# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Dr Guo-Xin Jin' _publ_contact_author_email gxjin@fudan.edu.cn _publ_section_title ; Syntheses, Reactions, and Ethylene Polymerization of Half-Sandwich Titanium Complexes containing Salicylbenzoxazoles and Salicylbenothiazoles Ligands ; _publ_author_name 'Guo-Xin Jin' # Attachment '- Complex-2a.cif' data_f70209b _database_code_depnum_ccdc_archive 'CCDC 823978' #TrackingRef '- Complex-2a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H13 Cl2 N2 O Ti' _chemical_formula_weight 392.10 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' 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 10.550(4) _cell_length_b 13.034(5) _cell_length_c 12.051(5) _cell_angle_alpha 90.00 _cell_angle_beta 93.628(5) _cell_angle_gamma 90.00 _cell_volume 1653.8(11) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 987 _cell_measurement_theta_min 2.304 _cell_measurement_theta_max 27.086 _exptl_crystal_description brown _exptl_crystal_colour block _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.575 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 796 _exptl_absorpt_coefficient_mu 0.847 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7852 _exptl_absorpt_correction_T_max 0.8834 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 6.97 _diffrn_reflns_number 7968 _diffrn_reflns_av_R_equivalents 0.0520 _diffrn_reflns_av_sigmaI/netI 0.0465 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.30 _diffrn_reflns_theta_max 27.12 _reflns_number_total 3578 _reflns_number_gt 2927 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0923P)^2^+0.1789P] 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 3578 _refine_ls_number_parameters 217 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0582 _refine_ls_R_factor_gt 0.0493 _refine_ls_wR_factor_ref 0.1432 _refine_ls_wR_factor_gt 0.1365 _refine_ls_goodness_of_fit_ref 1.052 _refine_ls_restrained_S_all 1.052 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.19105(4) 0.91212(3) 0.30439(3) 0.03410(16) Uani 1 1 d . . . N1 N 0.33320(18) 1.02555(15) 0.37763(16) 0.0360(4) Uani 1 1 d . . . N2 N 0.52130(16) 1.10380(14) 0.40564(16) 0.0319(4) Uani 1 1 d . . . O1 O 0.33552(16) 0.86776(14) 0.24097(15) 0.0452(4) Uani 1 1 d . . . Cl1 Cl 0.14935(7) 0.89427(5) 0.48957(5) 0.0496(2) Uani 1 1 d . . . Cl2 Cl 0.12005(7) 0.73980(5) 0.28967(6) 0.0538(2) Uani 1 1 d . . . C1 C 0.4437(2) 0.9030(2) 0.2027(2) 0.0405(5) Uani 1 1 d . . . C2 C 0.4957(3) 0.8545(3) 0.1124(2) 0.0542(7) Uani 1 1 d . . . H2 H 0.4542 0.7994 0.0771 0.065 Uiso 1 1 calc R . . C3 C 0.6093(3) 0.8898(3) 0.0769(3) 