# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Jingyu Liu' _publ_contact_author_email LJY@CIAC.JL.CN _publ_section_title ; Synthesis and characterization of the titanium complexes bearing two beta-enaminoketonato ligands with electron withdrawing groups/modified phenyls and their behaviors for ethylene (co-) polymerization ; loop_ _publ_author_name 'Jingyu Liu' 'Yuesheng Li' 'Bai-Xiang Li' 'Xin-Cui Shi' 'Weiping Ye' data_r313(2s) _database_code_depnum_ccdc_archive 'CCDC 763881' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H18 Cl6 F6 N2 O2 Ti' _chemical_formula_weight 837.08 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 Orthorhombic _symmetry_space_group_name_H-M Pbca loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 10.9398(6) _cell_length_b 13.7340(8) _cell_length_c 22.5112(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3382.2(3) _cell_formula_units_Z 4 _cell_measurement_temperature 187(2) _cell_measurement_reflns_used 7201 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 25.35 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.644 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1672 _exptl_absorpt_coefficient_mu 0.795 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.8040 _exptl_absorpt_correction_T_max 0.9428 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 187(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16839 _diffrn_reflns_av_R_equivalents 0.0200 _diffrn_reflns_av_sigmaI/netI 0.0142 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 1.81 _diffrn_reflns_theta_max 25.35 _reflns_number_total 3097 _reflns_number_gt 2723 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; 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^)+(0.0644P)^2^+4.7597P] 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 3097 _refine_ls_number_parameters 223 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0509 _refine_ls_R_factor_gt 0.0451 _refine_ls_wR_factor_ref 0.1251 _refine_ls_wR_factor_gt 0.1188 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.053 _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 0.0000 0.5000 1.0000 0.02716(19) Uani 1 2 d S . . O1 O 0.04519(19) 0.61234(13) 1.04355(8) 0.0335(4) Uani 1 1 d . . . N1 N 0.0565(2) 0.58338(15) 0.92427(9) 0.0264(5) Uani 1 1 d . . . Cl1 Cl 0.19479(7) 0.43958(6) 1.01070(4) 0.0446(2) Uani 1 1 d . . . Cl2 Cl -0.08501(9) 0.87690(7) 1.04810(4) 0.0603(3) Uani 1 1 d . . . Cl3 Cl 0.29352(8) 0.64556(6) 1.11382(4) 0.0507(2) Uani 1 1 d . . . F1 F 0.1435(3) 0.82011(16) 0.87388(9) 0.0891(9) Uani 1 1 d . . . F2 F 0.2185(2) 0.68551(18) 0.83997(9) 0.0662(6) Uani 1 1 d . . . F3 F 0.0309(2) 0.72239(15) 0.82784(8) 0.0602(6) Uani 1 1 d . . . C1 C -0.0653(3) 0.5288(3) 0.83981(13) 0.0430(7) Uani 1 1 d . . . H1 H -0.1315 0.5675 0.8535 0.052 Uiso 1 1 calc R . . C2 C -0.0787(4) 0.4706(3) 0.78968(15) 0.0567(10) Uani 1 1 d . . . H2 H -0.1540 0.4701 0.7687 0.068 Uiso 1 1 calc R . . C3 C 0.0172(4) 0.4137(2) 0.77042(14) 0.0569(10) Uani 1 1 d . . . H3 H 0.0079 0.3742 0.7361 0.068 Uiso 1 1 calc R . . C4 C 0.1250(4) 0.4138(2) 0.80047(14) 0.0539(9) Uani 1 1 d . . . H4 H 0.1903 0.3737 0.7872 0.065 Uiso 1 1 calc R . . C5 C 0.1407(3) 0.4722(2) 0.85050(12) 0.0417(7) Uani 1 1 d . . . H5 H 0.2162 0.4722 0.8713 0.050 Uiso 1 1 calc R . . C6 C 0.0450(3) 0.52996(18) 0.86940(11) 0.0285(6) Uani 1 1 d . . . C7 C 0.0921(3) 0.6745(2) 0.92533(12) 0.0361(6) Uani 1 1 d . . . C8 C 0.1058(3) 0.7322(2) 0.97698(13) 0.0434(8) Uani 1 1 d . . . H8 H 0.1316 0.7978 0.9723 0.052 Uiso 1 1 calc R . . C9 C 0.0841(2) 0.69901(19) 1.03292(12) 0.0299(6) Uani 1 1 d . . . C10 C 0.1009(2) 0.7613(2) 1.08701(11) 0.0309(6) Uani 1 1 d . . . C11 C 0.0259(3) 0.8409(2) 1.09894(13) 0.0397(7) Uani 1 1 d . . . C12 C 0.0361(3) 0.8932(2) 1.15124(14) 0.0480(8) Uani 1 1 d . . . H12 H -0.0162 0.9471 1.1586 0.058 Uiso 1 1 calc R . . C13 C 0.1233(3) 0.8663(2) 1.19276(14) 0.0478(8) Uani 1 1 d . . . H13 H 0.1291 0.9008 1.2292 0.057 Uiso 1 1 calc R . . C14 C 0.2021(3) 0.7895(2) 1.18154(13) 0.0427(7) Uani 1 1 d . . . H14 H 0.2633 0.7722 1.2096 0.051 Uiso 1 1 calc R . . C15 C 0.1904(3) 0.7384(2) 1.12882(12) 0.0353(6) Uani 1 1 d . . . C16 C 0.1212(4) 0.7270(2) 0.86605(14) 0.0475(8) 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 0.0331(4) 0.0209(3) 0.0275(4) 0.0009(2) 0.0012(3) -0.0016(3) O1 0.0527(12) 0.0257(9) 0.0222(9) -0.0021(7) 0.0007(8) -0.0074(9) N1 0.0330(11) 0.0264(11) 0.0198(10) -0.0010(8) 0.0010(9) -0.0021(9) Cl1 0.0375(4) 0.0502(5) 0.0461(4) 0.0047(3) 0.0028(3) 0.0109(3) Cl2 0.0647(6) 0.0713(6) 0.0450(5) -0.0121(4) -0.0121(4) 0.0214(5) Cl3 0.0493(5) 0.0514(5) 0.0516(5) -0.0092(4) -0.0099(4) 0.0060(4) F1 0.178(3) 0.0492(12) 0.0402(11) -0.0005(9) 0.0217(14) -0.0506(16) F2 0.0624(13) 0.0954(17) 0.0407(11) 0.0145(11) 0.0168(10) -0.0127(12) F3 0.0879(15) 0.0545(12) 0.0381(10) 0.0171(9) -0.0013(10) 0.0026(11) C1 0.0440(17) 0.0563(19) 0.0286(15) -0.0032(14) -0.0015(13) -0.0015(15) C2 0.059(2) 0.078(3) 0.0329(17) -0.0038(17) -0.0097(15) -0.024(2) C3 0.100(3) 0.0431(18) 0.0278(16) -0.0090(14) 0.0061(18) -0.0222(19) C4 0.092(3) 0.0386(17) 0.0311(16) -0.0042(13) 0.0127(18) 0.0119(18) C5 0.0553(19) 0.0424(16) 0.0273(14) -0.0007(12) 0.0021(13) 0.0115(14) C6 0.0405(15) 0.0243(12) 0.0207(12) 0.0013(10) 0.0028(11) -0.0040(11) C7 0.0480(17) 0.0349(14) 0.0254(14) 0.0000(11) 0.0051(12) -0.0094(13) C8 0.069(2) 0.0317(15) 0.0300(14) -0.0031(12) 0.0079(14) -0.0212(14) C9 0.0332(14) 0.0302(13) 0.0263(13) -0.0044(11) 0.0006(11) -0.0058(11) C10 0.0382(15) 0.0309(13) 0.0235(12) -0.0022(11) 0.0040(11) -0.0105(11) C11 0.0464(17) 0.0419(16) 0.0308(14) -0.0046(12) -0.0012(13) -0.0029(13) C12 0.064(2) 0.0432(18) 0.0372(17) -0.0127(14) 0.0021(15) 0.0056(16) C13 0.068(2) 0.0461(17) 0.0289(15) -0.0123(13) 0.0015(15) -0.0100(16) C14 0.0568(19) 0.0433(17) 0.0280(14) -0.0015(13) -0.0070(13) -0.0125(14) C15 0.0435(16) 0.0316(14) 0.0309(14) -0.0021(12) 0.0017(12) -0.0078(12) C16 0.070(2) 0.0393(17) 0.0335(16) -0.0072(13) 0.0154(16) -0.0192(16) _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 1.8937(18) 5_567 ? Ti1 O1 1.8937(18) . ? Ti1 N1 2.145(2) . ? Ti1 N1 2.145(2) 5_567 ? Ti1 Cl1 2.2995(7) . ? Ti1 Cl1 2.2995(7) 5_567 ? O1 C9 1.287(3) . ? N1 C7 1.311(4) . ? N1 C6 1.442(3) . ? Cl2 C11 1.740(3) . ? Cl3 C15 1.736(3) . ? F1 C16 1.314(4) . ? F2 C16 1.342(4) . ? F3 C16 1.311(4) . ? C1 C6 1.379(4) . ? C1 C2 1.391(5) . ? C1 H1 0.9500 . ? C2 C3 1.379(6) . ? C2 H2 0.9500 . ? C3 C4 1.360(6) . ? C3 H3 0.9500 . ? C4 C5 1.393(4) . ? C4 H4 0.9500 . ? C5 C6 1.381(4) . ? C5 H5 0.9500 . ? C7 C8 1.415(4) . ? C7 C16 1.550(4) . ? C8 C9 1.360(4) . ? C8 H8 0.9500 . ? C9 C10 1.500(4) . ? C10 C11 1.393(4) . ? C10 C15 1.394(4) . ? C11 C12 1.384(4) . ? C12 C13 1.386(5) . ? C12 H12 0.9500 . ? C13 C14 1.385(5) . ? C13 H13 0.9500 . ? C14 C15 1.384(4) . ? C14 H14 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 O1 180.000(1) 5_567 . ? O1 Ti1 N1 95.66(8) 5_567 . ? O1 Ti1 N1 84.34(8) . . ? O1 Ti1 N1 84.34(8) 5_567 5_567 ? O1 Ti1 N1 95.66(8) . 