656(9) 0.0557(8) -0.0127(7) 0.0163(6) -0.0261(7) F2 0.0917(11) 0.0325(7) 0.0569(9) -0.0049(6) 0.0327(8) -0.0178(7) C2 0.0369(10) 0.0271(10) 0.0293(10) 0.0064(8) 0.0123(8) -0.0006(8) F3 0.0857(11) 0.0522(9) 0.0479(8) -0.0211(7) 0.0351(8) -0.0195(8) N1 0.0277(8) 0.0353(9) 0.0224(8) 0.0007(6) 0.0066(6) -0.0019(7) C1 0.0262(9) 0.0319(10) 0.0274(9) 0.0085(8) 0.0071(7) 0.0069(8) C3 0.0315(10) 0.0319(10) 0.0314(10) -0.0018(8) 0.0131(8) -0.0004(8) C6 0.0369(11) 0.0392(11) 0.0268(10) -0.0010(8) 0.0060(8) -0.0049(9) C12 0.0500(13) 0.0453(13) 0.0302(11) 0.0041(9) 0.0083(9) -0.0063(10) C4 0.0564(14) 0.0403(13) 0.0377(12) -0.0088(10) 0.0233(10) -0.0128(10) C11 0.0303(10) 0.0340(11) 0.0258(9) 0.0061(8) 0.0059(7) 0.0085(8) C14 0.0656(15) 0.0528(14) 0.0240(10) 0.0056(10) 0.0111(10) 0.0099(12) C16 0.0378(11) 0.0469(13) 0.0293(10) 0.0077(9) 0.0082(8) -0.0007(9) C5 0.0373(11) 0.0431(12) 0.0244(10) 0.0010(8) 0.0058(8) -0.0085(9) C10 0.0415(12) 0.0803(19) 0.0326(11) 0.0048(12) 0.0027(9) -0.0216(12) C15 0.0544(14) 0.0553(15) 0.0314(11) 0.0122(10) 0.0156(10) 0.0028(11) C13 0.0681(16) 0.0527(15) 0.0308(11) -0.0026(10) 0.0055(11) -0.0080(12) C9 0.0515(15) 0.107(2) 0.0320(12) 0.0070(14) -0.0076(11) -0.0311(15) C8 0.0665(16) 0.087(2) 0.0241(11) 0.0058(12) -0.0006(11) -0.0254(15) C17 0.0380(12) 0.088(2) 0.0432(13) 0.0028(13) 0.0234(10) 0.0022(13) C7 0.0549(14) 0.0616(16) 0.0282(11) 0.0028(10) 0.0127(10) -0.0156(12) _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 O1 1.8494(13) . ? Ti1 O2 2.1430(13) . ? Ti1 N1 2.1455(16) . ? Ti1 Cl2 2.2501(6) . ? Ti1 Cl3 2.2824(6) . ? Ti1 Cl1 2.3106(6) . ? O1 C1 1.320(2) . ? O2 C6 1.395(2) . ? O2 C17 1.456(2) . ? F1 C4 1.335(3) . ? F2 C4 1.332(3) . ? C2 C1 1.370(3) . ? C2 C3 1.409(3) . ? C2 H2 0.9500 . ? F3 C4 1.328(2) . ? N1 C3 1.319(2) . ? N1 C5 1.425(2) . ? C1 C11 1.471(3) . ? C3 C4 1.534(3) . ? C6 C7 1.375(3) . ? C6 C5 1.398(3) . ? C12 C13 1.383(3) . ? C12 C11 1.392(3) . ? C12 H12 0.9500 . ? C11 C16 1.396(3) . ? C14 C15 1.378(4) . ? C14 C13 1.376(3) . ? C14 H14 0.9500 . ? C16 C15 1.381(3) . ? C16 H16 0.9500 . ? C5 C10 1.387(3) . ? C10 C9 1.384(3) . ? C10 H10 0.9500 . ? C15 H15 0.9500 . ? C13 H13 0.9500 . ? C9 C8 1.380(3) . ? C9 H9 0.9500 . ? C8 C7 1.385(3) . ? C8 H8 0.9500 . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C7 H7 0.9500 . ? 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 Ti1 O2 159.59(6) . . ? O1 Ti1 N1 85.53(6) . . ? O2 Ti1 N1 74.32(5) . . ? O1 Ti1 Cl2 104.51(5) . . ? O2 Ti1 Cl2 95.71(4) . . ? N1 Ti1 Cl2 169.91(4) . . ? O1 Ti1 Cl3 92.22(4) . . ? O2 Ti1 Cl3 83.50(4) . . ? N1 Ti1 Cl3 86.51(5) . . ? Cl2 Ti1 Cl3 94.01(3) . . ? O1 Ti1 Cl1 96.40(4) . . ? O2 Ti1 Cl1 85.39(4) . . ? N1 Ti1 Cl1 85.45(5) . . ? Cl2 Ti1 Cl1 92.30(3) . . ? Cl3 Ti1 Cl1 167.71(3) . . ? C1 O1 Ti1 134.15(13) . . ? C6 O2 C17 117.52(16) . . ? C6 O2 Ti1 114.58(11) . . ? C17 O2 Ti1 126.39(13) . . ? C1 C2 C3 125.84(18) . . ? C1 C2 H2 117.1 . . ? C3 C2 H2 117.1 . . ? C3 N1 C5 125.95(17) . . ? C3 N1 Ti1 121.11(13) . . ? C5 N1 Ti1 112.48(12) . . ? O1 C1 C2 120.39(17) . . ? O1 C1 C11 116.35(17) . . ? C2 C1 C11 123.23(17) . . ? N1 C3 C2 123.95(18) . . ? N1 C3 C4 122.49(17) . . ? C2 C3 C4 113.55(17) . . ? C7 C6 O2 123.01(18) . . ? C7 C6 C5 122.24(19) . . ? O2 C6 C5 114.68(17) . . ? C13 C12 C11 120.7(2) . . ? C13 C12 H12 119.6 . . ? C11 C12 H12 119.6 . . ? F3 C4 F2 106.68(19) . . ? F3 C4 F1 108.18(19) . . ? F2 C4 F1 106.56(18) . . ? F3 C4 C3 112.36(17) . . ? F2 C4 C3 110.76(18) . . ? F1 C4 C3 111.99(18) . . ? C12 C11 C16 118.39(18) . . ? C12 C11 C1 120.13(18) . . ? C16 C11 C1 121.47(18) . . ? C15 C14 C13 119.5(2) . . ? C15 C14 H14 120.2 . . ? C13 C14 H14 120.2 . . ? C15 C16 C11 120.3(2) . . ? C15 C16 H16 119.9 . . ? C11 C16 H16 119.9 . . ? C10 C5 C6 117.91(19) . . ? C10 C5 N1 126.38(19) . . ? C6 C5 N1 115.30(17) . . ? C9 C10 C5 119.9(2) . . ? C9 C10 H10 120.1 . . ? C5 C10 H10 120.1 . . ? C14 C15 C16 120.8(2) . . ? C14 C15 H15 119.6 . . ? C16 C15 H15 119.6 . . ? C14 C13 C12 120.4(2) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? C8 C9 C10 121.0(2) . . ? C8 C9 H9 119.5 . . ? C10 C9 H9 119.5 . . ? C9 C8 C7 120.0(2) . . ? C9 C8 H8 120.0 . . ? C7 C8 H8 120.0 . . ? O2 C17 H17A 109.5 . . ? O2 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? O2 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C6 C7 C8 118.6(2) . . ? C6 C7 H7 120.7 . . ? C8 C7 H7 120.7 . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.03 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.359 _refine_diff_density_min -0.202 _refine_diff_density_rms 0.054 data_2e _database_code_depnum_ccdc_archive 'CCDC 848392' #TrackingRef '- R.2a 2e 2f 4a.cif' #TrackingRef '- R.2a 2e 2f 4a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H19 Cl3 F3 N O S Ti' _chemical_formula_weight 532.67 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 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 18.5534(13) _cell_length_b 24.1288(17) _cell_length_c 10.7907(7) _cell_angle_alpha 90.00 _cell_angle_beta 104.4420(10) _cell_angle_gamma 90.00 _cell_volume 4678.0(6) _cell_formula_units_Z 8 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.513 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2160 _exptl_absorpt_coefficient_mu 0.834 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7881 _exptl_absorpt_correction_T_max 0.9066 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 185(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 25622 _diffrn_reflns_av_R_equivalents 0.0395 _diffrn_reflns_av_sigmaI/netI 0.0491 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -29 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 1.13 _diffrn_reflns_theta_max 26.14 _reflns_number_total 9284 _reflns_number_gt 6943 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0465P)^2^+6.1722P] 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 9284 _refine_ls_number_parameters 547 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0675 _refine_ls_R_factor_gt 0.0475 _refine_ls_wR_factor_ref 0.1219 _refine_ls_wR_factor_gt 0.1129 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.049 _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 Ti1 Ti 1.05238(3) 0.63978(3) 0.92427(6) 0.02468(15) Uani 1 1 d . . . S1 S 0.96235(5) 0.55604(4) 0.86978(8) 0.0269(2) Uani 1 1 d . . . Cl1 Cl 1.07448(5) 0.59555(4) 1.11821(8) 0.0313(2) Uani 1 1 d . . . Cl3 Cl 0.99923(5) 0.67001(4) 0.72223(8) 0.0332(2) Uani 1 1 d . . . Cl2 Cl 1.14766(5) 