0.0616(8) Uani 1 1 d . . . H3 H 0.6443 0.8583 0.0167 0.074 Uiso 1 1 calc R . . C4 C 0.6719(3) 0.9705(3) 0.1287(3) 0.0616(8) Uani 1 1 d . . . H4 H 0.7477 0.9939 0.1025 0.074 Uiso 1 1 calc R . . C5 C 0.6230(3) 1.0172(2) 0.2194(2) 0.0514(7) Uani 1 1 d . . . H5 H 0.6672 1.0704 0.2558 0.062 Uiso 1 1 calc R . . C6 C 0.5069(2) 0.9845(2) 0.2563(2) 0.0416(5) Uani 1 1 d . . . C7 C 0.4491(2) 1.03440(19) 0.3465(2) 0.0377(5) Uani 1 1 d . . . C8 C 0.3228(2) 1.09997(18) 0.4621(2) 0.0383(5) Uani 1 1 d . . . C9 C 0.2233(3) 1.1329(2) 0.5225(2) 0.0466(6) Uani 1 1 d . . . H9 H 0.1429 1.1039 0.5123 0.056 Uiso 1 1 calc R . . C10 C 0.2481(3) 1.2106(2) 0.5985(2) 0.0561(7) Uani 1 1 d . . . H10 H 0.1828 1.2348 0.6398 0.067 Uiso 1 1 calc R . . C11 C 0.3691(3) 1.2537(2) 0.6150(3) 0.0579(8) Uani 1 1 d . . . H11 H 0.3827 1.3050 0.6680 0.069 Uiso 1 1 calc R . . C12 C 0.4678(3) 1.2224(2) 0.5553(2) 0.0548(7) Uani 1 1 d . . . H12 H 0.5484 1.2511 0.5659 0.066 Uiso 1 1 calc R . . C13 C 0.4413(2) 1.1463(2) 0.4787(2) 0.0432(6) Uani 1 1 d . . . C14 C 0.1059(3) 1.0741(3) 0.2493(3) 0.0610(8) Uani 1 1 d . . . H14 H 0.1325 1.1333 0.2871 0.073 Uiso 1 1 calc R . . C15 C 0.1594(3) 1.0324(3) 0.1597(3) 0.0570(7) Uani 1 1 d . . . H15 H 0.2290 1.0588 0.1256 0.068 Uiso 1 1 calc R . . C16 C 0.0944(4) 0.9459(3) 0.1279(3) 0.0687(10) Uani 1 1 d . . . H16 H 0.1124 0.9040 0.0685 0.082 Uiso 1 1 calc R . . C17 C -0.0007(3) 0.9307(3) 0.1966(4) 0.0778(12) Uani 1 1 d . . . H17 H -0.0584 0.8767 0.1930 0.093 Uiso 1 1 calc R . . C18 C 0.0037(3) 1.0113(4) 0.2742(3) 0.0814(14) Uani 1 1 d . . . H18 H -0.0507 1.0211 0.3310 0.098 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 0.0343(3) 0.0311(3) 0.0368(3) -0.00097(16) 0.00183(16) 0.00000(15) N1 0.0399(10) 0.0315(10) 0.0365(10) -0.0004(8) 0.0003(8) 0.0014(8) N2 0.0281(9) 0.0281(9) 0.0383(10) 0.0013(8) -0.0069(7) -0.0045(7) O1 0.0409(9) 0.0430(10) 0.0526(10) -0.0108(9) 0.0086(7) -0.0003(7) Cl1 0.0627(4) 0.0450(4) 0.0422(4) -0.0007(3) 0.0114(3) -0.0079(3) Cl2 0.0655(5) 0.0353(4) 0.0608(4) -0.0084(3) 0.0049(3) -0.0093(3) C1 0.0374(12) 0.0421(14) 0.0424(13) 0.0029(10) 0.0061(9) 0.0059(10) C2 0.0572(16) 0.0554(18) 0.0507(15) -0.0078(14) 0.0091(12) 0.0031(13) C3 0.0624(19) 0.075(2) 0.0498(16) -0.0010(15) 0.0219(14) 0.0099(16) C4 0.0438(15) 0.079(2) 0.0640(19) 0.0118(17) 0.0166(13) 0.0005(15) C5 0.0410(14) 0.0552(17) 0.0581(16) 0.0063(14) 0.0031(12) -0.0014(12) C6 0.0389(12) 0.0412(14) 0.0446(13) 0.0073(11) 0.0025(10) 0.0067(10) C7 0.0376(12) 0.0321(12) 0.0427(12) 0.0059(10) -0.0037(9) 0.0002(9) C8 0.0488(14) 0.0295(12) 0.0359(12) 0.0004(9) -0.0029(9) -0.0006(9) C9 0.0550(15) 