5_567 ? N1 Ti1 N1 180.000(1) . 5_567 ? O1 Ti1 Cl1 90.12(7) 5_567 . ? O1 Ti1 Cl1 89.88(7) . . ? N1 Ti1 Cl1 90.51(6) . . ? N1 Ti1 Cl1 89.49(6) 5_567 . ? O1 Ti1 Cl1 89.88(7) 5_567 5_567 ? O1 Ti1 Cl1 90.12(7) . 5_567 ? N1 Ti1 Cl1 89.49(6) . 5_567 ? N1 Ti1 Cl1 90.51(6) 5_567 5_567 ? Cl1 Ti1 Cl1 180.0 . 5_567 ? C9 O1 Ti1 138.06(17) . . ? C7 N1 C6 121.8(2) . . ? C7 N1 Ti1 125.51(17) . . ? C6 N1 Ti1 112.59(15) . . ? C6 C1 C2 119.4(3) . . ? C6 C1 H1 120.3 . . ? C2 C1 H1 120.3 . . ? C3 C2 C1 120.1(3) . . ? C3 C2 H2 120.0 . . ? C1 C2 H2 120.0 . . ? C4 C3 C2 120.2(3) . . ? C4 C3 H3 119.9 . . ? C2 C3 H3 119.9 . . ? C3 C4 C5 120.7(3) . . ? C3 C4 H4 119.7 . . ? C5 C4 H4 119.7 . . ? C6 C5 C4 119.1(3) . . ? C6 C5 H5 120.5 . . ? C4 C5 H5 120.5 . . ? C1 C6 C5 120.6(3) . . ? C1 C6 N1 119.7(3) . . ? C5 C6 N1 119.4(3) . . ? N1 C7 C8 125.5(2) . . ? N1 C7 C16 119.3(2) . . ? C8 C7 C16 115.2(2) . . ? C9 C8 C7 123.7(3) . . ? C9 C8 H8 118.1 . . ? C7 C8 H8 118.1 . . ? O1 C9 C8 122.7(2) . . ? O1 C9 C10 114.7(2) . . ? C8 C9 C10 122.6(2) . . ? C11 C10 C15 117.4(2) . . ? C11 C10 C9 122.1(3) . . ? C15 C10 C9 120.4(2) . . ? C12 C11 C10 121.6(3) . . ? C12 C11 Cl2 117.9(3) . . ? C10 C11 Cl2 120.5(2) . . ? C11 C12 C13 119.4(3) . . ? C11 C12 H12 120.3 . . ? C13 C12 H12 120.3 . . ? C14 C13 C12 120.6(3) . . ? C14 C13 H13 119.7 . . ? C12 C13 H13 119.7 . . ? C15 C14 C13 119.0(3) . . ? C15 C14 H14 120.5 . . ? C13 C14 H14 120.5 . . ? C14 C15 C10 122.0(3) . . ? C14 C15 Cl3 118.6(2) . . ? C10 C15 Cl3 119.4(2) . . ? F3 C16 F1 105.9(3) . . ? F3 C16 F2 106.9(2) . . ? F1 C16 F2 108.9(3) . . ? F3 C16 C7 112.8(3) . . ? F1 C16 C7 112.1(2) . . ? F2 C16 C7 110.0(3) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.35 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.154 _refine_diff_density_min -0.706 _refine_diff_density_rms 0.074 # End of 2s # Attachment 'cif.txt' data_r459 _database_code_depnum_ccdc_archive 'CCDC 763882' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C34 H20 Cl2 F12 N2 O2 Ti' _chemical_formula_weight 835.32 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/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y, -z+1/2' '-x, -y, -z' 'x-1/2, -y, z-1/2' _cell_length_a 11.8417(9) _cell_length_b 8.2093(6) _cell_length_c 17.3695(12) _cell_angle_alpha 90.00 _cell_angle_beta 93.1170(10) _cell_angle_gamma 90.00 _cell_volume 1686.0(2) _cell_formula_units_Z 2 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used 3461 _cell_measurement_theta_min 2.35 _cell_measurement_theta_max 25.59 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.645 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 836 _exptl_absorpt_coefficient_mu 0.515 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.8209 _exptl_absorpt_correction_T_max 0.9712 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8793 _diffrn_reflns_av_R_equivalents 0.0200 _diffrn_reflns_av_sigmaI/netI 0.0237 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.03 _diffrn_reflns_theta_max 25.68 _reflns_number_total 3185 _reflns_number_gt 2773 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; 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^)+(0.0578P)^2^+1.6892P] 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 3185 _refine_ls_number_parameters 240 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0505 _refine_ls_R_factor_gt 0.0444 _refine_ls_wR_factor_ref 0.1181 _refine_ls_wR_factor_gt 0.1130 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _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 0.2500 0.36177(7) 0.2500 0.02588(18) Uani 1 2 d S . . N1 N 0.37470(16) 0.1706(2) 0.22682(11) 0.0260(4) Uani 1 1 d . . . O1 O 0.31395(13) 0.3351(2) 0.35062(9) 0.0286(4) Uani 1 1 d . . . Cl1 Cl 0.12174(6) 0.54595(9) 0.28925(4) 0.0425(2) Uani 1 1 d . . . F1 F 0.63926(12) -0.0028(2) 0.29835(9) 0.0440(4) Uani 1 1 d . . . F2 F 0.60564(14) 0.0975(2) 0.18630(10) 0.0550(5) Uani 1 1 d . . . F3 F 0.52253(14) -0.1215(2) 0.22019(11) 0.0508(5) Uani 1 1 d . . . F4 F 0.1512(2) 0.5677(4) 0.56437(12) 0.0940(9) Uani 1 1 d . . . F5 F 0.2670(2) 0.6550(4) 0.6519(2) 0.1254(13) Uani 1 1 d . . . F6 F 0.1799(2) 0.4388(4) 0.66635(15) 0.0971(9) Uani 1 1 d . . . C1 C 0.3074(2) -0.0432(4) 0.13797(16) 0.0371(6) Uani 1 1 d . . . H1 H 0.2794 -0.1009 0.1804 0.045 Uiso 1 1 calc R . . C2 C 0.2917(2) -0.1048(4) 0.06378(17) 0.0495(8) Uani 1 1 d . . . H2 H 0.2545 -0.2064 0.0556 0.059 Uiso 1 1 calc R . . C3 C 0.3295(3) -0.0201(5) 0.00201(17) 0.0548(9) Uani 1 1 d . . . H3 H 0.3171 -0.0619 -0.0487 0.066 Uiso 1 1 calc R . . C4 C 0.3856(3) 0.1257(5) 0.01386(16) 0.0516(9) Uani 1 1 d . . . H4 H 0.4122 0.1837 -0.0289 0.062 Uiso 1 1 calc R . . C5 C 0.4037(2) 0.1886(4) 0.08784(15) 0.0408(7) Uani 1 1 d . . . H5 H 0.4426 0.2888 0.0959 0.049 Uiso 1 1 calc R . . C6 C 0.3639(2) 0.1028(3) 0.14974(14) 0.0310(6) Uani 1 1 d . . . C7 C 0.46089(19) 0.1290(3) 0.27384(13) 0.0263(5) Uani 1 1 d . . . C8 C 0.4756(2) 0.1752(3) 0.35233(14) 0.0300(5) Uani 1 1 d . . . H8 H 0.5412 0.1378 0.3810 0.036 Uiso 1 1 calc R . . C9 C 0.40085(19) 0.2704(3) 0.38890(13) 0.0255(5) Uani 1 1 d . . . C10 C 0.40912(19) 0.3077(3) 0.47248(13) 0.0267(5) Uani 1 1 d . . . C11 C 0.3235(2) 0.3992(3) 0.50307(14) 0.0293(5) Uani 1 1 d . . . H11 H 0.2628 0.4391 0.4703 0.035 Uiso 1 1 calc R . . C12 C 0.3268(2) 0.4323(3) 0.58168(14) 0.0321(6) Uani 1 1 d . . . C13 C 0.4163(2) 0.3782(3) 0.63008(14) 0.0362(6) Uani 1 1 d . . . H13 H 0.4185 0.4020 0.6837 0.043 Uiso 1 1 calc R . . C14 C 0.5018(2) 0.2897(4) 0.59935(14) 0.0392(6) Uani 1 1 d . . . H14 H 0.5640 0.2541 0.6319 0.047 Uiso 1 1 calc R . . C15 C 0.4983(2) 0.2518(3) 0.52127(14) 0.0341(6) Uani 1 1 d . . . H15 H 0.5566 0.1878 0.5011 0.041 Uiso 1 1 calc R . . C16 C 0.5575(2) 0.0238(3) 0.24413(14) 0.0324(6) Uani 1 1 d . . . C17 C 0.2327(3) 0.5252(4) 0.61515(16) 0.0449(7) 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 0.0268(3) 0.0286(3) 0.0215(3) 0.000 -0.0053(2) 0.000 N1 0.0248(10) 0.0312(11) 0.0220(10) -0.0005(8) 0.0006(8) -0.0033(8) O1 0.0281(8) 0.0358(9) 0.0211(8) -0.0005(7) -0.0041(7) 0.0037(7) Cl1 0.0478(4) 0.0405(4) 0.0380(4) -0.0064(3) -0.0081(3) 0.0171(3) F1 0.0304(8) 0.0589(11) 0.0420(9) -0.0073(8) -0.0060(7) 0.0127(7) F2 0.0402(9) 0.0767(13) 0.0502(10) 0.0196(9) 0.0220(8) 0.0139(9) F3 0.0433(9) 0.0401(10) 0.0678(12) -0.0186(8) -0.0081(8) 0.0071(7) F4 0.0785(15) 0.149(2) 0.0537(13) -0.0120(14) -0.0017(11) 0.0682(16) F5 0.0753(16) 0.107(2) 