0.59718(4) 0.86737(10) 0.0427(2) Uani 1 1 d . . . O1 O 1.08830(12) 0.70904(10) 0.9785(2) 0.0285(5) Uani 1 1 d . . . F3 F 0.84128(12) 0.78604(11) 0.8396(2) 0.0515(7) Uani 1 1 d . . . N1 N 0.95114(15) 0.67102(12) 0.9688(3) 0.0255(6) Uani 1 1 d . . . F1 F 0.80343(12) 0.70560(11) 0.8752(3) 0.0532(7) Uani 1 1 d . . . F2 F 0.83713(13) 0.76436(11) 1.0289(2) 0.0521(6) Uani 1 1 d . . . C15 C 0.90811(19) 0.55298(15) 0.7091(3) 0.0299(8) Uani 1 1 d . . . C1 C 1.05929(19) 0.75882(15) 0.9600(3) 0.0262(7) Uani 1 1 d . . . C5 C 0.90330(19) 0.63200(15) 1.0066(3) 0.0277(8) Uani 1 1 d . . . C6 C 0.89911(19) 0.57822(15) 0.9588(3) 0.0296(8) Uani 1 1 d . . . C2 C 0.98433(19) 0.76608(15) 0.9371(3) 0.0281(8) Uani 1 1 d . . . H2 H 0.9648 0.8019 0.9122 0.034 Uiso 1 1 calc R . . C4 C 0.8529(2) 0.74434(17) 0.9249(4) 0.0360(9) Uani 1 1 d . . . C10 C 0.8636(2) 0.64453(17) 1.0977(4) 0.0392(9) Uani 1 1 d . . . H10 H 0.8699 0.6796 1.1390 0.047 Uiso 1 1 calc R . . C7 C 0.8515(2) 0.53972(17) 0.9910(4) 0.0402(9) Uani 1 1 d . . . H7 H 0.8490 0.5032 0.9573 0.048 Uiso 1 1 calc R . . C19 C 0.8084(3) 0.5808(2) 0.5358(4) 0.0564(13) Uani 1 1 d . . . H19 H 0.7658 0.6032 0.5032 0.068 Uiso 1 1 calc R . . C3 C 0.93364(18) 0.72349(15) 0.9482(3) 0.0264(7) Uani 1 1 d . . . C20 C 0.8460(2) 0.58555(19) 0.6619(4) 0.0478(11) Uani 1 1 d . . . H20 H 0.8296 0.6109 0.7163 0.057 Uiso 1 1 calc R . . C16 C 0.9313(2) 0.51573(17) 0.6303(4) 0.0393(9) Uani 1 1 d . . . H16 H 0.9732 0.4927 0.6634 0.047 Uiso 1 1 calc R . . C17 C 0.8932(3) 0.51192(19) 0.5027(4) 0.0518(12) Uani 1 1 d . . . H17 H 0.9096 0.4870 0.4472 0.062 Uiso 1 1 calc R . . C9 C 0.8156(2) 0.60653(19) 1.1277(4) 0.0497(11) Uani 1 1 d . . . H9 H 0.7875 0.6160 1.1872 0.060 Uiso 1 1 calc R . . C8 C 0.8078(2) 0.55439(19) 1.0718(5) 0.0518(12) Uani 1 1 d . . . H8 H 0.7725 0.5289 1.0892 0.062 Uiso 1 1 calc R . . C18 C 0.8309(3) 0.54478(19) 0.4566(4) 0.0474(11) Uani 1 1 d . . . H18 H 0.8040 0.5420 0.3695 0.057 Uiso 1 1 calc R . . Ti2 Ti 0.45110(3) 0.36118(3) 0.87364(6) 0.02392(15) Uani 1 1 d . . . S2 S 0.54133(5) 0.44554(4) 0.91726(8) 0.02462(19) Uani 1 1 d . . . Cl4 Cl 0.41009(5) 0.40651(4) 1.02869(8) 0.0301(2) Uani 1 1 d . . . Cl6 Cl 0.51678(5) 0.33328(4) 0.73276(8) 0.0336(2) Uani 1 1 d . . . Cl5 Cl 0.36068(5) 0.40007(4) 0.71531(9) 0.0413(2) Uani 1 1 d . . . O2 O 0.41574(12) 0.29114(10) 0.8903(2) 0.0278(5) Uani 1 1 d . . . N2 N 0.54475(14) 0.33147(11) 1.0221(2) 0.0222(6) Uani 1 1 d . . . C21 C 0.44636(18) 0.24179(14) 0.9039(3) 0.0245(7) Uani 1 1 d . . . C25 C 0.58431(17) 0.37078(14) 1.1129(3) 0.0236(7) Uani 1 1 d . . . C35 C 0.6092(2) 0.44767(15) 0.8267(3) 0.0292(8) Uani 1 1 d . . . C26 C 0.59073(18) 0.42497(14) 1.0733(3) 0.0245(7) Uani 1 1 d . . . C27 C 0.62791(19) 0.46431(15) 1.1589(3) 0.0306(8) Uani 1 1 d . . . H27 H 0.6337 0.5010 1.1308 0.037 Uiso 1 1 calc R . . C23 C 0.56651(18) 0.27989(14) 1.0205(3) 0.0244(7) Uani 1 1 d . . . C31 C 0.39356(19) 0.19552(15) 0.8476(3) 0.0273(8) Uani 1 1 d . . . C30 C 0.61015(18) 0.35758(15) 1.2418(3) 0.0274(8) Uani 1 1 d . . . H30 H 0.6027 0.3214 1.2708 0.033 Uiso 1 1 calc R . . C29 C 0.6467(2) 0.39701(16) 1.3279(3) 0.0338(9) Uani 1 1 d . . . H29 H 0.6650 0.3878 1.4157 0.041 Uiso 1 1 calc R . . C22 C 0.52071(18) 0.23609(14) 0.9592(3) 0.0259(7) Uani 1 1 d . . . H22 H 0.5428 0.2008 0.9562 0.031 Uiso 1 1 calc R . . C33 C 0.4298(2) 0.13817(16) 0.8722(4) 0.0388(9) Uani 1 1 d . . . H33A H 0.4724 0.1363 0.8339 0.058 Uiso 1 1 calc R . . H33B H 0.3933 0.1097 0.8338 0.058 Uiso 1 1 calc R . . H33C H 0.4467 0.1318 0.9646 0.058 Uiso 1 1 calc R . . C28 C 0.6566(2) 0.44990(16) 1.2857(4) 0.0363(9) Uani 1 1 d . . . H28 H 0.6833 0.4766 1.3442 0.044 Uiso 1 1 calc R . . C34 C 0.3701(2) 0.20671(16) 0.7025(3) 0.0324(8) Uani 1 1 d . . . H34A H 0.3455 0.2429 0.6868 0.049 Uiso 1 1 calc R . . H34B H 0.3357 0.1777 0.6603 0.049 Uiso 1 1 calc R . . H34C H 0.4143 0.2067 0.6682 0.049 Uiso 1 1 calc R . . C40 C 0.6754(2) 0.41925(19) 0.8606(4) 0.0450(10) Uani 1 1 d . . . H40 H 0.6870 0.3967 0.9351 0.054 Uiso 1 1 calc R . . C32 C 0.3259(2) 0.19814(18) 0.9051(4) 0.0399(10) Uani 1 1 d . . . H32A H 0.3416 0.1901 0.9970 0.060 Uiso 1 1 calc R . . H32B H 0.2889 0.1707 0.8630 0.060 Uiso 1 1 calc R . . H32C H 0.3039 0.2353 0.8922 0.060 Uiso 1 1 calc R . . C38 C 0.7080(3) 0.4561(2) 0.6757(5) 0.0610(14) Uani 1 1 d . . . H38 H 0.7421 0.4589 0.6234 0.073 Uiso 1 1 calc R . . C36 C 0.5915(3) 0.47998(19) 0.7181(4) 0.0514(12) Uani 1 1 d . . . H36 H 0.5454 0.4992 0.6947 0.062 Uiso 1 1 calc R . . C37 C 0.6424(3) 0.4839(2) 0.6435(5) 0.0682(15) Uani 1 1 d . . . H37 H 0.6311 0.5064 0.5688 0.082 Uiso 1 1 calc R . . C39 C 0.7250(2) 0.4241(2) 0.7840(5) 0.0593(14) Uani 1 1 d . . . H39 H 0.7712 0.4050 0.8068 0.071 Uiso 1 1 calc R . . F7 F 0.69569(11) 0.30275(9) 1.0841(2) 0.0404(5) Uani 1 1 d . . . F8 F 0.66629(11) 0.22225(10) 1.0075(2) 0.0463(6) Uani 1 1 d . . . F9 F 0.65829(11) 0.24130(10) 1.1967(2) 0.0438(6) Uani 1 1 d . . . C24 C 0.64770(19) 0.26196(15) 1.0800(3) 0.0301(8) Uani 1 1 d . . . C11 C 1.1151(2) 0.80472(15) 0.9614(3) 0.0309(8) Uani 1 1 d . . . C13 C 1.0794(2) 0.86196(16) 0.9458(4) 0.0407(10) Uani 1 1 d . . . H13A H 1.0423 0.8640 0.8634 0.061 Uiso 1 1 calc R . . H13B H 1.1177 0.8902 0.9485 0.061 Uiso 1 1 calc R . . H13C H 1.0551 0.8686 1.0153 0.061 Uiso 1 1 calc R . . C12 C 1.1744(2) 0.80191(18) 1.0887(4) 0.0398(10) Uani 1 1 d . . . H12A H 1.1511 0.8088 1.1594 0.060 Uiso 1 1 calc R . . H12B H 1.2126 0.8300 1.0894 0.060 Uiso 1 1 calc R . . H12C H 1.1973 0.7651 1.0986 0.060 Uiso 1 1 calc R . . C14 C 1.1508(2) 0.79295(17) 0.8503(4) 0.0354(9) Uani 1 1 d . . . H14A H 1.1738 0.7561 0.8613 0.053 Uiso 1 1 calc R . . H14B H 1.1888 0.8210 0.8493 0.053 Uiso 1 1 calc R . . H14C H 1.1124 0.7942 0.7693 0.053 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 0.0218(3) 0.0263(3) 0.0257(3) 0.0013(2) 0.0055(3) 0.0003(3) S1 0.0252(4) 0.0279(5) 0.0266(5) -0.0017(3) 0.0044(4) -0.0004(4) Cl1 0.0328(5) 0.0333(5) 0.0249(4) 0.0028(3) 0.0015(4) 0.0001(4) Cl3 0.0362(5) 0.0395(5) 0.0241(4) 0.0046(4) 0.0076(4) 0.0016(4) Cl2 0.0367(5) 0.0442(6) 0.0529(6) 0.0085(5) 0.0216(5) 0.0123(4) O1 0.0218(12) 0.0278(14) 0.0345(14) 0.0023(10) 0.0046(10) -0.0025(10) F3 0.0322(12) 0.0570(16) 0.0655(17) 0.0268(13) 0.0123(11) 0.0144(11) N1 0.0243(14) 0.0312(17) 0.0217(15) 0.0004(12) 0.0068(12) -0.0019(12) F1 0.0234(12) 0.0576(17) 0.0711(18) 0.0029(13) -0.0023(11) -0.0039(11) F2 0.0450(14) 0.0592(17) 0.0612(16) 0.0001(13) 0.0303(13) 