0.0359(13) 0.0493(14) -0.0024(11) 0.0055(11) 0.0014(11) C10 0.079(2) 0.0418(15) 0.0479(15) -0.0059(13) 0.0086(14) 0.0037(14) C11 0.087(2) 0.0369(14) 0.0484(16) -0.0084(12) -0.0086(15) 0.0006(14) C12 0.0691(19) 0.0401(15) 0.0523(16) 0.0010(12) -0.0187(13) -0.0092(13) C13 0.0523(14) 0.0341(13) 0.0418(13) 0.0047(11) -0.0075(10) 0.0012(10) C14 0.076(2) 0.0429(16) 0.0609(18) -0.0045(14) -0.0218(15) 0.0181(14) C15 0.0629(18) 0.0545(18) 0.0532(16) 0.0197(14) 0.0009(13) 0.0018(14) C16 0.094(3) 0.064(2) 0.0454(16) -0.0061(15) -0.0188(16) 0.0125(18) C17 0.0513(18) 0.070(2) 0.107(3) 0.029(2) -0.031(2) -0.0146(16) C18 0.060(2) 0.122(4) 0.064(2) 0.035(2) 0.0191(16) 0.052(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.8409(18) . ? Ti1 N1 2.246(2) . ? Ti1 Cl1 2.3135(11) . ? Ti1 C16 2.342(3) . ? Ti1 C17 2.347(3) . ? Ti1 C15 2.353(3) . ? Ti1 Cl2 2.3706(11) . ? Ti1 C18 2.371(3) . ? Ti1 C14 2.372(3) . ? N1 C7 1.307(3) . ? N1 C8 1.415(3) . ? N2 C7 1.355(3) . ? N2 C13 1.375(3) . ? O1 C1 1.339(3) . ? C1 C6 1.391(4) . ? C1 C2 1.400(4) . ? C2 C3 1.378(4) . ? C3 C4 1.371(5) . ? C4 C5 1.380(4) . ? C5 C6 1.396(4) . ? C6 C7 1.436(4) . ? C8 C9 1.384(4) . ? C8 C13 1.391(4) . ? C9 C10 1.379(4) . ? C10 C11 1.398(5) . ? C11 C12 1.365(5) . ? C12 C13 1.372(4) . ? C14 C15 1.363(5) . ? C14 C18 1.401(6) . ? C15 C16 1.361(5) . ? C16 C17 1.355(5) . ? C17 C18 1.406(6) . ? 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 79.64(8) . . ? O1 Ti1 Cl1 125.58(7) . . ? N1 Ti1 Cl1 81.38(6) . . ? O1 Ti1 C16 90.37(12) . . ? N1 Ti1 C16 118.33(11) . . ? Cl1 Ti1 C16 142.81(11) . . ? O1 Ti1 C17 120.65(14) . . ? N1 Ti1 C17 132.87(11) . . ? Cl1 Ti1 C17 109.55(12) . . ? C16 Ti1 C17 33.59(14) . . ? O1 Ti1 C15 89.09(10) . . ? N1 Ti1 C15 85.00(10) . . ? Cl1 Ti1 C15 139.04(9) . . ? C16 Ti1 C15 33.71(12) . . ? C17 Ti1 C15 56.21(12) . . ? O1 Ti1 Cl2 86.41(6) . . ? N1 Ti1 Cl2 148.52(6) . . ? Cl1 Ti1 Cl2 84.17(3) . . ? C16 Ti1 Cl2 89.59(10) . . ? C17 Ti1 Cl2 78.41(10) . . ? C15 Ti1 Cl2 123.11(9) . . ? O1 Ti1 C18 144.25(11) . . ? N1 Ti1 C18 103.35(15) . . ? Cl1 Ti1 C18 89.74(9) . . ? C16 Ti1 C18 56.41(13) . . ? C17 Ti1 C18 34.66(15) . . ? C15 Ti1 C18 56.27(12) . . ? Cl2 Ti1 C18 104.40(14) . . ? O1 Ti1 C14 118.16(11) . . ? N1 Ti1 C14 75.87(10) . . ? Cl1 Ti1 C14 105.53(9) . . ? C16 Ti1 C14 56.15(12) . . ? C17 Ti1 C14 57.01(13) . . ? C15 Ti1 C14 33.52(12) . . ? Cl2 Ti1 C14 135.22(9) . . ? C18 Ti1 C14 34.36(14) . . ? C7 N1 C8 105.2(2) . . ? C7 N1 Ti1 123.99(16) . . ? C8 N1 Ti1 130.80(16) . . ? C7 N2 C13 104.97(19) . . ? C1 O1 Ti1 141.40(17) . . ? O1 C1 C6 119.8(2) . . ? O1 C1 C2 119.8(2) . . ? C6 C1 C2 120.4(2) . . ? C3 