0.195(3) -0.105(2) 0.0200(18) 0.0046(15) F6 0.0827(16) 0.128(2) 0.0857(17) 0.0260(16) 0.0487(14) 0.0286(16) C1 0.0303(13) 0.0463(16) 0.0346(14) -0.0100(12) 0.0011(11) -0.0015(11) C2 0.0367(15) 0.067(2) 0.0443(17) -0.0256(16) -0.0035(13) 0.0024(14) C3 0.0452(17) 0.087(3) 0.0313(15) -0.0206(16) -0.0042(13) 0.0184(17) C4 0.0493(18) 0.080(2) 0.0269(14) 0.0049(15) 0.0102(13) 0.0249(17) C5 0.0402(15) 0.0525(17) 0.0304(14) 0.0017(13) 0.0095(11) 0.0081(13) C6 0.0253(12) 0.0428(15) 0.0247(12) -0.0036(11) -0.0003(9) 0.0070(11) C7 0.0251(11) 0.0279(12) 0.0258(12) 0.0028(10) 0.0013(9) -0.0032(9) C8 0.0258(12) 0.0378(14) 0.0258(12) 0.0009(10) -0.0044(9) 0.0013(10) C9 0.0238(11) 0.0279(12) 0.0243(12) 0.0023(10) -0.0022(9) -0.0051(9) C10 0.0272(12) 0.0299(12) 0.0229(12) 0.0022(10) -0.0012(9) -0.0040(10) C11 0.0303(12) 0.0327(13) 0.0243(12) 0.0029(10) -0.0030(10) -0.0005(10) C12 0.0369(14) 0.0344(14) 0.0250(12) 0.0001(10) 0.0009(10) -0.0026(11) C13 0.0436(15) 0.0440(15) 0.0207(12) 0.0011(11) -0.0007(11) -0.0032(12) C14 0.0382(14) 0.0534(18) 0.0247(13) 0.0035(12) -0.0094(11) 0.0047(13) C15 0.0306(13) 0.0446(15) 0.0267(13) -0.0001(11) -0.0032(10) 0.0052(11) C16 0.0275(12) 0.0395(15) 0.0300(13) -0.0004(11) 0.0000(10) 0.0011(11) C17 0.0482(17) 0.0566(19) 0.0300(14) -0.0039(13) 0.0027(13) 0.0072(14) _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 1.8793(15) 2 ? Ti1 O1 1.8793(15) . ? Ti1 N1 2.207(2) 2 ? Ti1 N1 2.207(2) . ? Ti1 Cl1 2.2738(8) 2 ? Ti1 Cl1 2.2738(8) . ? N1 C7 1.317(3) . ? N1 C6 1.449(3) . ? O1 C9 1.307(3) . ? F1 C16 1.331(3) . ? F2 C16 1.327(3) . ? F3 C16 1.322(3) . ? F4 C17 1.319(3) . ? F5 C17 1.296(4) . ? F6 C17 1.322(4) . ? C1 C6 1.383(4) . ? C1 C2 1.387(4) . ? C1 H1 0.9500 . ? C2 C3 1.374(5) . ? C2 H2 0.9500 . ? C3 C4 1.379(5) . ? C3 H3 0.9500 . ? C4 C5 1.391(4) . ? C4 H4 0.9500 . ? C5 C6 1.389(4) . ? C5 H5 0.9500 . ? C7 C8 1.417(3) . ? C7 C16 1.545(3) . ? C8 C9 1.364(3) . ? C8 H8 0.9500 . ? C9 C10 1.482(3) . ? C10 C11 1.391(3) . ? C10 C15 1.395(3) . ? C11 C12 1.391(3) . ? C11 H11 0.9500 . ? C12 C13 1.389(4) . ? C12 C17 1.494(4) . ? C13 C14 1.377(4) . ? C13 H13 0.9500 . ? C14 C15 1.390(3) . ? C14 H14 0.9500 . ? C15 H15 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 O1 166.63(11) 2 . ? O1 Ti1 N1 81.20(7) 2 2 ? O1 Ti1 N1 89.27(7) . 2 ? O1 Ti1 N1 89.27(7) 2 . ? O1 Ti1 N1 81.20(7) . . ? N1 Ti1 N1 89.34(10) 2 . ? O1 Ti1 Cl1 92.32(5) 2 2 ? O1 Ti1 Cl1 96.57(5) . 2 ? N1 Ti1 Cl1 172.77(5) 2 2 ? N1 Ti1 Cl1 87.35(5) . 2 ? O1 Ti1 Cl1 96.57(5) 2 . ? O1 Ti1 Cl1 92.32(5) . . ? N1 Ti1 Cl1 87.35(5) 2 . ? N1 Ti1 Cl1 172.77(5) . . ? Cl1 Ti1 Cl1 96.64(5) 2 . ? C7 N1 C6 120.0(2) . . ? C7 N1 Ti1 125.08(16) . . ? C6 N1 Ti1 114.54(14) . . ? C9 O1 Ti1 141.86(15) . . ? C6 C1 C2 119.5(3) . . ? C6 C1 H1 120.2 . . ? C2 C1 H1 120.2 . . ? C3 C2 C1 120.5(3) . . ? C3 C2 H2 119.7 . . ? C1 C2 H2 119.7 . . ? C2 C3 C4 119.8(3) . . ? C2 C3 H3 120.1 . . ? C4 C3 H3 120.1 . . ? C3 C4 C5 120.6(3) . . ? C3 C4 H4 119.7 . . ? C5 C4 H4 119.7 . . ? C6 C5 C4 119.0(3) . . ? C6 C5 H5 120.5 . . ? C4 C5 H5 120.5 . . ? C1 C6 C5 120.5(2) . . ? C1 C6 N1 119.2(2) . . ? C5 C6 N1 120.2(2) . . ? N1 C7 C8 125.3(2) . . ? N1 C7 C16 120.1(2) . . ? C8 C7 C16 114.6(2) . . ? C9 C8 C7 123.5(2) . . ? C9 C8 H8 118.2 . . ? C7 C8 H8 118.2 . . ? O1 C9 C8 120.6(2) . . ? O1 C9 C10 115.0(2) . . ? C8 C9 C10 124.4(2) . . ? C11 C10 C15 119.3(2) . . ? C11 C10 C9 118.4(2) . . ? C15 C10 C9 122.3(2) . . ? C12 C11 C10 119.9(2) . . ? C12 C11 H11 120.1 . . ? C10 C11 H11 120.1 . . ? C13 C12 C11 120.8(2) . . ? C13 C12 C17 119.2(2) . . ? C11 C12 C17 120.0(2) . . ? C14 C13 C12 119.1(2) . . ? C14 C13 H13 120.4 . . ? C12 C13 H13 120.4 . . ? C13 C14 C15 120.9(2) . . ? C13 C14 H14 119.6 . . ? C15 C14 H14 119.6 . . ? C14 C15 C10 120.0(2) . . ? C14 C15 H15 120.0 . . ? C10 C15 H15 120.0 . . ? F3 C16 F2 108.2(2) . . ? F3 C16 F1 106.1(2) . . ? F2 C16 F1 106.5(2) . . ? F3 C16 C7 112.6(2) . . ? F2 C16 C7 110.8(2) . . ? F1 C16 C7 112.3(2) . . ? F5 C17 F4 108.1(3) . . ? F5 C17 F6 104.9(3) . . ? F4 C17 F6 103.6(3) . . ? F5 C17 C12 113.0(3) . . ? F4 C17 C12 114.2(2) . . ? F6 C17 C12 112.2(3) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.68 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.835 _refine_diff_density_min -0.367 _refine_diff_density_rms 0.061 data_r460(2m) _database_code_depnum_ccdc_archive 'CCDC 763883' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H18 Cl2 F10 N2 O2 Ti' _chemical_formula_weight 771.28 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 18.949(7) _cell_length_b 8.403(3) _cell_length_c 20.493(7) _cell_angle_alpha 90.00 _cell_angle_beta 100.738(5) _cell_angle_gamma 90.00 _cell_volume 3206(2) _cell_formula_units_Z 4 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used 3437 _cell_measurement_theta_min 2.66 _cell_measurement_theta_max 23.23 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.31 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.598 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1544 _exptl_absorpt_coefficient_mu 0.526 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8531 _exptl_absorpt_correction_T_max 0.9183 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _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 APEX CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15682 _diffrn_reflns_av_R_equivalents 0.0508 _diffrn_reflns_av_sigmaI/netI 0.0635 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 1.62 _diffrn_reflns_theta_max 25.03 _reflns_number_total 5619 _reflns_number_gt 4088 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; 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^)+(0.0556P)^2^+37.6676P] 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 5619 _refine_ls_number_parameters 435 _refine_ls_number_restraints 22 _refine_ls_R_factor_all 0.1562 _refine_ls_R_factor_gt 0.1248 _refine_ls_wR_factor_ref 0.2918 _refine_ls_wR_factor_gt 0.2767 _refine_ls_goodness_of_fit_ref 1.165 _refine_ls_restrained_S_all 1.170 _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 1.00955(8) 0.0484(2) 0.24677(7) 0.0345(4) Uani 1 1 d . . . Cl1 Cl 1.11023(16) -0.0866(3) 0.28887(13) 0.0574(8) Uani 1 1 d . . . Cl2 Cl 0.9371(2) -0.1670(4) 0.21517(14) 0.0479(14) Uani 0.854(13) 1 d P . . Cl2' Cl 0.9098(13) -0.080(4) 0.2154(10) 0.061(8) Uiso 0.146(13) 1 d P . . F1 F 0.8510(4) 0.4094(9) 0.0453(3) 0.081(2) Uani 1 1 d . . . F2 F 0.7965(3) 0.3412(11) 0.1230(4) 0.091(3) Uani 1 1 d . . . F3 F 0.8716(4) 0.5319(8) 0.1373(3) 0.073(2) Uani 1 1 d . . . F4 F 1.0297(4) 0.2904(9) -0.0205(3) 0.080(2) Uani 1 1 d . . . F5 F 1.2182(6) -0.0309(12) -0.0535(4) 0.129(4) Uani 1 1 d . . . F6 F 1.1755(5) 0.4825(13) 0.3469(4) 0.125(4) Uani 1 1 d U . . F7 F 1.0797(7) 