0.0137(12) C15 0.0275(18) 0.031(2) 0.0279(19) -0.0040(15) 0.0006(15) -0.0032(15) C1 0.0289(18) 0.0282(19) 0.0218(17) 0.0001(14) 0.0073(14) -0.0026(15) C5 0.0248(18) 0.033(2) 0.0270(19) 0.0037(14) 0.0085(15) 0.0004(15) C6 0.0265(18) 0.035(2) 0.0266(19) -0.0015(15) 0.0061(15) -0.0039(15) C2 0.0296(19) 0.0266(19) 0.0285(19) 0.0018(14) 0.0078(15) 0.0018(15) C4 0.0264(19) 0.040(2) 0.042(2) 0.0045(18) 0.0095(17) 0.0004(17) C10 0.044(2) 0.039(2) 0.039(2) -0.0019(17) 0.0195(19) -0.0003(19) C7 0.041(2) 0.036(2) 0.048(2) -0.0056(18) 0.0210(19) -0.0104(18) C19 0.041(3) 0.069(3) 0.047(3) -0.014(2) -0.012(2) 0.011(2) C3 0.0247(17) 0.031(2) 0.0228(18) -0.0010(14) 0.0049(14) 0.0029(15) C20 0.039(2) 0.057(3) 0.039(2) -0.016(2) -0.0060(19) 0.013(2) C16 0.046(2) 0.038(2) 0.034(2) -0.0002(17) 0.0084(18) 0.0036(18) C17 0.081(3) 0.049(3) 0.026(2) -0.0082(18) 0.017(2) 0.001(2) C9 0.052(3) 0.050(3) 0.060(3) 0.005(2) 0.038(2) -0.002(2) C8 0.050(3) 0.043(3) 0.073(3) 0.006(2) 0.034(2) -0.009(2) C18 0.056(3) 0.049(3) 0.030(2) 0.0001(19) -0.004(2) -0.012(2) Ti2 0.0205(3) 0.0248(3) 0.0238(3) -0.0004(2) 0.0006(2) 0.0015(2) S2 0.0241(4) 0.0255(4) 0.0230(4) 0.0014(3) 0.0036(3) 0.0006(3) Cl4 0.0309(4) 0.0305(5) 0.0309(5) 0.0015(3) 0.0116(4) 0.0041(4) Cl6 0.0379(5) 0.0370(5) 0.0265(5) -0.0036(4) 0.0091(4) 0.0012(4) Cl5 0.0380(5) 0.0415(6) 0.0336(5) -0.0027(4) -0.0112(4) 0.0110(4) O2 0.0233(12) 0.0247(13) 0.0328(14) -0.0006(10) 0.0021(10) -0.0003(10) N2 0.0225(14) 0.0239(15) 0.0183(14) 0.0002(11) 0.0014(11) -0.0003(12) C21 0.0286(18) 0.0244(18) 0.0204(17) 0.0004(13) 0.0058(14) 0.0003(14) C25 0.0182(16) 0.0251(18) 0.0254(18) -0.0018(13) 0.0016(13) 0.0002(13) C35 0.0311(19) 0.033(2) 0.0249(18) -0.0038(15) 0.0091(15) -0.0060(16) C26 0.0210(16) 0.0287(19) 0.0225(17) 0.0030(14) 0.0032(13) 0.0021(14) C27 0.0305(19) 0.027(2) 0.031(2) -0.0006(15) 0.0035(15) -0.0024(16) C23 0.0219(17) 0.0276(19) 0.0219(17) -0.0002(14) 0.0022(13) 0.0016(14) C31 0.0264(18) 0.029(2) 0.0245(18) -0.0041(14) 0.0036(14) -0.0061(15) C30 0.0264(18) 0.0277(19) 0.0261(18) 0.0025(14) 0.0029(14) 0.0014(15) C29 0.037(2) 0.036(2) 0.0233(19) -0.0005(15) -0.0009(16) 0.0028(17) C22 0.0262(17) 0.0231(18) 0.0266(18) 0.0011(14) 0.0031(14) 0.0005(14) C33 0.038(2) 0.027(2) 0.044(2) -0.0040(17) -0.0036(18) -0.0077(17) C28 0.037(2) 0.037(2) 0.030(2) -0.0063(16) -0.0025(16) -0.0035(17) C34 0.034(2) 0.038(2) 0.0232(19) -0.0053(15) 0.0045(15) -0.0056(17) C40 0.029(2) 0.066(3) 0.039(2) 0.004(2) 0.0077(18) 0.001(2) C32 0.037(2) 0.047(3) 0.038(2) -0.0066(18) 0.0153(18) -0.0154(19) C38 0.066(3) 0.071(4) 0.059(3) -0.015(3) 0.041(3) -0.018(3) C36 0.067(3) 0.052(3) 0.042(3) 0.011(2) 0.028(2) 0.013(2) C37 0.100(4) 0.064(4) 0.054(3) 0.012(2) 0.045(3) 0.007(3) C39 0.028(2) 0.096(4) 0.056(3) -0.010(3) 0.015(2) -0.003(2) F7 0.0212(10) 0.0347(13) 0.0637(15) -0.0018(11) 0.0073(10) -0.0024(9) F8 0.0273(11) 0.0448(14) 0.0616(16) -0.0192(11) 0.0015(11) 0.0103(10) F9 0.0322(12) 0.0498(15) 0.0411(14) 0.0125(11) -0.0065(10) 0.0047(10) C24 0.0235(18) 0.030(2) 0.034(2) -0.0043(15) 0.0009(15) 0.0010(15) C11 0.0310(19) 0.031(2) 0.034(2) 0.0004(15) 0.0145(16) -0.0069(16) C13 0.049(2) 0.030(2) 0.050(3) 0.0029(17) 0.025(2) -0.0039(18) C12 0.034(2) 0.045(3) 0.040(2) -0.0048(18) 0.0086(18) -0.0163(18) C14 0.035(2) 0.038(2) 0.037(2) 0.0054(16) 0.0156(17) 0.0008(17) _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 O1 1.840(2) . ? Ti1 N1 2.186(3) . ? Ti1 Cl2 2.2583(11) . ? Ti1 Cl3 2.2771(10) . ? Ti1 Cl1 2.2931(10) . ? Ti1 S1 2.5938(11) . ? S1 C6 1.774(4) . ? S1 C15 1.776(4) . ? O1 C1 1.311(4) . ? F3 C4 1.344(4) . ? N1 C3 1.312(4) . ? N1 C5 1.422(4) . ? F1 C4 1.326(4) . ? F2 C4 1.320(5) . ? C15 C16 1.377(5) . ? C15 C20 1.383(5) . ? C1 C2 1.362(5) . ? C1 C11 1.514(5) . ? C5 C6 1.391(5) . ? C5 C10 1.400(5) . ? C6 C7 1.384(5) . ? C2 C3 1.418(5) . ? C2 H2 0.9500 . ? C4 C3 1.540(5) . ? C10 C9 1.372(6) . ? C10 H10 0.9500 . ? C7 C8 1.377(6) . ? C7 H7 0.9500 . ? C19 C18 1.356(6) . ? C19 C20 1.370(6) . ? C19 H19 0.9500 . ? C20 H20 0.9500 . ? C16 C17 1.385(6) . ? C16 H16 0.9500 . ? C17 C18 1.387(6) . ? C17 H17 0.9500 . ? C9 C8 1.387(6) . ? C9 H9 0.9500 . ? C8 H8 0.9500 . ? C18 H18 0.9500 . ? Ti2 O2 1.838(2) . ? Ti2 N2 2.170(3) . ? Ti2 Cl6 2.2745(10) . ? Ti2 Cl5 2.2769(10) . ? Ti2 Cl4 2.2823(10) . ? Ti2 S2 2.6026(11) . ? S2 C26 1.775(3) . ? S2 C35 1.776(4) . ? O2 C21 1.312(4) . ? N2 C23 1.310(4) . ? N2 C25 1.428(4) . ? C21 C22 1.367(5) . ? C21 C31 1.509(5) . ? C25 C26 1.390(5) . ? C25 C30 1.390(5) . ? C35 C40 1.375(5) . ? C35 C36 1.377(5) . ? C26 C27 1.383(5) . ? C27 C28 1.383(5) . ? C27 H27 0.9500 . ? C23 C22 1.413(5) . ? C23 C24 1.545(5) . ? C31 C33 1.532(5) . ? C31 C32 1.535(5) . ? C31 C34 1.540(5) . ? C30 C29 1.384(5) . ? C30 H30 0.9500 . ? C29 C28 1.382(5) . ? C29 H29 0.9500 . ? C22 H22 0.9500 . ? C33 H33A 0.9800 . ? C33 H33B 0.9800 . ? C33 H33C 0.9800 . ? C28 H28 0.9500 . ? C34 H34A 0.9800 . ? C34 H34B 0.9800 . ? C34 H34C 0.9800 . ? C40 C39 1.386(6) . ? C40 H40 0.9500 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? C38 C37 1.357(7) . ? C38 C39 1.371(7) . ? C38 H38 0.9500 . ? C36 C37 1.389(6) . ? C36 H36 0.9500 . ? C37 H37 0.9500 . ? C39 H39 0.9500 . ? F7 C24 1.320(4) . ? F8 C24 1.335(4) . ? F9 C24 1.323(4) . ? C11 C13 1.523(5) . ? C11 C12 1.532(5) . ? C11 C14 1.533(5) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? 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 Ti1 N1 83.09(11) . . ? O1 Ti1 Cl2 104.71(8) . . ? N1 Ti1 Cl2 172.15(9) . . ? O1 Ti1 Cl3 92.84(8) . . ? N1 Ti1 Cl3 84.79(8) . . ? Cl2 Ti1 Cl3 93.84(4) . . ? O1 Ti1 Cl1 99.46(8) . . ? N1 Ti1 Cl1 85.86(8) . . ? Cl2 Ti1 Cl1 93.58(4) . . ? Cl3 Ti1 Cl1 163.54(4) . . ? O1 Ti1 S1 160.28(8) . . ? N1 Ti1 S1 77.20(8) . . ? Cl2 Ti1 S1 95.01(4) . . ? Cl3 Ti1 S1 86.09(4) . . ? Cl1 Ti1 S1 78.63(3) . . ? C6 S1 C15 104.54(17) . . ? C6 S1 Ti1 96.77(12) . . ? C15 S1 Ti1 115.45(12) . . ? C1 O1 Ti1 133.0(2) . . ? C3 N1 C5 122.8(3) . . ? C3 N1 Ti1 119.0(2) . . ? C5 N1 Ti1 117.8(2) . . ? C16 C15 C20 120.2(4) . . ? C16 C15 S1 116.2(3) . . ? C20 C15 S1 123.6(3) . . ? O1 C1 C2 120.5(3) . . ? O1 C1 C11 114.5(3) . . ? C2 C1 C11 125.0(3) . . ? C6 C5 C10 118.1(3) . . ? C6 C5 N1 119.5(3) . . ? C10 C5 N1 122.3(3) . . ? C7 C6 C5 120.9(3) . . ? C7 C6 S1 118.9(3) . . ? C5 C6 S1 119.9(3) . . ? C1 C2 C3 124.1(3) . . ? C1 C2 H2 118.0 . . ? C3 C2 H2 118.0 . . ? F2 C4 F1 108.9(3) . . ? F2 C4 F3 106.1(3) . . ? F1 C4 F3 105.9(3) . . ? F2 C4 C3 113.2(3) . . ? F1 C4 C3 112.5(3) . . ? F3 C4 C3 109.8(3) . . ? C9 C10 C5 120.5(4) . . ? C9 C10 H10 119.8 . . ? C5 C10 H10 119.8 . . ? C8 C7 C6 120.0(4) . . ? C8 C7 H7 120.0 . . ? C6 C7 H7 120.0 . . ? C18 C19 C20 121.3(4) . . ? C18 C19 H19 119.4 . . ? C20 C19 H19 119.4 . . ? N1 C3 C2 124.9(3) . . ? N1 C3 C4 122.2(3) . . ? C2 C3 C4 112.8(3) . . ? C19 C20 C15 119.3(4) . . ? C19 C20 H20 120.4 . . ? C15 C20 H20 120.4 . . ? C15 C16 C17 119.8(4) . . ? C15 C16 H16 120.1 . . ? C17 C16 H16 120.1 . . ? C16 C17 C18 119.4(4) . . ? C16 C17 H17 120.3 . . ? C18 C17 H17 120.3 . . ? C10 C9 C8 120.5(4) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C7 C8 C9 119.7(4) . . ? C7 C8 H8 120.2 . . ? C9 C8 H8 120.2 . . ? C19 C18 C17 120.0(4) . . ? C19 C18 H18 120.0 . . ? C17 C18 H18 120.0 . . ? O2 Ti2 N2 82.16(10) . . ? O2 Ti2 Cl6 93.28(8) . . ? N2 Ti2 Cl6 86.08(8) . . ? O2 Ti2 Cl5 103.79(8) . . ? N2 Ti2 Cl5 173.90(8) . . ? Cl6 Ti2 Cl5 92.16(4) . . ? O2 Ti2 Cl4 100.16(8) . . ? N2 Ti2 Cl4 88.24(8) . . ? Cl6 Ti2 Cl4 164.56(4) . . ? Cl5 Ti2 Cl4 91.99(4) . . ? O2 Ti2 S2 158.53(8) . . ? N2 Ti2 S2 76.37(8) . . ? Cl6 Ti2 S2 85.68(4) . . ? Cl5 Ti2 S2 97.68(4) . . ? Cl4 Ti2 S2 79.03(3) . . ? C26 S2 C35 105.12(16) . . ? C26 S2 Ti2 96.29(12) . . ? C35 S2 Ti2 115.80(12) . . ? C21 O2 Ti2 133.7(2) . . ? C23 N2 C25 122.2(3) . . ? C23 N2 Ti2 119.8(2) . . ? C25 N2 Ti2 117.8(2) . . ? O2 C21 C22 120.1(3) . . ? O2 C21 C31 114.0(3) . . ? C22 C21 C31 125.8(3) . . ? C26 C25 C30 119.2(3) . . ? C26 C25 N2 118.9(3) . . ? C30 C25 N2 121.6(3) . . ? C40 C35 C36 121.1(4) . . ? C40 C35 S2 123.3(3) . . ? C36 C35 S2 115.7(3) . . ? C27 C26 C25 120.5(3) . . ? C27 C26 S2 119.7(3) . . ? C25 C26 S2 119.4(3) . . ? C26 C27 C28 119.5(3) . . ? C26 C27 H27 120.2 . . ? C28 C27 H27 120.2 . . ? N2 C23 C22 124.4(3) . . ? N2 C23 C24 122.2(3) . . ? C22 C23 C24 113.3(3) . . ? C21 C31 C33 112.7(3) . . ? C21 C31 C32 108.7(3) . . ? C33 C31 C32 109.6(3) . . ? C21 C31 C34 105.6(3) . . ? C33 C31 C34 109.6(3) . . ? C32 C31 C34 110.6(3) . . ? C29 C30 C25 120.2(3) . . ? C29 C30 H30 119.9 . . ? C25 C30 H30 119.9 . . ? C28 C29 C30 119.8(3) . . ? C28 C29 H29 120.1 . . ? C30 C29 H29 120.1 . . ? C21 C22 C23 123.6(3) . . ? C21 C22 H22 118.2 . . ? C23 C22 H22 118.2 . . ? C31 C33 H33A 109.5 . . ? C31 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? C31 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? C27 C28 C29 120.5(3) . . ? C27 C28 H28 119.7 . . ? C29 C28 H28 119.7 . . ? C31 C34 H34A 109.5 . . ? C31 C34 H34B 109.5 . . ? H34A C34 H34B 109.5 . . ? C31 C34 H34C 109.5 . . ? H34A C34 H34C 109.5 . . ? H34B C34 H34C 109.5 . . ? C35 C40 C39 118.8(4) . . ? C35 C40 H40 120.6 . . ? C39 C40 H40 120.6 . . ? C31 C32 H32A 109.5 . . ? C31 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C31 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C37 C38 C39 119.8(4) . . ? C37 C38 H38 120.1 . . ? C39 C38 H38 120.1 . . ? C35 C36 C37 118.7(4) . . ? C35 C36 H36 120.7 . . ? C37 C36 H36 120.7 . . ? C38 C37 C36 120.9(5) . . ? C38 C37 H37 119.5 . . ? C36 C37 H37 119.5 . . ? C38 C39 C40 120.7(5) . . ? C38 C39 H39 119.7 . . ? C40 C39 H39 119.7 . . ? F7 C24 F9 108.0(3) . . ? F7 C24 F8 106.5(3) . . ? F9 C24 F8 106.8(3) . . ? F7 C24 C23 112.6(3) . . ? F9 C24 C23 113.5(3) . . ? F8 C24 C23 109.0(3) . . ? C1 C11 C13 112.6(3) . . ? C1 C11 C12 108.2(3) . . ? C13 C11 C12 109.6(3) . . ? C1 C11 C14 106.5(3) . . ? C13 C11 C14 110.0(3) . . ? C12 C11 C14 109.9(3) . . ? 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 . . ? C11 C12 H12A 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C11 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C11 C14 H14A 109.5 . . ? C11 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C11 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 26.14 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.625 _refine_diff_density_min -0.364 _refine_diff_density_rms 0.078 data_2f _database_code_depnum_ccdc_archive 'CCDC 848393' #TrackingRef '- R.2a 2e 2f 4a.cif' #TrackingRef '- R.2a 2e 2f 4a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H20 Cl3 F3 N O P Ti' _chemical_formula_weight 628.67 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' P P 0.1023 0.0942 '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)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 9.0938(5) _cell_length_b 18.1497(11) _cell_length_c 17.1168(10) _cell_angle_alpha 90.00 _cell_angle_beta 92.9540(10) _cell_angle_gamma 90.00 _cell_volume 2821.4(3) _cell_formula_units_Z 4 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.480 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1272 _exptl_absorpt_coefficient_mu 0.687 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8204 _exptl_absorpt_correction_T_max 0.8863 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 185(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14108 _diffrn_reflns_av_R_equivalents 0.0355 _diffrn_reflns_av_sigmaI/netI 0.0391 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.24 _diffrn_reflns_theta_max 25.12 _reflns_number_total 5022 _reflns_number_gt 3827 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0533P)^2^+0.9773P] 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 5022 _refine_ls_number_parameters 343 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0580 _refine_ls_R_factor_gt 0.0377 _refine_ls_wR_factor_ref 0.1041 _refine_ls_wR_factor_gt 0.0930 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _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 Ti1 Ti 0.16080(5) 0.20598(3) 0.96841(3) 0.02834(14) Uani 1 1 d . . . P1 P 0.13073(8) 0.13086(4) 0.83832(4) 0.02634(17) Uani 1 1 d . . . Cl1 Cl 0.04458(8) 0.11196(4) 1.02866(4) 0.03685(18) Uani 1 1 d . . . Cl3 Cl 0.25303(9) 0.29564(4) 0.89020(4) 0.0468(2) Uani 1 1 d . . . O1 O 0.1154(2) 0.28068(10) 1.04007(10) 0.0332(4) Uani 1 1 d . . . N1 N -0.0579(2) 0.23136(11) 0.91473(11) 0.0263(5) Uani 1 1 d . . . C17 C 0.1528(3) 0.17344(14) 0.74381(14) 0.0293(6) Uani 1 1 d . . . F3 F -0.0041(3) 0.45792(12) 1.08280(13) 0.0868(8) Uani 1 1 d . . . C6 C -0.0647(3) 0.11579(14) 0.84309(14) 0.0276(6) Uani 1 1 d . . . C23 C 0.2204(3) 0.04161(14) 0.82971(15) 0.0276(6) Uani 1 1 d . . . C5 C -0.1419(3) 0.17138(14) 0.87973(14) 0.0269(6) Uani 1 1 d . . . C18 C 0.2871(3) 0.20522(15) 0.72737(16) 0.0371(7) Uani 1 1 d . . . H18 H 0.3648 0.2077 0.7666 0.045 Uiso 1 1 calc R . . C28 C 0.2421(3) -0.00209(15) 0.89591(17) 0.0368(7) Uani 1 1 d . . . H28 H 