0.6015(9) 0.3566(4) 0.129(4) Uani 1 1 d . . . F8 F 1.1391(4) 0.4649(8) 0.4368(3) 0.0694(19) Uani 1 1 d . . . F9 F 0.9552(4) 0.3078(8) 0.4987(3) 0.083(2) Uani 1 1 d . . . F10 F 0.8061(3) -0.0976(8) 0.5492(3) 0.0656(18) Uani 1 1 d . . . O1 O 1.0387(3) 0.0733(7) 0.1650(3) 0.0375(15) Uani 1 1 d . . . O2 O 0.9753(3) 0.0657(8) 0.3262(3) 0.0395(15) Uani 1 1 d . . . N1 N 0.9280(4) 0.2200(9) 0.1989(3) 0.0353(17) Uani 1 1 d . . . N2 N 1.0685(4) 0.2667(8) 0.2865(3) 0.0319(16) Uani 1 1 d . . . C1 C 0.8908(7) 0.4050(17) 0.2758(6) 0.074(3) Uani 1 1 d U . . H1 H 0.9273 0.4776 0.2693 0.088 Uiso 1 1 calc R . . C2 C 0.8461(7) 0.4370(18) 0.3216(6) 0.074(3) Uani 1 1 d . . . H2 H 0.8539 0.5313 0.3475 0.088 Uiso 1 1 calc R . . C3 C 0.7937(8) 0.341(3) 0.3297(7) 0.100(6) Uani 1 1 d . . . H3 H 0.7634 0.3693 0.3599 0.120 Uiso 1 1 calc R . . C4 C 0.7816(7) 0.197(3) 0.2948(8) 0.113(7) Uani 1 1 d . . . H4 H 0.7445 0.1264 0.3016 0.136 Uiso 1 1 calc R . . C5 C 0.8255(6) 0.1623(19) 0.2502(6) 0.077(4) Uani 1 1 d . . . H5 H 0.8185 0.0662 0.2255 0.092 Uiso 1 1 calc R . . C6 C 0.8803(5) 0.2662(14) 0.2409(5) 0.049(2) Uani 1 1 d U . . C7 C 0.9210(5) 0.2732(11) 0.1385(5) 0.040(2) Uani 1 1 d . . . C8 C 0.9671(5) 0.2386(12) 0.0926(5) 0.043(2) Uani 1 1 d . . . H8 H 0.9567 0.2863 0.0499 0.052 Uiso 1 1 calc R . . C9 C 1.0239(5) 0.1428(11) 0.1068(4) 0.037(2) Uani 1 1 d . . . C10 C 1.0748(5) 0.1013(11) 0.0631(4) 0.040(2) Uani 1 1 d . . . C11 C 1.1249(6) -0.0162(12) 0.0822(5) 0.050(3) Uani 1 1 d . . . H11 H 1.1253 -0.0688 0.1233 0.060 Uiso 1 1 calc R . . C12 C 1.1746(7) -0.0611(13) 0.0443(5) 0.065(3) Uani 1 1 d . . . H12 H 1.2090 -0.1417 0.0591 0.078 Uiso 1 1 calc R . . C13 C 1.1728(8) 0.0145(16) -0.0158(6) 0.074(4) Uani 1 1 d . . . C14 C 1.1245(7) 0.1337(15) -0.0370(5) 0.068(3) Uani 1 1 d . . . H14 H 1.1245 0.1867 -0.0779 0.082 Uiso 1 1 calc R . . C15 C 1.0766(6) 0.1742(13) 0.0019(5) 0.051(3) Uani 1 1 d . . . C16 C 0.8600(6) 0.3882(15) 0.1111(5) 0.057(3) Uani 1 1 d . . . C17 C 1.0756(7) 0.4807(14) 0.2075(5) 0.063(3) Uani 1 1 d . . . H17 H 1.0326 0.5238 0.2178 0.075 Uiso 1 1 calc R . . C18 C 1.1083(8) 0.5549(18) 0.1584(6) 0.087(4) Uani 1 1 d U . . H18 H 1.0893 0.6502 0.1370 0.104 Uiso 1 1 calc R . . C19 C 1.1691(8) 0.483(2) 0.1427(7) 0.094(4) Uani 1 1 d U . . H19 H 1.1909 0.5271 0.1086 0.113 Uiso 1 1 calc R . . C20 C 1.1969(8) 0.355(2) 0.1741(7) 0.094(4) Uani 1 1 d U . . H20 H 1.2396 0.3115 0.1633 0.113 Uiso 1 1 calc R . . C21 C 1.1654(5) 0.2792(15) 0.2234(6) 0.061(3) Uani 1 1 d . . . H21 H 1.1850 0.1842 0.2446 0.073 Uiso 1 1 calc R . . C22 C 1.1050(5) 0.3499(13) 0.2395(5) 0.044(2) Uani 1 1 d . . . C23 C 1.0722(5) 0.3209(11) 0.3468(4) 0.039(2) Uani 1 1 d . . . C24 C 1.0306(5) 0.2656(11) 0.3939(4) 0.039(2) Uani 1 1 d . . . H24 H 1.0366 0.3172 0.4358 0.047 Uiso 1 1 calc R . . C25 C 0.9831(4) 0.1435(12) 0.3817(4) 0.036(2) Uani 1 1 d . . . C26 C 0.9370(5) 0.0852(12) 0.4279(4) 0.040(2) Uani 1 1 d . . . C27 C 0.9247(6) 0.1624(13) 0.4834(5) 0.054(3) Uani 1 1 d . . . C28 C 0.8804(6) 0.1048(15) 0.5251(5) 0.060(3) Uani 1 1 d . . . H28 H 0.8728 0.1622 0.5631 0.071 Uiso 1 1 calc R . . C29 C 0.8484(5) -0.0376(15) 0.5084(5) 0.049(3) Uani 1 1 d . . . C30 C 0.8592(5) -0.1250(13) 0.4553(5) 0.051(3) Uani 1 1 d . . . H30 H 0.8376 -0.2266 0.4464 0.061 Uiso 1 1 calc R . . C31 C 0.9025(5) -0.0616(14) 0.4148(5) 0.050(3) Uani 1 1 d . . . H31 H 0.9092 -0.1198 0.3766 0.060 Uiso 1 1 calc R . . C32 C 1.1193(7) 0.4672(16) 0.3705(6) 0.069(4) 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 0.0392(9) 0.0390(9) 0.0266(8) 0.0089(7) 0.0096(6) -0.0063(8) Cl1 0.0750(18) 0.0542(16) 0.0446(14) 0.0202(12) 0.0154(13) 0.0223(14) Cl2 0.065(2) 0.035(2) 0.0461(17) -0.0030(13) 0.0161(14) -0.0209(18) F1 0.088(5) 0.095(6) 0.051(4) 0.017(4) -0.009(3) 0.040(4) F2 0.032(3) 0.130(7) 0.105(6) 0.034(5) -0.001(3) 0.015(4) F3 0.093(5) 0.061(4) 0.064(4) 0.014(4) 0.007(4) 0.034(4) F4 0.093(5) 0.094(5) 0.056(4) 0.043(4) 0.025(4) 0.019(4) F5 0.199(10) 0.138(8) 0.070(5) 0.026(5) 0.079(6) 0.068(8) F6 0.131(7) 0.180(9) 0.077(5) -0.057(5) 0.051(5) -0.118(7) F7 0.246(13) 0.043(5) 0.087(6) 0.009(4) -0.001(7) -0.020(6) F8 0.091(5) 0.074(4) 0.043(3) -0.011(3) 0.013(3) -0.036(4) F9 0.130(6) 0.066(5) 0.074(5) -0.019(4) 0.073(5) -0.014(4) F10 0.056(4) 0.096(5) 0.055(4) 0.010(3) 0.037(3) -0.009(3) O1 0.047(4) 0.040(4) 0.026(3) 0.015(3) 0.007(3) -0.005(3) O2 0.038(3) 0.048(4) 0.035(3) 0.013(3) 0.014(3) -0.007(3) N1 0.034(4) 0.036(4) 0.036(4) 0.009(3) 0.008(3) -0.010(3) N2 0.028(4) 0.032(4) 0.039(4) 0.015(3) 0.013(3) 0.004(3) C1 0.075(6) 0.091(6) 0.057(5) -0.001(5) 0.020(4) 0.042(5) C2 0.075(6) 0.091(6) 0.057(5) -0.001(5) 0.020(4) 0.042(5) C3 0.072(10) 0.167(18) 0.075(10) 0.036(11) 0.046(8) 0.059(12) C4 0.047(8) 0.19(2) 0.109(13) 0.053(14) 0.042(8) 0.005(11) C5 0.043(6) 0.107(11) 0.085(9) 0.019(8) 0.028(6) 0.001(7) C6 0.033(5) 0.066(6) 0.050(6) 0.015(5) 0.012(4) 0.006(5) C7 0.034(5) 0.039(5) 0.045(5) 0.007(4) 0.002(4) -0.004(4) C8 0.048(6) 0.046(6) 0.036(5) 0.010(4) 0.008(4) -0.006(5) C9 0.036(5) 0.041(5) 0.033(5) 0.006(4) 0.003(4) -0.012(4) C10 0.054(6) 0.040(5) 0.025(4) 0.007(4) 0.007(4) -0.013(5) C11 0.064(7) 0.049(6) 0.037(5) 0.013(5) 0.010(5) -0.005(5) C12 0.108(10) 0.047(6) 0.046(6) 0.009(5) 0.034(6) 0.021(7) C13 0.105(10) 0.075(9) 0.047(7) -0.001(6) 0.029(7) 0.002(8) C14 0.105(10) 0.071(8) 0.033(6) 0.016(6) 0.025(6) 0.009(8) C15 0.062(7) 0.056(7) 0.035(5) 0.012(5) 0.006(5) -0.003(6) C16 0.052(7) 0.068(8) 0.047(6) 0.013(6) -0.002(5) 0.005(6) C17 0.074(8) 0.061(8) 0.058(7) 0.004(6) 0.028(6) -0.029(6) C18 0.110(10) 0.084(9) 0.070(8) 0.009(7) 0.027(7) -0.052(7) C19 0.096(8) 0.116(10) 0.085(8) -0.027(6) 0.058(7) -0.066(7) C20 0.096(8) 0.116(10) 0.085(8) -0.027(6) 0.058(7) -0.066(7) C21 0.043(6) 0.071(8) 0.074(8) -0.027(6) 0.027(5) -0.020(6) C22 0.043(5) 0.054(6) 0.039(5) -0.008(5) 0.017(4) -0.019(5) C23 0.041(5) 0.037(5) 0.040(5) 0.007(4) 0.009(4) -0.006(4) C24 0.051(6) 0.046(6) 0.024(4) 0.003(4) 0.016(4) 0.002(5) C25 0.032(5) 0.052(6) 0.026(4) 0.004(4) 0.007(4) 0.004(4) C26 0.041(5) 0.058(6) 0.027(4) 0.015(4) 0.018(4) 0.003(5) C27 0.070(7) 0.051(7) 0.048(6) 0.004(5) 0.029(5) -0.001(6) C28 0.065(7) 0.074(8) 0.051(6) 0.000(6) 0.040(6) 0.004(6) C29 0.041(5) 0.078(8) 0.032(5) 0.004(5) 0.015(4) -0.001(6) C30 0.053(6) 0.056(7) 0.044(6) 0.010(5) 0.008(5) -0.018(5) C31 0.048(6) 0.072(7) 0.031(5) -0.004(5) 0.012(4) -0.014(6) C32 0.091(9) 0.068(9) 0.054(7) -0.021(6) 0.027(7) -0.031(8) _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 O2 1.866(6) . ? Ti1 O1 1.872(6) . ? Ti1 Cl2' 2.17(2) . ? Ti1 N1 2.204(7) . ? Ti1 N2 2.221(7) . ? Ti1 Cl1 2.249(3) . ? Ti1 Cl2 2.290(3) . ? Cl2 Cl2' 0.89(3) . ? F1 C16 1.337(12) . ? F2 C16 1.333(12) . ? F3 C16 