0.2078 0.0137 0.9447 0.044 Uiso 1 1 calc R . . C1 C 0.0463(3) 0.34246(15) 1.02584(16) 0.0351(7) Uani 1 1 d . . . C19 C 0.3065(4) 0.23327(16) 0.65292(17) 0.0458(8) Uani 1 1 d . . . H19 H 0.3976 0.2552 0.6412 0.055 Uiso 1 1 calc R . . C2 C -0.0524(3) 0.35502(15) 0.96595(16) 0.0363(7) Uani 1 1 d . . . H2 H -0.0860 0.4041 0.9579 0.044 Uiso 1 1 calc R . . C4 C -0.2297(3) 0.32309(14) 0.85646(16) 0.0316(6) Uani 1 1 d . . . F1 F 0.0971(3) 0.37763(12) 1.15663(11) 0.0821(7) Uani 1 1 d . . . C10 C -0.2914(3) 0.16284(15) 0.88975(15) 0.0321(6) Uani 1 1 d . . . H10 H -0.3450 0.2004 0.9145 0.038 Uiso 1 1 calc R . . C24 C 0.2717(3) 0.01788(15) 0.75921(17) 0.0369(7) Uani 1 1 d . . . H24 H 0.2571 0.0475 0.7137 0.044 Uiso 1 1 calc R . . C3 C -0.1108(3) 0.29873(14) 0.91306(15) 0.0292(6) Uani 1 1 d . . . C12 C -0.3259(4) 0.33070(17) 0.72390(18) 0.0511(9) Uani 1 1 d . . . H12 H -0.3178 0.3197 0.6700 0.061 Uiso 1 1 calc R . . C25 C 0.3444(3) -0.04913(16) 0.75494(18) 0.0422(7) Uani 1 1 d . . . H25 H 0.3793 -0.0654 0.7065 0.051 Uiso 1 1 calc R . . C9 C -0.3619(3) 0.09925(17) 0.86340(17) 0.0411(7) Uani 1 1 d . . . H9 H -0.4641 0.0933 0.8705 0.049 Uiso 1 1 calc R . . C22 C 0.0404(4) 0.16972(16) 0.68561(16) 0.0402(7) Uani 1 1 d . . . H22 H -0.0513 0.1479 0.6965 0.048 Uiso 1 1 calc R . . C15 C -0.3467(3) 0.36559(16) 0.87964(18) 0.0406(7) Uani 1 1 d . . . H15 H -0.3531 0.3789 0.9330 0.049 Uiso 1 1 calc R . . C27 C 0.3145(3) -0.06894(16) 0.89008(19) 0.0458(8) Uani 1 1 d . . . H27 H 0.3286 -0.0992 0.9351 0.055 Uiso 1 1 calc R . . F2 F 0.2190(3) 0.42930(15) 1.07169(16) 0.1043(10) Uani 1 1 d . . . C26 C 0.3658(3) -0.09190(16) 0.8205(2) 0.0442(8) Uani 1 1 d . . . H26 H 0.4164 -0.1375 0.8176 0.053 Uiso 1 1 calc R . . C11 C -0.2193(3) 0.30623(16) 0.77788(16) 0.0395(7) Uani 1 1 d . . . H11 H -0.1388 0.2778 0.7613 0.047 Uiso 1 1 calc R . . C7 C -0.1378(3) 0.05281(16) 0.81655(17) 0.0381(7) Uani 1 1 d . . . H7 H -0.0855 0.0153 0.7910 0.046 Uiso 1 1 calc R . . C21 C 0.0621(4) 0.19797(18) 0.61150(18) 0.0517(9) Uani 1 1 d . . . H21 H -0.0143 0.1955 0.5716 0.062 Uiso 1 1 calc R . . C8 C -0.2860(3) 0.04447(17) 0.82702(18) 0.0444(8) Uani 1 1 d . . . H8 H -0.3357 0.0011 0.8092 0.053 Uiso 1 1 calc R . . C20 C 0.1943(5) 0.22924(18) 0.59661(17) 0.0540(10) Uani 1 1 d . . . H20 H 0.2087 0.2487 0.5460 0.065 Uiso 1 1 calc R . . C14 C -0.4541(3) 0.38849(17) 0.8247(2) 0.0475(8) Uani 1 1 d . . . H14 H -0.5355 0.4166 0.8406 0.057 Uiso 1 1 calc R . . C13 C -0.4435(4) 0.37081(17) 0.7473(2) 0.0511(9) Uani 1 1 d . . . H13 H -0.5177 0.3864 0.7098 0.061 Uiso 1 1 calc R . . C16 C 0.0898(4) 0.40244(18) 1.08473(19) 0.0520(9) Uani 1 1 d . . . Cl2 Cl 0.38258(8) 0.16022(5) 1.00514(5) 0.0503(2) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.0282(3) 0.0332(3) 0.0234(2) -0.0021(2) -0.0011(2) -0.0037(2) P1 0.0291(4) 0.0271(4) 0.0227(3) 0.0010(3) -0.0009(3) -0.0013(3) Cl1 0.0417(4) 0.0401(4) 0.0286(3) 0.0068(3) 0.0000(3) -0.0049(3) Cl3 0.0588(5) 0.0401(4) 0.0429(4) -0.0043(3) 0.0171(4) -0.0177(4) O1 0.0381(11) 0.0362(11) 0.0250(9) -0.0056(8) -0.0020(8) -0.0018(9) N1 0.0297(13) 0.0279(12) 0.0212(10) -0.0008(9) -0.0007(9) -0.0012(9) C17 0.0391(17) 0.0256(14) 0.0231(13) -0.0004(10) -0.0002(12) 0.0059(12) F3 0.123(2) 0.0540(13) 0.0791(15) -0.0359(12) -0.0316(14) 0.0237(14) C6 0.0292(15) 0.0294(14) 0.0236(13) 0.0011(11) -0.0039(11) -0.0020(11) C23 0.0236(14) 0.0277(14) 0.0311(14) 0.0010(11) -0.0026(11) -0.0018(11) C5 0.0309(15) 0.0280(14) 0.0212(12) 0.0028(10) -0.0050(11) -0.0027(11) C18 0.0467(18) 0.0327(15) 0.0326(15) -0.0017(12) 0.0088(14) -0.0009(13) C28 0.0365(17) 0.0351(16) 0.0387(16) 0.0052(13) 0.0017(13) 0.0024(13) C1 0.0390(17) 0.0350(16) 0.0312(15) -0.0069(12) 0.0008(13) -0.0074(13) C19 0.066(2) 0.0343(16) 0.0392(17) -0.0001(13) 0.0233(17) 0.0002(15) C2 0.0473(19) 0.0290(15) 0.0321(15) -0.0030(12) -0.0028(14) 0.0002(13) C4 0.0346(16) 0.0283(14) 0.0314(14) 0.0043(11) -0.0021(12) -0.0001(12) F1 0.139(2) 0.0672(14) 0.0378(11) -0.0188(10) -0.0185(13) -0.0068(14) C10 0.0293(15) 0.0385(16) 0.0281(14) -0.0008(12) -0.0017(12) 0.0010(12) C24 0.0437(18) 0.0319(15) 0.0350(15) -0.0004(12) 0.0000(14) -0.0018(13) C3 0.0315(15) 0.0294(14) 0.0267(13) 0.0010(11) 0.0016(12) -0.0015(12) C12 0.073(3) 0.0458(19) 0.0327(16) 0.0039(14) -0.0148(17) 0.0065(18) C25 0.0445(18) 0.0351(16) 0.0479(18) -0.0076(14) 0.0099(15) -0.0005(14) C9 0.0285(16) 0.0487(19) 0.0460(17) -0.0020(14) -0.0011(14) -0.0096(14) C22 0.0473(19) 0.0408(17) 0.0320(15) -0.0025(13) -0.0022(14) 0.0096(14) C15 0.0439(19) 0.0398(17) 0.0380(16) 0.0049(13) 0.0027(14) 0.0058(14) C27 0.0468(19) 0.0386(17) 0.0519(19) 0.0144(15) 0.0023(16) 0.0062(15) F2 0.0951(19) 0.107(2) 0.113(2) -0.0592(16) 0.0207(16) -0.0613(16) C26 0.0373(18) 0.0288(16) 0.067(2) 0.0044(15) 0.0056(16) 0.0045(13) C11 0.0504(19) 0.0358(16) 0.0317(15) 0.0022(13) -0.0029(14) 0.0057(14) C7 0.0367(17) 0.0327(16) 0.0446(17) -0.0084(13) -0.0021(14) -0.0027(13) C21 0.074(3) 0.051(2) 0.0288(16) 0.0034(14) -0.0053(17) 0.0194(18) C8 0.0380(18) 0.0408(17) 0.0536(19) -0.0085(15) -0.0053(15) -0.0128(14) C20 0.095(3) 0.0440(19) 0.0245(16) 0.0084(14) 0.0140(19) 0.0209(19) C14 0.0374(18) 0.0383(17) 0.067(2) 0.0152(16) 0.0026(16) 0.0061(14) C13 0.059(2) 0.0369(18) 0.054(2) 0.0129(15) -0.0232(18) -0.0023(16) C16 0.070(3) 0.0404(19) 0.0450(19) -0.0139(15) -0.0044(18) -0.0066(18) Cl2 0.0315(4) 0.0620(5) 0.0562(5) -0.0109(4) -0.0095(4) 0.0041(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.8881(18) . ? Ti1 N1 2.197(2) . ? Ti1 Cl2 2.2410(9) . ? Ti1 Cl1 2.2815(8) . ? Ti1 Cl3 2.2933(8) . ? Ti1 P1 2.6133(8) . ? P1 C6 1.804(3) . ? P1 C17 1.813(3) . ? P1 C23 1.823(3) . ? O1 C1 1.302(3) . ? N1 C3 1.314(3) . ? N1 C5 1.442(3) . ? C17 C22 1.392(4) . ? C17 C18 1.393(4) . ? F3 C16 1.320(4) . ? C6 C7 1.387(4) . ? C6 C5 1.396(4) . ? C23 C24 1.385(4) . ? C23 C28 1.389(4) . ? C5 C10 1.387(4) . ? C18 C19 1.392(4) . ? C18 H18 0.9500 . ? C28 C27 1.386(4) . ? C28 H28 0.9500 . ? C1 C2 1.347(4) . ? C1 C16 1.522(4) . ? C19 C20 1.369(5) . ? C19 H19 0.9500 . ? C2 C3 1.448(4) . ? C2 H2 0.9500 . ? C4 C15 1.389(4) . ? C4 C11 1.387(4) . ? C4 C3 1.481(4) . ? F1 C16 1.309(4) . ? C10 C9 1.385(4) . ? C10 H10 0.9500 . ? C24 C25 1.388(4) . ? C24 H24 0.9500 . ? C12 C13 1.370(5) . ? C12 C11 1.378(4) . ? C12 H12 0.9500 . ? C25 C26 1.370(4) . ? C25 H25 0.9500 . ? C9 C8 1.377(4) . ? C9 H9 0.9500 . ? C22 C21 1.392(4) . ? C22 H22 0.9500 . ? C15 C14 1.385(4) . ? C15 H15 0.9500 . ? C27 C26 1.367(4) . ? C27 H27 0.9500 . ? F2 C16 1.302(4) . ? C26 H26 0.9500 . ? C11 H11 0.9500 . ? C7 C8 1.377(4) . ? C7 H7 0.9500 . ? C21 C20 1.365(5) . ? C21 H21 0.9500 . ? C8 H8 0.9500 . ? C20 H20 0.9500 . ? C14 C13 1.371(5) . ? C14 H14 0.9500 . ? C13 H13 0.9500 . ? 