1.324(13) . ? F4 C15 1.343(12) . ? F5 C13 1.315(14) . ? F6 C32 1.256(14) . ? F7 C32 1.356(16) . ? F8 C32 1.342(13) . ? F9 C27 1.363(13) . ? F10 C29 1.359(10) . ? O1 C9 1.311(10) . ? O2 C25 1.298(10) . ? N1 C7 1.300(11) . ? N1 C6 1.414(12) . ? N2 C23 1.307(11) . ? N2 C22 1.464(11) . ? C1 C6 1.363(17) . ? C1 C2 1.403(15) . ? C1 H1 0.9500 . ? C2 C3 1.32(2) . ? C2 H2 0.9500 . ? C3 C4 1.40(2) . ? C3 H3 0.9500 . ? C4 C5 1.376(19) . ? C4 H4 0.9500 . ? C5 C6 1.396(15) . ? C5 H5 0.9500 . ? C7 C8 1.427(13) . ? C7 C16 1.531(14) . ? C8 C9 1.333(13) . ? C8 H8 0.9500 . ? C9 C10 1.474(13) . ? C10 C11 1.375(14) . ? C10 C15 1.403(12) . ? C11 C12 1.380(14) . ? C11 H11 0.9500 . ? C12 C13 1.381(15) . ? C12 H12 0.9500 . ? C13 C14 1.372(17) . ? C14 C15 1.357(15) . ? C14 H14 0.9500 . ? C17 C22 1.346(15) . ? C17 C18 1.420(15) . ? C17 H17 0.9500 . ? C18 C19 1.39(2) . ? C18 H18 0.9500 . ? C19 C20 1.31(2) . ? C19 H19 0.9500 . ? C20 C21 1.417(16) . ? C20 H20 0.9500 . ? C21 C22 1.384(14) . ? C21 H21 0.9500 . ? C23 C24 1.433(12) . ? C23 C32 1.543(15) . ? C24 C25 1.357(13) . ? C24 H24 0.9500 . ? C25 C26 1.484(11) . ? C26 C27 1.367(13) . ? C26 C31 1.399(14) . ? C27 C28 1.391(13) . ? C28 C29 1.356(16) . ? C28 H28 0.9500 . ? C29 C30 1.359(14) . ? C30 C31 1.378(13) . ? C30 H30 0.9500 . ? C31 H31 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 O2 Ti1 O1 168.7(3) . . ? O2 Ti1 Cl2' 82.6(6) . . ? O1 Ti1 Cl2' 100.2(6) . . ? O2 Ti1 N1 90.5(3) . . ? O1 Ti1 N1 80.1(3) . . ? Cl2' Ti1 N1 72.2(9) . . ? O2 Ti1 N2 81.3(3) . . ? O1 Ti1 N2 91.3(3) . . ? Cl2' Ti1 N2 150.6(9) . . ? N1 Ti1 N2 83.4(3) . . ? O2 Ti1 Cl1 96.5(2) . . ? O1 Ti1 Cl1 91.7(2) . . ? Cl2' Ti1 Cl1 119.5(9) . . ? N1 Ti1 Cl1 167.0(2) . . ? N2 Ti1 Cl1 86.8(2) . . ? O2 Ti1 Cl2 91.2(2) . . ? O1 Ti1 Cl2 95.5(2) . . ? Cl2' Ti1 Cl2 22.9(8) . . ? N1 Ti1 Cl2 93.3(2) . . ? N2 Ti1 Cl2 171.8(2) . . ? Cl1 Ti1 Cl2 97.51(16) . . ? Cl2' Cl2 Ti1 70.8(14) . . ? Cl2 Cl2' Ti1 86.2(15) . . ? C9 O1 Ti1 144.7(6) . . ? C25 O2 Ti1 143.5(6) . . ? C7 N1 C6 121.4(8) . . ? C7 N1 Ti1 126.0(6) . . ? C6 N1 Ti1 112.6(6) . . ? C23 N2 C22 120.4(8) . . ? C23 N2 Ti1 124.7(6) . . ? C22 N2 Ti1 114.9(6) . . ? C6 C1 C2 117.9(14) . . ? C6 C1 H1 121.1 . . ? C2 C1 H1 121.1 . . ? C3 C2 C1 122.1(15) . . ? C3 C2 H2 118.9 . . ? C1 C2 H2 118.9 . . ? C2 C3 C4 121.3(13) . . ? C2 C3 H3 119.3 . . ? C4 C3 H3 119.3 . . ? C5 C4 C3 117.5(15) . . ? C5 C4 H4 121.3 . . ? C3 C4 H4 121.3 . . ? C4 C5 C6 121.0(16) . . ? C4 C5 H5 119.5 . . ? C6 C5 H5 119.5 . . ? C1 C6 C5 120.2(11) . . ? C1 C6 N1 120.4(10) . . ? C5 C6 N1 119.2(11) . . ? N1 C7 C8 126.2(9) . . ? N1 C7 C16 120.3(9) . . ? C8 C7 C16 113.5(8) . . ? C9 C8 C7 123.2(9) . . ? C9 C8 H8 118.4 . . ? C7 C8 H8 118.4 . . ? O1 C9 C8 119.6(8) . . ? O1 C9 C10 113.2(8) . . ? C8 C9 C10 127.2(8) . . ? C11 C10 C15 116.0(9) . . ? C11 C10 C9 119.5(8) . . ? C15 C10 C9 124.5(9) . . ? C12 C11 C10 122.9(9) . . ? C12 C11 H11 118.5 . . ? C10 C11 H11 118.5 . . ? C11 C12 C13 118.0(11) . . ? C11 C12 H12 121.0 . . ? C13 C12 H12 121.0 . . ? F5 C13 C14 119.8(11) . . ? F5 C13 C12 118.7(12) . . ? C14 C13 C12 121.5(11) . . ? C15 C14 C13 118.5(10) . . ? C15 C14 H14 120.7 . . ? C13 C14 H14 120.7 . . ? F4 C15 C14 117.0(9) . . ? F4 C15 C10 119.9(9) . . ? C14 C15 C10 123.0(10) . . ? F3 C16 F2 106.4(10) . . ? F3 C16 F1 105.6(9) . . ? F2 C16 F1 105.9(9) . . ? F3 C16 C7 111.8(9) . . ? F2 C16 C7 113.0(9) . . ? F1 C16 C7 113.6(9) . . ? C22 C17 C18 120.5(12) . . ? C22 C17 H17 119.7 . . ? C18 C17 H17 119.7 . . ? C19 C18 C17 117.5(14) . . ? C19 C18 H18 121.2 . . ? C17 C18 H18 121.2 . . ? C20 C19 C18 121.1(13) . . ? C20 C19 H19 119.4 . . ? C18 C19 H19 119.4 . . ? C19 C20 C21 122.3(15) . . ? C19 C20 H20 118.8 . . ? C21 C20 H20 118.8 . . ? C22 C21 C20 117.0(13) . . ? C22 C21 H21 121.5 . . ? C20 C21 H21 121.5 . . ? C17 C22 C21 121.4(10) . . ? C17 C22 N2 120.5(9) . . ? C21 C22 N2 117.7(10) . . ? N2 C23 C24 125.8(8) . . ? N2 C23 C32 120.1(8) . . ? C24 C23 C32 113.9(8) . . ? C25 C24 C23 123.4(8) . . ? C25 C24 H24 118.3 . . ? C23 C24 H24 118.3 . . ? O2 C25 C24 120.3(8) . . ? O2 C25 C26 114.2(8) . . ? C24 C25 C26 125.6(8) . . ? C27 C26 C31 115.6(8) . . ? C27 C26 C25 125.8(9) . . ? C31 C26 C25 118.5(8) . . ? F9 C27 C26 119.1(9) . . ? F9 C27 C28 116.7(10) . . ? C26 C27 C28 124.1(11) . . ? C29 C28 C27 116.4(10) . . ? C29 C28 H28 121.8 . . ? C27 C28 H28 121.8 . . ? C28 C29 F10 117.3(9) . . ? C28 C29 C30 123.5(9) . . ? F10 C29 C30 119.1(10) . . ? C29 C30 C31 118.0(10) . . ? C29 C30 H30 121.0 . . ? C31 C30 H30 121.0 . . ? C30 C31 C26 122.3(9) . . ? C30 C31 H31 118.9 . . ? C26 C31 H31 118.9 . . ? F6 C32 F8 107.0(11) . . ? F6 C32 F7 108.1(12) . . ? F8 C32 F7 105.3(10) . . ? F6 C32 C23 116.3(10) . . ? F8 C32 C23 110.1(9) . . ? F7 C32 C23 109.4(10) . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 1.149 _refine_diff_density_min -0.775 _refine_diff_density_rms 0.119 data_r468(2K) _database_code_depnum_ccdc_archive 'CCDC 763884' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H20 Br2 Cl2 F6 N2 O2 Ti' _chemical_formula_weight 857.12 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' Br Br -0.2901 2.4595 '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 11.2111(10) _cell_length_b 15.5277(14) _cell_length_c 19.3685(17) _cell_angle_alpha 90.00 _cell_angle_beta 102.674(2) _cell_angle_gamma 90.00 _cell_volume 3289.6(5) _cell_formula_units_Z 4 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used 2612 _cell_measurement_theta_min 2.28 _cell_measurement_theta_max 22.26 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.731 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1688 _exptl_absorpt_coefficient_mu 2.919 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5739 _exptl_absorpt_correction_T_max 0.7689 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _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 APEX CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16828 _diffrn_reflns_av_R_equivalents 0.0482 _diffrn_reflns_av_sigmaI/netI 0.0624 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.70 _diffrn_reflns_theta_max 25.03 _reflns_number_total 5809 _reflns_number_gt 3754 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; 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^)+(0.1348P)^2^+14.7023P] 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 5809 _refine_ls_number_parameters 418 _refine_ls_number_restraints 12 _refine_ls_R_factor_all 0.1290 _refine_ls_R_factor_gt 0.0874 _refine_ls_wR_factor_ref 0.2656 _refine_ls_wR_factor_gt 0.2359 _refine_ls_goodness_of_fit_ref 1.099 _refine_ls_restrained_S_all 1.109 _refine_ls_shift/su_max 0.006 _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 0.79643(13) 0.02636(9) 0.32953(7) 0.0294(4) Uani 1 1 d . . . Cl1 Cl 0.9638(2) -0.02532(18) 0.40534(12) 0.0544(7) Uani 1 1 d . . . Cl2 Cl 0.6995(2) -0.10247(14) 0.30237(13) 0.0484(6) Uani 1 1 d . . . F1 F 1.1085(7) 0.2879(5) 0.2897(4) 0.086(2) Uani 1 1 d . . . F2 F 1.1264(6) 0.2482(4) 0.3968(4) 0.078(2) Uani 1 1 d . . . F3 F 0.9832(6) 0.3289(4) 0.3507(4) 0.073(2) Uani 1 1 d . . . F4 F 0.3885(6) 0.0765(7) 0.1801(4) 0.109(3) Uani 1 1 d . . . F5 F 0.4323(6) 0.2082(6) 0.2033(4) 0.089(3) Uani 1 1 d . . . F6 F 0.3236(5) 0.1404(6) 0.2607(4) 0.083(2) Uani 1 1 d . . . O1 O 0.8711(5) 0.0222(3) 0.2511(3) 0.0305(12) Uani 1 1 d . . . O2 O 0.7165(5) 0.0558(4) 0.4007(3) 0.0359(14) Uani 1 1 d . . . N1 N 0.8839(6) 0.1554(4) 0.3427(3) 0.0299(15) Uani 1 1 d . . . N2 N 0.6355(6) 0.0876(4) 0.2645(3) 0.0296(15) Uani 1 1 d . . . C1 C 0.9165(8) 0.1940(6) 0.4670(4) 0.038(2) Uani 1 1 d U . . H1 H 0.9807 0.1528 0.4769 0.046 Uiso 1 1 calc R . . C2 C 0.8854(10) 0.2415(7) 0.5219(5) 0.050(3) Uani 1 1 d . . . H2 H 0.9288 0.2329 0.5694 0.060 Uiso 1 1 calc R . . C3 C 0.7921(10) 0.3003(8) 0.5070(6) 0.063(3) Uani 1 1 d . . . H3 H 0.7725 0.3333 0.5443 0.076 Uiso 1 1 calc R . . C4 C 0.7273(10) 0.3122(7) 0.4397(7) 0.060(3) Uani 1 1 d . . . H4 H 0.6615 0.3521 0.4304 0.072 Uiso 1 1 calc R . . C5 C 0.7576(9) 0.2653(6) 0.3836(5) 0.047(2) Uani 1 1 d U . . H5 H 0.7130 0.2731 0.3363 0.057 Uiso 1 1 calc R . . C6 C 0.8538(8) 0.2075(5) 0.3991(4) 0.0330(18) Uani 1 1 d U . . C7 C 0.9722(7) 0.1797(5) 0.3133(4) 0.0306(18) Uani 1 1 d . . . C8 C 1.0147(7) 0.1328(6) 0.2600(4) 0.036(2) Uani 1 1 d . . . H8 H 1.0826 0.1550 0.2437 0.043 Uiso 1 1 calc R . . C9 C 0.9632(7) 0.0583(5) 0.2316(4) 0.0311(18) Uani 1 1 d . . . C10 C 1.0191(8) 0.0006(6) 0.1828(4) 0.041(2) Uani 1 1 d D . . C11 C 1.0388(9) -0.0904(6) 0.2049(6) 0.069(2) Uani 1 1 d DU . . H11 H 1.0168 -0.1148 0.2453 0.083 Uiso 1 1 calc R . . C12 C 1.0940(12) -0.1351(9) 0.1579(7) 0.077(3) Uani 1 1 d U . . H12 H 1.1081 -0.1948 0.1663 0.093 Uiso 1 1 calc R . . C13 C 1.1294(11) -0.1010(8) 0.1011(7) 0.069(3) Uani 1 1 d U . . H13 H 1.1670 -0.1381 0.0732 0.083 Uiso 1 1 calc R . . C14 C 1.1147(9) -0.0179(8) 0.0819(7) 0.069(2) Uani 1 1 d U . . H14 H 1.1409 0.0036 0.0418 0.083 Uiso 1 1 calc R . . C15 C 1.0571(9) 0.0372(7) 0.1253(5) 0.053(3) Uani 1 1 d DU . . C16 C 1.0466(9) 0.2618(6) 0.3367(5) 0.044(2) Uani 1 1 d . . . C17 C 0.6227(10) 0.0317(6) 0.1439(5) 0.048(2) Uani 1 1 d . . . H17 H 0.6005 -0.0233 0.1585 0.058 Uiso 1 1 calc R . . C18 C 0.6359(11) 0.0443(8) 0.0763(5) 0.060(3) Uani 1 1 d . . . H18 H 0.6213 -0.0022 0.0437 0.072 Uiso 1 1 calc R . . C19 C 0.6692(10) 0.1219(9) 0.0547(5) 0.061(3) Uani 1 1 d . . . H19 H 0.6780 0.1296 0.0074 0.073 Uiso 1 1 calc R . . C20 C 0.6903(9) 0.1894(8) 0.1015(5) 0.053(3) Uani 1 1 d . . . H20 H 0.7140 0.2438 0.0865 0.064 Uiso 1 1 calc R . . C21 C 0.6773(8) 0.1790(6) 0.1695(5) 0.038(2) Uani 1 1 d . . . H21 H 0.6924 0.2259 0.2017 0.045 Uiso 1 1 calc R . . C22 C 0.6424(7) 0.1004(5) 0.1912(4) 0.0322(19) Uani 1 1 d . . . C23 C 0.5347(8) 0.1046(5) 0.2855(5) 0.036(2) Uani 1 1 d . . . C24 C 0.5197(8) 0.1019(6) 0.3566(5) 0.042(2) Uani 1 1 d . . . H24 H 0.4413 0.1142 0.3653 0.051 Uiso 1 1 calc R . . C25 C 0.6116(8) 0.0828(5) 0.4122(5) 0.036(2) Uani 1 1 d . . . C26 C 0.6119(9) 0.0878(5) 0.4899(5) 0.040(2) Uani 1 1 d . . . C27 C 0.5218(10) 0.1237(6) 0.5213(5) 0.049(3) Uani 1 1 d . . . C28 C 0.5370(12) 0.1252(6) 0.5950(6) 0.058(3) Uani 1 1 d . . . H28 H 0.4749 0.1496 0.6152 0.069 Uiso 1 1 calc R . . C29 C 0.6385(12) 0.0926(7) 0.6378(6) 0.058(3) Uani 1 1 d . . . H29 H 0.6478 0.0949 0.6877 0.069 Uiso 1 1 calc R . . C30 C 0.7285(10) 0.0562(8) 0.6090(5) 0.058(3) Uani 1 1 d . . . H30 H 0.8001 0.0333 0.6389 0.069 Uiso 1 1 calc R . . C31 C 0.7137(9) 0.0533(7) 0.5365(5) 0.050(3) Uani 1 1 d . . . H31 H 0.7755 0.0266 0.5174 0.060 Uiso 1 1 calc R . . C32 C 0.4194(9) 0.1300(9) 0.2315(6) 0.065(3) Uani 1 1 d . . . Br1 Br 1.03053(13) 0.15181(8) 0.09430(7) 0.0722(5) Uani 1 1 d . . . Br2 Br 0.37230(13) 0.17270(9) 0.47102(7) 0.0747(5) 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 0.0327(8) 0.0307(8) 0.0274(8) 0.0036(6) 0.0123(6) 0.0060(6) Cl1 0.0561(15) 0.0688(17) 0.0369(13) 0.0106(11) 0.0073(11) 0.0328(13) Cl2 0.0639(16) 0.0297(11) 0.0600(15) 0.0028(10) 0.0319(13) -0.0006(11) F1 0.110(6) 0.078(5) 0.091(5) -0.025(4) 0.066(5) -0.052(4) F2 0.060(4) 0.077(5) 0.078(5) -0.004(4) -0.023(4) -0.017(3) F3 0.062(4) 0.042(3) 0.119(6) -0.005(3) 0.030(4) 0.000(3) F4 0.049(4) 0.164(9) 0.094(6) -0.059(6) -0.028(4) 0.021(5) F5 0.062(4) 0.127(7) 0.082(5) 0.050(5) 0.023(4) 0.049(4) F6 0.032(3) 0.145(7) 0.075(5) 0.012(4) 0.012(3) 0.015(4) O1 0.028(3) 0.033(3) 0.033(3) -0.005(2) 0.012(2) 0.003(2) O2 0.040(3) 0.041(3) 0.031(3) 0.001(3) 0.018(3) 0.009(3) N1 0.024(4) 0.041(4) 0.024(3) 0.000(3) 0.002(3) 0.005(3) N2 0.030(4) 0.026(3) 0.034(4) -0.001(3) 0.010(3) -0.002(3) C1 0.038(5) 0.045(5) 0.030(4) -0.006(4) 0.004(4) -0.003(4) C2 0.051(6) 0.063(7) 0.035(5) -0.013(5) 0.011(5) -0.014(5) C3 0.052(7) 0.081(8) 0.064(8) -0.038(6) 0.026(6) -0.010(6) C4 0.043(6) 0.056(7) 0.081(8) -0.029(6) 0.015(6) 0.007(5) C5 0.042(5) 0.049(6) 0.046(6) -0.012(4) 0.001(4) 0.008(4) C6 0.032(4) 0.032(4) 0.037(4) -0.008(4) 0.010(4) -0.001(3) C7 0.028(4) 0.034(4) 0.029(4) 0.001(3) 0.004(4) -0.001(4) C8 0.021(4) 0.053(5) 0.035(5) -0.007(4) 0.010(4) -0.004(4) C9 0.028(4) 0.038(5) 0.027(4) 0.003(4) 0.005(3) 0.003(4) C10 0.026(4) 0.064(6) 0.037(5) -0.007(4) 0.015(4) -0.005(4) C11 0.037(4) 0.084(5) 0.094(6) -0.059(4) 0.030(4) -0.005(4) C12 0.080(9) 0.068(8) 0.094(9) -0.018(6) 0.043(7) 0.008(7) C13 0.071(8) 0.071(6) 0.076(8) -0.029(6) 0.037(6) -0.003(6) C14 0.037(4) 0.084(5) 0.094(6) -0.059(4) 0.030(4) -0.005(4) C15 0.049(6) 0.054(6) 0.060(7) 0.002(5) 0.023(5) 0.007(5) C16 0.036(5) 0.044(5) 0.054(6) -0.010(5) 0.017(5) 0.001(4) C17 0.069(7) 0.035(5) 0.036(5) -0.003(4) 0.003(5) 0.006(5) C18 0.078(8) 0.064(7) 0.034(6) -0.005(5) 0.002(5) 0.029(6) C19 0.054(7) 0.097(9) 0.033(5) 0.016(6) 0.012(5) 0.032(6) C20 0.046(6) 0.069(7) 0.048(6) 0.021(6) 0.016(5) 0.003(5) C21 0.038(5) 0.037(5) 0.038(5) 0.006(4) 0.009(4) -0.002(4) C22 0.027(4) 0.039(5) 0.029(4) 0.005(4) 0.002(3) 0.005(4) C23 0.028(4) 0.031(4) 0.048(5) -0.001(4) 0.008(4) -0.003(4) C24 0.032(5) 0.054(6) 0.045(6) -0.010(4) 0.017(4) 0.003(4) C25 0.037(5) 0.029(4) 0.047(5) -0.005(4) 0.023(4) -0.003(4) C26 0.052(6) 0.032(5) 0.046(5) -0.006(4) 0.035(5) -0.004(4) C27 0.066(7) 0.035(5) 0.058(6) 0.003(4) 0.041(6) -0.007(5) C28 0.097(9) 0.035(5) 0.063(7) 0.003(5) 0.064(7) 0.005(6) C29 0.098(9) 0.046(6) 0.042(6) 0.004(5) 0.043(6) -0.005(6) C30 0.058(7) 0.077(8) 0.041(6) -0.002(5) 0.017(5) -0.003(6) C31 0.050(6) 0.069(7) 0.037(5) -0.004(5) 0.023(5) 0.001(5) C32 0.031(6) 0.103(10) 0.059(7) -0.001(7) 0.008(5) 