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 Ti1 N1 84.13(8) . . ? O1 Ti1 Cl2 107.91(6) . . ? N1 Ti1 Cl2 167.84(6) . . ? O1 Ti1 Cl1 96.98(6) . . ? N1 Ti1 Cl1 85.15(6) . . ? Cl2 Ti1 Cl1 91.55(3) . . ? O1 Ti1 Cl3 88.19(6) . . ? N1 Ti1 Cl3 87.57(6) . . ? Cl2 Ti1 Cl3 94.35(4) . . ? Cl1 Ti1 Cl3 170.57(4) . . ? O1 Ti1 P1 155.70(6) . . ? N1 Ti1 P1 72.56(6) . . ? Cl2 Ti1 P1 95.67(3) . . ? Cl1 Ti1 P1 87.96(3) . . ? Cl3 Ti1 P1 84.16(3) . . ? C6 P1 C17 105.04(12) . . ? C6 P1 C23 108.34(12) . . ? C17 P1 C23 103.66(11) . . ? C6 P1 Ti1 95.77(8) . . ? C17 P1 Ti1 121.75(9) . . ? C23 P1 Ti1 120.33(9) . . ? C1 O1 Ti1 128.04(17) . . ? C3 N1 C5 120.5(2) . . ? C3 N1 Ti1 121.80(17) . . ? C5 N1 Ti1 117.65(16) . . ? C22 C17 C18 119.7(3) . . ? C22 C17 P1 120.5(2) . . ? C18 C17 P1 119.7(2) . . ? C7 C6 C5 119.9(2) . . ? C7 C6 P1 124.5(2) . . ? C5 C6 P1 115.48(19) . . ? C24 C23 C28 119.5(3) . . ? C24 C23 P1 121.3(2) . . ? C28 C23 P1 119.1(2) . . ? C10 C5 C6 119.6(2) . . ? C10 C5 N1 122.3(2) . . ? C6 C5 N1 117.7(2) . . ? C19 C18 C17 119.4(3) . . ? C19 C18 H18 120.3 . . ? C17 C18 H18 120.3 . . ? C23 C28 C27 119.3(3) . . ? C23 C28 H28 120.4 . . ? C27 C28 H28 120.4 . . ? O1 C1 C2 125.8(3) . . ? O1 C1 C16 112.7(3) . . ? C2 C1 C16 121.5(3) . . ? C20 C19 C18 120.0(3) . . ? C20 C19 H19 120.0 . . ? C18 C19 H19 120.0 . . ? C1 C2 C3 124.4(3) . . ? C1 C2 H2 117.8 . . ? C3 C2 H2 117.8 . . ? C15 C4 C11 119.4(3) . . ? C15 C4 C3 121.5(3) . . ? C11 C4 C3 119.0(2) . . ? C9 C10 C5 119.5(3) . . ? C9 C10 H10 120.2 . . ? C5 C10 H10 120.2 . . ? C23 C24 C25 120.1(3) . . ? C23 C24 H24 120.0 . . ? C25 C24 H24 120.0 . . ? N1 C3 C2 121.4(2) . . ? N1 C3 C4 123.1(2) . . ? C2 C3 C4 115.5(2) . . ? C13 C12 C11 120.5(3) . . ? C13 C12 H12 119.7 . . ? C11 C12 H12 119.7 . . ? C26 C25 C24 120.1(3) . . ? C26 C25 H25 120.0 . . ? C24 C25 H25 120.0 . . ? C8 C9 C10 121.0(3) . . ? C8 C9 H9 119.5 . . ? C10 C9 H9 119.5 . . ? C17 C22 C21 120.1(3) . . ? C17 C22 H22 120.0 . . ? C21 C22 H22 120.0 . . ? C14 C15 C4 119.8(3) . . ? C14 C15 H15 120.1 . . ? C4 C15 H15 120.1 . . ? C26 C27 C28 121.0(3) . . ? C26 C27 H27 119.5 . . ? C28 C27 H27 119.5 . . ? C27 C26 C25 120.0(3) . . ? C27 C26 H26 120.0 . . ? C25 C26 H26 120.0 . . ? C12 C11 C4 119.9(3) . . ? C12 C11 H11 120.0 . . ? C4 C11 H11 120.0 . . ? C8 C7 C6 120.3(3) . . ? C8 C7 H7 119.9 . . ? C6 C7 H7 119.9 . . ? C20 C21 C22 119.4(3) . . ? C20 C21 H21 120.3 . . ? C22 C21 H21 120.3 . . ? C7 C8 C9 119.7(3) . . ? C7 C8 H8 120.1 . . ? C9 C8 H8 120.1 . . ? C21 C20 C19 121.5(3) . . ? C21 C20 H20 119.3 . . ? C19 C20 H20 119.3 . . ? C13 C14 C15 120.2(3) . . ? C13 C14 H14 119.9 . . ? C15 C14 H14 119.9 . . ? C12 C13 C14 120.1(3) . . ? C12 C13 H13 119.9 . . ? C14 C13 H13 119.9 . . ? F2 C16 F1 106.7(3) . . ? F2 C16 F3 107.4(3) . . ? F1 C16 F3 106.7(3) . . ? F2 C16 C1 111.1(3) . . ? F1 C16 C1 112.1(3) . . ? F3 C16 C1 112.5(3) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.12 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.422 _refine_diff_density_min -0.326 _refine_diff_density_rms 0.059 data_4a _database_code_depnum_ccdc_archive 'CCDC 848394' #TrackingRef '- R.2a 2e 2f 4a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C34 H26 Cl2 F6 N2 O4 Ti' _chemical_formula_weight 759.37 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' F F 0.0171 0.0103 '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 37.165(2) _cell_length_b 9.1989(5) _cell_length_c 19.2847(11) _cell_angle_alpha 90.00 _cell_angle_beta 95.2820(10) _cell_angle_gamma 90.00 _cell_volume 6564.9(6) _cell_formula_units_Z 8 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used 3923 _cell_measurement_theta_min 2.20 _cell_measurement_theta_max 25.71 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.537 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3088 _exptl_absorpt_coefficient_mu 0.500 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8524 _exptl_absorpt_correction_T_max 0.9288 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 185(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 APEXII CCD' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 17735 _diffrn_reflns_av_R_equivalents 0.0538 _diffrn_reflns_av_sigmaI/netI 0.0660 _diffrn_reflns_limit_h_min -45 _diffrn_reflns_limit_h_max 43 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.10 _diffrn_reflns_theta_max 26.05 _reflns_number_total 6470 _reflns_number_gt 3917 _reflns_threshold_expression >2\s(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution ? _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ? _computing_publication_material ? _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^ > 2\s(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. Benzene should be a planar moluculae, but the C5--C10 atoms are not in an ideal plane in refinements. We use "afix 66" to restrain the benzene ring. ; _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^)+(0.0558P)^2^+22.0835P] 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 6470 _refine_ls_number_parameters 448 _refine_ls_number_restraints 48 _refine_ls_R_factor_all 0.1243 _refine_ls_R_factor_gt 0.0746 _refine_ls_wR_factor_ref 0.1926 _refine_ls_wR_factor_gt 0.1706 _refine_ls_goodness_of_fit_ref 1.202 _refine_ls_restrained_S_all 1.207 _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 Ti1 Ti 0.62965(2) 0.57750(10) 0.10002(4) 0.0322(2) Uani 1 1 d . . . N1 N 0.65343(11) 0.7479(6) 0.0392(2) 0.0478(13) Uani 1 1 d . . . O1 O 0.66837(8) 0.6272(4) 0.16501(16) 0.0326(8) Uani 1 1 d . . . Cl1 Cl 0.66090(4) 0.41602(18) 0.03779(7) 0.0541(4) Uani 1 1 d . . . C1 C 0.69854(12) 0.6996(5) 0.1698(2) 0.0303(11) Uani 1 1 d . . . F1 F 0.6931(4) 0.8739(16) -0.0632(7) 0.084(5) Uani 0.50 1 d P . . F1' F 0.7057(3) 0.8079(14) -0.0651(7) 0.051(3) Uani 0.50 1 d P . . N2 N 0.59803(11) 0.7386(5) 0.1554(2) 0.0344(10) Uani 1 1 d . . . O2 O 0.58821(8) 0.5849(4) 0.03743(16) 0.0336(8) Uani 1 1 d . . . Cl2 Cl 0.60934(4) 0.39827(15) 0.16900(7) 0.0442(4) Uani 1 1 d . . . F2 F 0.73808(8) 0.9170(4) 0.01339(15) 0.0533(9) Uani 1 1 d . . . C2 C 0.70926(13) 0.7726(6) 0.1131(2) 0.0354(12) Uani 1 1 d . . . H2A H 0.7333 0.8084 0.1156 0.042 Uiso 1 1 calc R . . C3 C 0.68667(13) 0.7974(6) 0.0518(2) 0.0365(12) Uani 1 1 d . . . O3 O 0.61252(11) 0.9803(5) 0.0298(2) 0.0620(12) Uani 1 1 d . . . F3 F 0.6909(4) 1.0484(17) 0.0096(7) 0.075(4) Uani 0.50 1 d P . . F3' F 0.6858(4) 1.0014(15) -0.0184(7) 0.054(3) Uani 0.50 1 d P . . O4 O 0.64444(10) 0.9583(4) 0.1827(2) 0.0532(11) Uani 1 1 d . . . F4 F 0.53716(10) 0.8422(4) 0.23337(19) 0.0765(12) Uani 1 1 d . . . C4 C 0.70313(16) 0.8942(9) -0.0019(3) 0.0583(18) Uani 1 1 d . . . F5 F 0.51789(9) 0.9577(4) 0.14315(18) 0.0640(10) Uani 1 1 d . . . C5 C 0.63274(10) 0.7728(4) -0.02883(16) 0.0671(17) Uani 1 1 d GU . . F6 F 0.56813(9) 1.0172(4) 0.1958(2) 0.0690(11) Uani 1 1 d . . . C6 C 0.60956(11) 0.8917(4) -0.03133(19) 0.0698(19) Uani 1 1 d GU . . C7 C 0.58691(10) 0.9196(4) -0.0913(2) 0.0583(17) Uani 1 1 d GU . . H7A H 0.5711 1.0008 -0.0930 0.070 Uiso 1 1 calc R . . C8 C 0.58745(11) 0.8287(5) -0.14874(19) 0.103(3) Uani 1 1 d GU . . H8A H 0.5720 0.8477 -0.1897 0.124 Uiso 1 1 calc R . . C9 C 0.61063(13) 0.7098(5) -0.14625(17) 0.073(2) Uani 1 1 d GU . . H9A H 0.6110 0.6477 -0.1855 0.088 Uiso 1 1 calc R . . C10 C 0.63327(10) 0.6819(4) -0.08629(19) 0.0563(17) Uani 1 1 d GU . . H10A H 0.6491 0.6007 -0.0846 0.068 Uiso 1 1 calc R . . C11 C 0.71815(13) 0.7015(5) 0.2401(2) 0.0331(11) Uani 1 1 d . . . C12 C 0.70617(13) 0.6153(6) 0.2922(2) 0.0363(12) Uani 1 1 d . . . H12A H 0.6869 0.5492 0.2813 0.044 Uiso 1 1 calc R . . C13 C 0.72204(15) 0.6244(7) 0.3600(3) 0.0478(15) Uani 1 1 d . . . H13A H 0.7138 0.5638 0.3951 0.057 Uiso 1 1 calc R . . C14 C 0.75014(16) 0.7229(7) 0.3764(3) 0.0508(15) Uani 1 1 d . . . H14A H 0.7608 0.7305 0.4230 0.061 Uiso 1 1 calc R . . C15 C 0.76230(16) 0.8089(7) 0.3251(3) 0.0541(16) Uani 1 1 d . . . H15A H 0.7815 0.8756 0.3362 0.065 Uiso 1 1 calc R . . C16 C 0.74665(15) 0.7986(6) 0.2571(3) 0.0457(14) Uani 1 1 d . . . H16A H 0.7553 0.8578 0.2219 0.055 Uiso 1 1 calc R . . C17 C 0.58806(19) 1.0979(7) 0.0184(5) 0.086(3) Uani 1 1 d . . . H17A H 0.5895 1.1602 0.0598 0.129 Uiso 1 1 calc R . . H17B H 0.5634 1.0602 0.0093 0.129 Uiso 1 1 calc R . . H17C H 0.5943 1.1546 -0.0218 0.129 Uiso 1 1 calc R . . C18 C 0.55766(12) 0.6546(6) 0.0244(2) 0.0332(11) Uani 1 1 d . . . C19 C 0.54772(13) 0.7587(6) 0.0687(3) 0.0366(12) Uani 1 1 d . . . H19A H 0.5261 0.8108 0.0559 0.044 Uiso 1 1 calc R . . C20 C 0.56725(13) 0.7948(6) 0.1323(3) 0.0358(12) Uani 1 1 d . . . C21 C 0.54813(15) 0.9044(7) 0.1765(3) 0.0468(14) Uani 1 1 d . . . C22 C 0.61238(14) 0.7678(6) 0.2275(3) 0.0383(12) Uani 1 1 d . . . C23 C 0.63685(14) 0.8786(6) 0.2410(3) 0.0435(14) Uani 1 1 d . . . C24 C 0.65221(15) 0.9057(6) 0.3081(3) 0.0477(15) Uani 1 1 d . . . H24A H 0.6688 0.9832 0.3175 0.057 Uiso 1 1 calc R . . C25 C 0.64240(16) 0.8150(7) 0.3611(3) 0.0560(17) Uani 1 1 d . . . H25A H 0.6524 0.8323 0.4075 0.067 Uiso 1 1 calc R . . C26 C 0.61879(15) 0.7014(7) 0.3483(3) 0.0466(14) Uani 1 1 d . . . H26A H 0.6128 0.6388 0.3847 0.056 Uiso 1 1 calc R . . C27 C 0.60411(15) 0.6816(6) 0.2812(2) 0.0423(13) Uani 1 1 d . . . H27A H 0.5874 0.6043 0.2717 0.051 Uiso 1 1 calc R . . C28 C 0.53540(12) 0.6087(6) -0.0397(3) 0.0337(12) Uani 1 1 d . . . C29 C 0.54312(14) 0.4806(6) -0.0710(3) 0.0423(13) Uani 1 1 d . . . H29A H 0.5627 0.4221 -0.0519 0.051 Uiso 1 1 calc R . . C30 C 0.52223(15) 0.4358(7) -0.1309(3) 0.0512(15) Uani 1 1 d . . . H30A H 0.5278 0.3473 -0.1529 0.061 Uiso 1 1 calc R . . C31 C 0.49384(16) 0.5184(8) -0.1580(3) 0.0583(18) Uani 1 1 d . . . H31A H 0.4793 0.4858 -0.1981 0.070 Uiso 1 1 calc R . . C32 C 0.48621(16) 0.6480(8) -0.1277(3) 0.0569(17) Uani 1 1 d . . . H32A H 0.4667 0.7060 -0.1471 0.068 Uiso 1 1 calc R . . C33 C 0.50713(14) 0.6945(6) -0.0683(3) 0.0469(14) Uani 1 1 d . . . H33A H 0.5021 0.7848 -0.0473 0.056 Uiso 1 1 calc R . . C34 C 0.66870(17) 1.0777(6) 0.1947(4) 0.068(2) Uani 1 1 d . . . H34A H 0.6721 1.1255 0.1504 0.103 Uiso 1 1 calc R . . H34B H 0.6920 1.0423 0.2160 0.103 Uiso 1 1 calc R . . H34C H 0.6586 1.1475 0.2261 0.103 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 0.0282(5) 0.0442(6) 0.0232(5) -0.0016(4) -0.0028(3) 0.0032(4) N1 0.038(3) 0.074(4) 0.029(2) 0.019(2) -0.0098(19) -0.009(2) O1 0.0313(18) 0.040(2) 0.0254(17) 0.0020(15) -0.0029(14) 0.0005(15) Cl1 0.0487(8) 0.0764(11) 0.0362(8) -0.0128(7) -0.0016(6) 0.0208(8) C1 0.025(2) 0.035(3) 0.030(3) -0.003(2) -0.002(2) 0.007(2) F1 0.085(10) 0.131(15) 0.034(6) 0.024(9) -0.011(7) -0.060(8) F1' 0.042(5) 0.085(8) 0.027(4) -0.005(5) 0.008(4) 0.002(4) N2 0.034(2) 0.043(3) 0.025(2) -0.0026(19) -0.0024(17) 0.005(2) O2 0.0292(18) 0.047(2) 0.0234(17) 0.0007(15) -0.0052(13) 0.0045(16) Cl2 0.0492(8) 0.0476(8) 0.0345(7) 0.0042(6) -0.0030(6) -0.0043(6) F2 0.0396(18) 0.077(2) 0.0435(19) 0.0103(17) 0.0029(14) -0.0131(17) C2 0.027(3) 0.047(3) 0.031(3) -0.001(2) -0.002(2) 0.001(2) C3 0.032(3) 0.049(3) 0.027(3) 0.006(2) -0.002(2) -0.001(2) O3 0.060(3) 0.067(3) 0.057(3) 0.014(2) -0.003(2) -0.005(2) F3 0.054(6) 0.088(11) 0.081(10) 0.042(7) -0.001(7) -0.004(7) F3' 0.051(6) 0.049(7) 0.059(8) 0.024(6) -0.003(6) -0.007(5) O4 0.049(2) 0.045(2) 0.066(3) -0.001(2) 0.009(2) -0.0030(19) F4 0.083(3) 0.093(3) 0.059(2) 0.012(2) 0.032(2) 0.040(2) C4 0.038(3) 0.095(6) 0.040(4) 0.026(4) -0.006(3) -0.012(4) F5 0.046(2) 0.071(2) 0.072(2) -0.0102(19) -0.0082(17) 0.0276(18) C5 0.068(4) 0.069(4) 0.064(4) 0.014(3) 0.002(3) -0.015(3) F6 0.053(2) 0.067(2) 0.086(3) -0.037(2) -0.0008(19) 0.0113(19) C6 0.045(4) 0.063(4) 0.101(5) 0.044(4) 0.003(3) -0.010(3) C7 0.053(4) 0.067(4) 0.050(4) 0.031(3) -0.019(3) -0.026(3) C8 0.119(7) 0.092(6) 0.090(5) 0.046(4) -0.033(5) -0.037(5) C9 0.102(6) 0.064(4) 0.049(4) 0.015(3) -0.016(3) -0.042(4) C10 0.086(4) 0.068(4) 0.013(2) 0.001(2) -0.003(3) -0.044(3) C11 0.031(3) 0.038(3) 0.029(3) -0.004(2) -0.007(2) 0.007(2) C12 0.034(3) 0.044(3) 0.030(3) -0.001(2) 0.000(2) 0.005(2) C13 0.053(3) 0.060(4) 0.028(3) 0.006(3) -0.005(3) 0.013(3) C14 0.058(4) 0.060(4) 0.031(3) -0.004(3) -0.015(3) 0.008(3) C15 0.059(4) 0.050(4) 0.047(4) -0.005(3) -0.025(3) -0.001(3) C16 0.047(3) 0.046(3) 0.041(3) 0.002(3) -0.012(3) 0.001(3) C17 0.070(5) 0.043(4) 0.154(8) 0.035(5) 0.054(5) 0.024(3) C18 0.027(3) 0.042(3) 0.030(3) 0.010(2) 0.000(2) -0.004(2) C19 0.030(3) 0.042(3) 0.037(3) 0.004(2) -0.004(2) 0.004(2) C20 0.035(3) 0.039(3) 0.034(3) 0.007(2) 0.003(2) 0.003(2) C21 0.043(3) 0.055(4) 0.042(3) 0.001(3) 0.002(3) 0.013(3) C22 0.040(3) 0.040(3) 0.035(3) -0.003(2) 0.003(2) 0.008(2) C23 0.033(3) 0.034(3) 0.063(4) -0.012(3) 0.004(3) 0.002(2) C24 