0.009(6) Br1 0.0972(10) 0.0631(8) 0.0710(8) 0.0182(6) 0.0500(7) 0.0222(7) Br2 0.0821(9) 0.0759(9) 0.0802(9) 0.0120(6) 0.0486(7) 0.0389(7) _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 O2 1.859(5) . ? Ti1 O1 1.889(5) . ? Ti1 N2 2.180(7) . ? Ti1 N1 2.221(7) . ? Ti1 Cl1 2.261(3) . ? Ti1 Cl2 2.282(3) . ? F1 C16 1.322(11) . ? F2 C16 1.321(11) . ? F3 C16 1.322(11) . ? F4 C32 1.285(14) . ? F5 C32 1.353(15) . ? F6 C32 1.328(12) . ? O1 C9 1.302(10) . ? O2 C25 1.312(10) . ? N1 C7 1.301(10) . ? N1 C6 1.458(10) . ? N2 C23 1.309(11) . ? N2 C22 1.452(10) . ? C1 C6 1.365(12) . ? C1 C2 1.400(13) . ? C1 H1 0.9500 . ? C2 C3 1.371(16) . ? C2 H2 0.9500 . ? C3 C4 1.359(16) . ? C3 H3 0.9500 . ? C4 C5 1.411(14) . ? C4 H4 0.9500 . ? C5 C6 1.384(12) . ? C5 H5 0.9500 . ? C7 C8 1.427(12) . ? C7 C16 1.536(12) . ? C8 C9 1.355(12) . ? C8 H8 0.9500 . ? C9 C10 1.533(12) . ? C10 C15 1.397(8) . ? C10 C11 1.478(9) . ? C11 C12 1.394(15) . ? C11 H11 0.9500 . ? C12 C13 1.355(18) . ? C12 H12 0.9500 . ? C13 C14 1.342(18) . ? C13 H13 0.9500 . ? C14 C15 1.447(13) . ? C14 H14 0.9500 . ? C15 Br1 1.882(10) . ? C17 C18 1.363(14) . ? C17 C22 1.393(12) . ? C17 H17 0.9500 . ? C18 C19 1.355(17) . ? C18 H18 0.9500 . ? C19 C20 1.372(16) . ? C19 H19 0.9500 . ? C20 C21 1.365(13) . ? C20 H20 0.9500 . ? C21 C22 1.375(12) . ? C21 H21 0.9500 . ? C23 C24 1.423(12) . ? C23 C32 1.526(14) . ? C24 C25 1.350(13) . ? C24 H24 0.9500 . ? C25 C26 1.506(12) . ? C26 C31 1.398(14) . ? C26 C27 1.403(12) . ? C27 C28 1.400(14) . ? C27 Br2 1.903(11) . ? C28 C29 1.350(16) . ? C28 H28 0.9500 . ? C29 C30 1.376(15) . ? C29 H29 0.9500 . ? C30 C31 1.378(14) . ? C30 H30 0.9500 . ? C31 H31 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 O2 Ti1 O1 167.3(3) . . ? O2 Ti1 N2 81.3(3) . . ? O1 Ti1 N2 90.4(2) . . ? O2 Ti1 N1 88.1(3) . . ? O1 Ti1 N1 82.0(2) . . ? N2 Ti1 N1 87.8(2) . . ? O2 Ti1 Cl1 94.13(19) . . ? O1 Ti1 Cl1 93.39(18) . . ? N2 Ti1 Cl1 173.8(2) . . ? N1 Ti1 Cl1 87.88(19) . . ? O2 Ti1 Cl2 96.0(2) . . ? O1 Ti1 Cl2 93.28(18) . . ? N2 Ti1 Cl2 87.55(19) . . ? N1 Ti1 Cl2 173.33(19) . . ? Cl1 Ti1 Cl2 97.11(11) . . ? C9 O1 Ti1 137.6(5) . . ? C25 O2 Ti1 143.1(6) . . ? C7 N1 C6 119.4(7) . . ? C7 N1 Ti1 124.8(5) . . ? C6 N1 Ti1 114.7(5) . . ? C23 N2 C22 120.8(7) . . ? C23 N2 Ti1 124.7(6) . . ? C22 N2 Ti1 114.2(5) . . ? C6 C1 C2 119.3(9) . . ? C6 C1 H1 120.3 . . ? C2 C1 H1 120.3 . . ? C3 C2 C1 119.8(9) . . ? C3 C2 H2 120.1 . . ? C1 C2 H2 120.1 . . ? C4 C3 C2 120.9(10) . . ? C4 C3 H3 119.5 . . ? C2 C3 H3 119.5 . . ? C3 C4 C5 120.1(10) . . ? C3 C4 H4 119.9 . . ? C5 C4 H4 119.9 . . ? C6 C5 C4 118.4(9) . . ? C6 C5 H5 120.8 . . ? C4 C5 H5 120.8 . . ? C1 C6 C5 121.4(8) . . ? C1 C6 N1 118.8(7) . . ? C5 C6 N1 119.7(8) . . ? N1 C7 C8 125.1(8) . . ? N1 C7 C16 121.9(7) . . ? C8 C7 C16 113.0(7) . . ? C9 C8 C7 123.3(8) . . ? C9 C8 H8 118.3 . . ? C7 C8 H8 118.3 . . ? O1 C9 C8 123.0(8) . . ? O1 C9 C10 112.7(7) . . ? C8 C9 C10 123.7(7) . . ? C15 C10 C11 124.6(9) . . ? C15 C10 C9 119.4(8) . . ? C11 C10 C9 115.8(7) . . ? C12 C11 C10 110.3(11) . . ? C12 C11 H11 124.9 . . ? C10 C11 H11 124.9 . . ? C13 C12 C11 125.9(13) . . ? C13 C12 H12 117.1 . . ? C11 C12 H12 117.1 . . ? C14 C13 C12 124.1(11) . . ? C14 C13 H13 118.0 . . ? C12 C13 H13 118.0 . . ? C13 C14 C15 116.8(12) . . ? C13 C14 H14 121.6 . . ? C15 C14 H14 121.6 . . ? C10 C15 C14 118.4(10) . . ? C10 C15 Br1 125.8(7) . . ? C14 C15 Br1 115.7(8) . . ? F2 C16 F3 103.6(8) . . ? F2 C16 F1 107.4(8) . . ? F3 C16 F1 106.7(8) . . ? F2 C16 C7 110.3(8) . . ? F3 C16 C7 115.6(8) . . ? F1 C16 C7 112.6(8) . . ? C18 C17 C22 119.1(10) . . ? C18 C17 H17 120.4 . . ? C22 C17 H17 120.4 . . ? C19 C18 C17 121.4(10) . . ? C19 C18 H18 119.3 . . ? C17 C18 H18 119.3 . . ? C18 C19 C20 119.6(10) . . ? C18 C19 H19 120.2 . . ? C20 C19 H19 120.2 . . ? C21 C20 C19 120.5(10) . . ? C21 C20 H20 119.8 . . ? C19 C20 H20 119.8 . . ? C20 C21 C22 119.9(9) . . ? C20 C21 H21 120.1 . . ? C22 C21 H21 120.1 . . ? C21 C22 C17 119.5(8) . . ? C21 C22 N2 120.1(8) . . ? C17 C22 N2 120.2(8) . . ? N2 C23 C24 126.1(8) . . ? N2 C23 C32 119.9(8) . . ? C24 C23 C32 114.1(8) . . ? C25 C24 C23 123.1(8) . . ? C25 C24 H24 118.5 . . ? C23 C24 H24 118.5 . . ? O2 C25 C24 119.4(8) . . ? O2 C25 C26 112.3(8) . . ? C24 C25 C26 128.3(8) . . ? C31 C26 C27 115.8(9) . . ? C31 C26 C25 116.6(8) . . ? C27 C26 C25 127.6(9) . . ? C28 C27 C26 120.7(10) . . ? C28 C27 Br2 114.3(8) . . ? C26 C27 Br2 125.0(8) . . ? C29 C28 C27 121.1(9) . . ? C29 C28 H28 119.4 . . ? C27 C28 H28 119.4 . . ? C28 C29 C30 119.9(10) . . ? C28 C29 H29 120.0 . . ? C30 C29 H29 120.0 . . ? C29 C30 C31 119.4(11) . . ? C29 C30 H30 120.3 . . ? C31 C30 H30 120.3 . . ? C30 C31 C26 123.0(9) . . ? C30 C31 H31 118.5 . . ? C26 C31 H31 118.5 . . ? F4 C32 F6 107.7(10) . . ? F4 C32 F5 107.5(11) . . ? F6 C32 F5 103.4(10) . . ? F4 C32 C23 114.1(10) . . ? F6 C32 C23 112.5(9) . . ? F5 C32 C23 111.0(9) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 4.761 _refine_diff_density_min -0.983 _refine_diff_density_rms 0.161 data_r464(2n) _database_code_depnum_ccdc_archive 'CCDC 763886' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H18 Cl2 F10 N2 O2 Ti' _chemical_formula_weight 771.28 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' 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' 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 21.721(2) _cell_length_b 8.4944(8) _cell_length_c 19.0168(17) _cell_angle_alpha 90.00 _cell_angle_beta 118.4900(10) _cell_angle_gamma 90.00 _cell_volume 3083.8(5) _cell_formula_units_Z 4 _cell_measurement_temperature 185(2) _cell_measurement_reflns_used 3496 _cell_measurement_theta_min 2.35 _cell_measurement_theta_max 26.02 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.37 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.661 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1544 _exptl_absorpt_coefficient_mu 0.547 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.8254 _exptl_absorpt_correction_T_max 0.9413 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8403 _diffrn_reflns_av_R_equivalents 0.0204 _diffrn_reflns_av_sigmaI/netI 0.0242 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.13 _diffrn_reflns_theta_max 26.03 _reflns_number_total 3035 _reflns_number_gt 2584 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; 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^+2.1768P] 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 3035 _refine_ls_number_parameters 222 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0402 _refine_ls_R_factor_gt 0.0325 _refine_ls_wR_factor_ref 0.0869 _refine_ls_wR_factor_gt 0.0827 _refine_ls_goodness_of_fit_ref 1.052 _refine_ls_restrained_S_all 1.052 _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 