0.049(3) 0.046(4) 0.047(3) -0.018(3) -0.003(3) 0.008(3) C25 0.061(4) 0.068(4) 0.036(3) -0.019(3) -0.008(3) 0.013(3) C26 0.056(4) 0.053(4) 0.032(3) -0.004(3) 0.008(3) 0.010(3) C27 0.059(4) 0.046(3) 0.023(3) -0.001(2) 0.006(2) 0.017(3) C28 0.026(2) 0.044(3) 0.031(3) 0.007(2) -0.002(2) -0.008(2) C29 0.034(3) 0.055(4) 0.038(3) 0.001(3) -0.001(2) -0.004(3) C30 0.047(3) 0.067(4) 0.039(3) -0.009(3) 0.001(3) -0.009(3) C31 0.048(4) 0.083(5) 0.041(4) 0.005(3) -0.014(3) -0.019(3) C32 0.044(3) 0.071(5) 0.052(4) 0.010(3) -0.018(3) -0.001(3) C33 0.042(3) 0.047(3) 0.048(3) 0.005(3) -0.015(3) -0.003(3) C34 0.051(4) 0.037(3) 0.118(6) 0.003(4) 0.014(4) -0.004(3) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 O2 1.868(3) . ? Ti1 O1 1.876(3) . ? Ti1 N1 2.192(5) . ? Ti1 N2 2.224(4) . ? Ti1 Cl2 2.2896(16) . ? Ti1 Cl1 2.2918(16) . ? N1 C3 1.318(6) . ? N1 C5 1.475(5) . ? O1 C1 1.300(5) . ? C1 C2 1.372(7) . ? C1 C11 1.480(6) . ? F1 F1' 0.770(15) . ? F1 C4 1.221(13) . ? F1 F3' 1.497(19) . ? F1' C4 1.464(15) . ? N2 C20 1.296(6) . ? N2 C22 1.467(6) . ? O2 C18 1.308(6) . ? F2 C4 1.322(6) . ? C2 C3 1.405(6) . ? C2 H2A 0.9500 . ? C3 C4 1.536(7) . ? O3 C17 1.417(7) . ? O3 C6 1.429(5) . ? F3 F3' 0.705(14) . ? F3 C4 1.512(18) . ? F3' C4 1.205(16) . ? O4 C23 1.393(7) . ? O4 C34 1.427(7) . ? F4 C21 1.334(6) . ? F5 C21 1.335(6) . ? C5 C6 1.3900 . ? C5 C10 1.3900 . ? F6 C21 1.310(7) . ? C6 C7 1.3900 . ? C7 C8 1.3900 . ? C7 H7A 0.9500 . ? C8 C9 1.3900 . ? C8 H8A 0.9500 . ? C9 C10 1.3900 . ? C9 H9A 0.9500 . ? C10 H10A 0.9500 . ? C11 C12 1.384(7) . ? C11 C16 1.401(7) . ? C12 C13 1.386(7) . ? C12 H12A 0.9500 . ? C13 C14 1.397(8) . ? C13 H13A 0.9500 . ? C14 C15 1.376(8) . ? C14 H14A 0.9500 . ? C15 C16 1.387(7) . ? C15 H15A 0.9500 . ? C16 H16A 0.9500 . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 C19 1.357(7) . ? C18 C28 1.484(6) . ? C19 C20 1.406(7) . ? C19 H19A 0.9500 . ? C20 C21 1.535(7) . ? C22 C27 1.362(7) . ? C22 C23 1.375(7) . ? C23 C24 1.388(7) . ? C24 C25 1.394(8) . ? C24 H24A 0.9500 . ? C25 C26 1.372(8) . ? C25 H25A 0.9500 . ? C26 C27 1.370(7) . ? C26 H26A 0.9500 . ? C27 H27A 0.9500 . ? C28 C29 1.366(7) . ? C28 C33 1.387(7) . ? C29 C30 1.393(7) . ? C29 H29A 0.9500 . ? C30 C31 1.365(8) . ? C30 H30A 0.9500 . ? C31 C32 1.369(9) . ? C31 H31A 0.9500 . ? C32 C33 1.391(7) . ? C32 H32A 0.9500 . ? C33 H33A 0.9500 . ? C34 H34A 0.9800 . ? C34 H34B 0.9800 . ? C34 H34C 0.9800 . ? 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 O2 Ti1 O1 163.50(16) . . ? O2 Ti1 N1 88.69(15) . . ? O1 Ti1 N1 82.02(15) . . ? O2 Ti1 N2 81.11(14) . . ? O1 Ti1 N2 85.62(14) . . ? N1 Ti1 N2 92.14(18) . . ? O2 Ti1 Cl2 96.05(11) . . ? O1 Ti1 Cl2 93.49(11) . . ? N1 Ti1 Cl2 175.24(12) . . ? N2 Ti1 Cl2 89.09(12) . . ? O2 Ti1 Cl1 96.46(11) . . ? O1 Ti1 Cl1 96.50(11) . . ? N1 Ti1 Cl1 86.23(14) . . ? N2 Ti1 Cl1 177.12(11) . . ? Cl2 Ti1 Cl1 92.72(7) . . ? C3 N1 C5 120.9(4) . . ? C3 N1 Ti1 124.4(3) . . ? C5 N1 Ti1 112.6(3) . . ? C1 O1 Ti1 140.9(3) . . ? O1 C1 C2 120.4(4) . . ? O1 C1 C11 114.8(4) . . ? C2 C1 C11 124.7(4) . . ? F1' F1 C4 92(2) . . ? F1' F1 F3' 142(2) . . ? C4 F1 F3' 51.4(8) . . ? F1 F1' C4 56.4(16) . . ? C20 N2 C22 119.0(4) . . ? C20 N2 Ti1 126.1(3) . . ? C22 N2 Ti1 114.5(3) . . ? C18 O2 Ti1 142.3(3) . . ? C1 C2 C3 123.7(5) . . ? C1 C2 H2A 118.1 . . ? C3 C2 H2A 118.1 . . ? N1 C3 C2 125.3(5) . . ? N1 C3 C4 120.0(4) . . ? C2 C3 C4 114.7(4) . . ? C17 O3 C6 108.0(5) . . ? F3' F3 C4 51(2) . . ? F3 F3' C4 102(3) . . ? F3 F3' F1 151(3) . . ? C4 F3' F1 52.4(8) . . ? C23 O4 C34 116.5(5) . . ? F3' C4 F2 114.9(9) . . ? F1 C4 F2 116.5(8) . . ? F3' C4 F1' 107.4(8) . . ? F1 C4 F3 102.5(10) . . ? F2 C4 F3 96.9(7) . . ? F3' C4 C3 114.6(9) . . ? F1 C4 C3 117.4(8) . . ? F2 C4 C3 112.7(5) . . ? F1' C4 C3 107.9(8) . . ? F3 C4 C3 107.5(8) . . ? C6 C5 C10 120.0 . . ? C6 C5 N1 115.1(3) . . ? C10 C5 N1 124.8(3) . . ? C7 C6 C5 120.0 . . ? C7 C6 O3 125.1(3) . . ? C5 C6 O3 114.8(3) . . ? C6 C7 C8 120.0 . . ? C6 C7 H7A 120.0 . . ? C8 C7 H7A 120.0 . . ? C7 C8 C9 120.0 . . ? C7 C8 H8A 120.0 . . ? C9 C8 H8A 120.0 . . ? C10 C9 C8 120.0 . . ? C10 C9 H9A 120.0 . . ? C8 C9 H9A 120.0 . . ? C9 C10 C5 120.0 . . ? C9 C10 H10A 120.0 . . ? C5 C10 H10A 120.0 . . ? C12 C11 C16 118.8(5) . . ? C12 C11 C1 119.6(5) . . ? C16 C11 C1 121.4(5) . . ? C11 C12 C13 120.8(5) . . ? C11 C12 H12A 119.6 . . ? C13 C12 H12A 119.6 . . ? C12 C13 C14 119.9(5) . . ? C12 C13 H13A 120.1 . . ? C14 C13 H13A 120.1 . . ? C15 C14 C13 119.8(5) . . ? C15 C14 H14A 120.1 . . ? C13 C14 H14A 120.1 . . ? C14 C15 C16 120.2(6) . . ? C14 C15 H15A 119.9 . . ? C16 C15 H15A 119.9 . . ? C15 C16 C11 120.5(5) . . ? C15 C16 H16A 119.8 . . ? C11 C16 H16A 119.8 . . ? O3 C17 H17A 109.5 . . ? O3 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? O3 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? O2 C18 C19 120.5(4) . . ? O2 C18 C28 115.3(4) . . ? C19 C18 C28 124.2(5) . . ? C18 C19 C20 124.6(5) . . ? C18 C19 H19A 117.7 . . ? C20 C19 H19A 117.7 . . ? N2 C20 C19 125.0(5) . . ? N2 C20 C21 120.7(5) . . ? C19 C20 C21 114.3(4) . . ? F6 C21 F4 108.3(5) . . ? F6 C21 F5 106.0(5) . . ? F4 C21 F5 104.2(5) . . ? F6 C21 C20 113.5(5) . . ? F4 C21 C20 111.5(5) . . ? F5 C21 C20 112.7(5) . . ? C27 C22 C23 118.6(5) . . ? C27 C22 N2 121.8(5) . . ? C23 C22 N2 119.5(5) . . ? C22 C23 C24 121.2(6) . . ? C22 C23 O4 114.6(5) . . ? C24 C23 O4 124.2(5) . . ? C23 C24 C25 117.6(6) . . ? C23 C24 H24A 121.2 . . ? C25 C24 H24A 121.2 . . ? C26 C25 C24 122.0(5) . . ? C26 C25 H25A 119.0 . . ? C24 C25 H25A 119.0 . . ? C25 C26 C27 117.6(6) . . ? C25 C26 H26A 121.2 . . ? C27 C26 H26A 121.2 . . ? C22 C27 C26 122.9(6) . . ? C22 C27 H27A 118.6 . . ? C26 C27 H27A 118.6 . . ? C29 C28 C33 119.8(5) . . ? C29 C28 C18 119.3(5) . . ? C33 C28 C18 120.9(5) . . ? C28 C29 C30 119.8(5) . . ? C28 C29 H29A 120.1 . . ? C30 C29 H29A 120.1 . . ? C31 C30 C29 120.4(6) . . ? C31 C30 H30A 119.8 . . ? C29 C30 H30A 119.8 . . ? C30 C31 C32 120.3(6) . . ? C30 C31 H31A 119.9 . . ? C32 C31 H31A 119.9 . . ? C31 C32 C33 119.8(6) . . ? C31 C32 H32A 120.1 . . ? C33 C32 H32A 120.1 . . ? C28 C33 C32 119.9(6) . . ? C28 C33 H33A 120.1 . . ? C32 C33 H33A 120.1 . . ? O4 C34 H34A 109.5 . . ? O4 C34 H34B 109.5 . . ? H34A C34 H34B 109.5 . . ? O4 C34 H34C 109.5 . . ? H34A C34 H34C 109.5 . . ? H34B C34 H34C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 26.05 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 1.637 _refine_diff_density_min -0.906 _refine_diff_density_rms 0.088