0.0000 0.14353(5) 0.2500 0.02125(13) Uani 1 2 d S . . N1 N -0.01423(7) -0.04263(17) 0.32324(8) 0.0216(3) Uani 1 1 d . . . O1 O 0.09407(6) 0.11088(14) 0.32532(7) 0.0240(3) Uani 1 1 d . . . Cl1 Cl -0.02232(3) 0.32185(6) 0.32399(3) 0.03494(15) Uani 1 1 d . . . F1 F 0.06566(6) -0.19532(16) 0.52362(7) 0.0444(3) Uani 1 1 d . . . F2 F -0.04253(6) -0.14576(16) 0.44967(7) 0.0424(3) Uani 1 1 d . . . F3 F 0.00583(7) -0.33896(14) 0.42118(8) 0.0469(3) Uani 1 1 d . . . F4 F 0.19478(6) 0.27696(14) 0.33457(7) 0.0387(3) Uani 1 1 d . . . F5 F 0.24108(6) -0.10878(18) 0.53339(8) 0.0552(4) Uani 1 1 d . . . C1 C -0.09238(10) -0.2645(2) 0.25558(12) 0.0313(4) Uani 1 1 d . . . H1 H -0.0533 -0.3227 0.2600 0.038 Uiso 1 1 calc R . . C2 C -0.15903(12) -0.3290(3) 0.21651(13) 0.0389(5) Uani 1 1 d . . . H2 H -0.1656 -0.4322 0.1948 0.047 Uiso 1 1 calc R . . C3 C -0.21603(11) -0.2431(3) 0.20910(12) 0.0375(5) Uani 1 1 d . . . H3 H -0.2618 -0.2866 0.1814 0.045 Uiso 1 1 calc R . . C4 C -0.20634(10) -0.0947(3) 0.24195(12) 0.0343(5) Uani 1 1 d . . . H4 H -0.2454 -0.0366 0.2374 0.041 Uiso 1 1 calc R . . C5 C -0.13971(9) -0.0297(2) 0.28168(11) 0.0280(4) Uani 1 1 d . . . H5 H -0.1331 0.0726 0.3043 0.034 Uiso 1 1 calc R . . C6 C -0.08293(9) -0.1153(2) 0.28805(11) 0.0239(4) Uani 1 1 d . . . C7 C 0.03354(9) -0.0806(2) 0.39602(11) 0.0242(4) Uani 1 1 d . . . C8 C 0.10442(9) -0.0325(2) 0.43369(11) 0.0279(4) Uani 1 1 d . . . H8 H 0.1332 -0.0605 0.4882 0.034 Uiso 1 1 calc R . . C9 C 0.13389(9) 0.0520(2) 0.39604(10) 0.0225(4) Uani 1 1 d . . . C10 C 0.21020(9) 0.0782(2) 0.42930(10) 0.0229(4) Uani 1 1 d . . . C11 C 0.23835(10) 0.1845(2) 0.39600(11) 0.0270(4) Uani 1 1 d . . . C12 C 0.30864(10) 0.2033(2) 0.42219(12) 0.0322(4) Uani 1 1 d . . . H12 H 0.3246 0.2766 0.3967 0.039 Uiso 1 1 calc R . . C13 C 0.35608(10) 0.1149(3) 0.48601(12) 0.0367(5) Uani 1 1 d . . . H13 H 0.4049 0.1261 0.5044 0.044 Uiso 1 1 calc R . . C14 C 0.33200(10) 0.0102(3) 0.52278(12) 0.0392(5) Uani 1 1 d . . . H14 H 0.3640 -0.0505 0.5672 0.047 Uiso 1 1 calc R . . C15 C 0.26142(10) -0.0050(3) 0.49452(12) 0.0328(4) Uani 1 1 d . . . C16 C 0.01516(10) -0.1910(2) 0.44766(12) 0.0307(4) 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 0.0171(2) 0.0214(2) 0.0212(2) 0.000 0.00587(19) 0.000 N1 0.0170(7) 0.0217(7) 0.0250(8) -0.0020(6) 0.0093(6) -0.0022(6) O1 0.0169(6) 0.0284(7) 0.0228(6) 0.0031(5) 0.0062(5) -0.0015(5) Cl1 0.0356(3) 0.0303(3) 0.0340(3) -0.0088(2) 0.0127(2) 0.00290(19) F1 0.0345(7) 0.0660(9) 0.0274(6) 0.0137(6) 0.0105(5) -0.0093(6) F2 0.0312(7) 0.0600(8) 0.0448(7) 0.0104(6) 0.0252(6) -0.0006(6) F3 0.0606(9) 0.0300(7) 0.0485(8) 0.0049(5) 0.0248(7) -0.0068(6) F4 0.0246(6) 0.0431(7) 0.0403(7) 0.0188(5) 0.0089(5) -0.0016(5) F5 0.0270(7) 0.0754(10) 0.0543(8) 0.0416(7) 0.0122(6) 0.0033(6) C1 0.0286(10) 0.0292(10) 0.0365(11) -0.0028(8) 0.0160(9) -0.0030(8) C2 0.0398(12) 0.0343(12) 0.0380(12) -0.0074(9) 0.0149(10) -0.0130(9) C3 0.0255(11) 0.0481(13) 0.0318(11) 0.0025(9) 0.0078(9) -0.0131(9) C4 0.0231(10) 0.0455(12) 0.0352(11) 0.0069(9) 0.0146(9) -0.0004(8) C5 0.0243(10) 0.0300(10) 0.0304(10) 0.0001(8) 0.0136(8) -0.0020(7) C6 0.0199(9) 0.0272(9) 0.0231(9) 0.0005(7) 0.0091(7) -0.0039(7) C7 0.0227(9) 0.0254(9) 0.0253(9) -0.0008(7) 0.0122(8) -0.0004(7) C8 0.0202(9) 0.0370(11) 0.0220(9) 0.0042(8) 0.0063(8) -0.0024(8) C9 0.0207(9) 0.0234(9) 0.0212(9) -0.0010(7) 0.0083(7) 0.0001(7) C10 0.0187(9) 0.0268(9) 0.0221(9) -0.0024(7) 0.0088(7) -0.0014(7) C11 0.0232(9) 0.0298(10) 0.0239(9) 0.0021(8) 0.0078(8) -0.0011(7) C12 0.0256(10) 0.0391(11) 0.0326(11) 0.0016(9) 0.0145(9) -0.0074(8) C13 0.0183(10) 0.0531(13) 0.0361(11) 0.0016(10) 0.0108(9) -0.0027(9) C14 0.0210(10) 0.0535(13) 0.0354(11) 0.0140(10) 0.0072(9) 0.0057(9) C15 0.0248(10) 0.0403(11) 0.0320(10) 0.0092(9) 0.0124(8) 0.0001(8) C16 0.0234(10) 0.0366(11) 0.0301(10) 0.0036(8) 0.0113(8) -0.0042(8) _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 1.8738(12) . ? Ti1 O1 1.8738(12) 2 ? Ti1 N1 2.2241(15) 2 ? Ti1 N1 2.2241(15) . ? Ti1 Cl1 2.2716(6) 2 ? Ti1 Cl1 2.2716(6) . ? N1 C7 1.314(2) . ? N1 C6 1.450(2) . ? O1 C9 1.303(2) . ? F1 C16 1.334(2) . ? F2 C16 1.329(2) . ? F3 C16 1.333(2) . ? F4 C11 1.350(2) . ? F5 C15 1.353(2) . ? C1 C6 1.382(3) . ? C1 C2 1.386(3) . ? C1 H1 0.9500 . ? C2 C3 1.385(3) . ? C2 H2 0.9500 . ? C3 C4 1.378(3) . ? C3 H3 0.9500 . ? C4 C5 1.388(3) . ? C4 H4 0.9500 . ? C5 C6 1.386(3) . ? C5 H5 0.9500 . ? C7 C8 1.414(3) . ? C7 C16 1.542(3) . ? C8 C9 1.369(3) . ? C8 H8 0.9500 . ? C9 C10 1.482(2) . ? C10 C15 1.400(3) . ? C10 C11 1.400(3) . ? C11 C12 1.371(3) . ? C12 C13 1.381(3) . ? C12 H12 0.9500 . ? C13 C14 1.379(3) . ? C13 H13 0.9500 . ? C14 C15 1.367(3) . ? C14 H14 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 O1 162.98(8) . 2 ? O1 Ti1 N1 86.95(5) . 2 ? O1 Ti1 N1 80.95(5) 2 2 ? O1 Ti1 N1 80.95(5) . . ? O1 Ti1 N1 86.95(5) 2 . ? N1 Ti1 N1 89.37(7) 2 . ? O1 Ti1 Cl1 95.45(4) . 2 ? O1 Ti1 Cl1 95.87(4) 2 2 ? N1 Ti1 Cl1 87.23(4) 2 2 ? N1 Ti1 Cl1 175.19(4) . 2 ? O1 Ti1 Cl1 95.87(4) . . ? O1 Ti1 Cl1 95.45(4) 2 . ? N1 Ti1 Cl1 175.19(4) 2 . ? N1 Ti1 Cl1 87.23(4) . . ? Cl1 Ti1 Cl1 96.35(3) 2 . ? C7 N1 C6 120.23(15) . . ? C7 N1 Ti1 123.94(12) . . ? C6 N1 Ti1 115.68(11) . . ? C9 O1 Ti1 142.26(12) . . ? C6 C1 C2 119.77(19) . . ? C6 C1 H1 120.1 . . ? C2 C1 H1 120.1 . . ? C3 C2 C1 120.05(19) . . ? C3 C2 H2 120.0 . . ? C1 C2 H2 120.0 . . ? C4 C3 C2 120.00(19) . . ? C4 C3 H3 120.0 . . ? C2 C3 H3 120.0 . . ? C3 C4 C5 120.32(19) . . ? C3 C4 H4 119.8 . . ? C5 C4 H4 119.8 . . ? C6 C5 C4 119.47(18) . . ? C6 C5 H5 120.3 . . ? C4 C5 H5 120.3 . . ? C1 C6 C5 120.38(17) . . ? C1 C6 N1 119.83(16) . . ? C5 C6 N1 119.60(16) . . ? N1 C7 C8 125.80(17) . . ? N1 C7 C16 120.40(16) . . ? C8 C7 C16 113.78(15) . . ? C9 C8 C7 123.66(17) . . ? C9 C8 H8 118.2 . . ? C7 C8 H8 118.2 . . ? O1 C9 C8 119.69(16) . . ? O1 C9 C10 116.08(15) . . ? C8 C9 C10 124.19(16) . . ? C15 C10 C11 113.11(16) . . ? C15 C10 C9 123.84(17) . . ? C11 C10 C9 123.00(16) . . ? F4 C11 C12 116.47(17) . . ? F4 C11 C10 119.32(16) . . ? C12 C11 C10 124.21(17) . . ? C11 C12 C13 119.38(18) . . ? C11 C12 H12 120.3 . . ? C13 C12 H12 120.3 . . ? C14 C13 C12 119.47(19) . . ? C14 C13 H13 120.3 . . ? C12 C13 H13 120.3 . . ? C15 C14 C13 119.14(19) . . ? C15 C14 H14 120.4 . . ? C13 C14 H14 120.4 . . ? F5 C15 C14 116.36(17) . . ? F5 C15 C10 118.98(16) . . ? C14 C15 C10 124.66(18) . . ? F2 C16 F3 107.95(16) . . ? F2 C16 F1 106.04(16) . . ? F3 C16 F1 106.37(16) . . ? F2 C16 C7 112.10(16) . . ? F3 C16 C7 111.84(16) . . ? F1 C16 C7 112.17(15) . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 26.03 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.290 _refine_diff_density_min -0.291 _refine_diff_density_rms 0.052