C2 C1 118.8(3) . . ? C4 C3 C2 121.2(3) . . ? C3 C4 C5 120.4(3) . . ? C4 C5 C6 119.8(3) . . ? C1 C6 C5 119.4(2) . . ? C1 C6 C7 118.9(2) . . ? C5 C6 C7 121.7(3) . . ? N1 C7 N2 114.4(2) . . ? N1 C7 C6 128.8(2) . . ? N2 C7 C6 116.7(2) . . ? C9 C8 C13 119.6(2) . . ? C9 C8 N1 133.4(2) . . ? C13 C8 N1 106.9(2) . . ? C10 C9 C8 117.3(3) . . ? C9 C10 C11 121.5(3) . . ? C12 C11 C10 121.7(3) . . ? C11 C12 C13 116.1(3) . . ? C12 C13 N2 127.9(3) . . ? C12 C13 C8 123.7(3) . . ? N2 C13 C8 108.4(2) . . ? C15 C14 C18 107.4(3) . . ? C15 C14 Ti1 72.49(17) . . ? C18 C14 Ti1 72.77(19) . . ? C16 C15 C14 109.1(3) . . ? C16 C15 Ti1 72.67(18) . . ? C14 C15 Ti1 73.99(18) . . ? C17 C16 C15 109.2(3) . . ? C17 C16 Ti1 73.41(19) . . ? C15 C16 Ti1 73.61(17) . . ? C16 C17 C18 107.6(3) . . ? C16 C17 Ti1 73.00(19) . . ? C18 C17 Ti1 73.60(18) . . ? C14 C18 C17 106.7(3) . . ? C14 C18 Ti1 72.87(17) . . ? C17 C18 Ti1 71.74(18) . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 27.12 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.809 _refine_diff_density_min -0.561 _refine_diff_density_rms 0.100 # Attachment '- Complex-2b.cif' data_f70105a _database_code_depnum_ccdc_archive 'CCDC 823979' #TrackingRef '- Complex-2b.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H15 Cl2 N O2 Ti' _chemical_formula_weight 408.12 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' Ti Ti 0.2776 0.4457 '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' _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 11.758(5) _cell_length_b 10.740(5) _cell_length_c 14.181(6) _cell_angle_alpha 90.00 _cell_angle_beta 102.971(6) _cell_angle_gamma 90.00 _cell_volume 1745.1(13) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 870 _cell_measurement_theta_min 2.600 _cell_measurement_theta_max 25.752 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.553 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 832 _exptl_absorpt_coefficient_mu 0.809 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8681 _exptl_absorpt_correction_T_max 0.9235 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 8.89 _diffrn_reflns_number 8511 _diffrn_reflns_av_R_equivalents 0.0597 _diffrn_reflns_av_sigmaI/netI 0.0590 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max 27.16 _reflns_number_total 3792 _reflns_number_gt 2714 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0756P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3792 _refine_ls_number_parameters 227 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0687 _refine_ls_R_factor_gt 0.0500 _refine_ls_wR_factor_ref 0.1272 _refine_ls_wR_factor_gt 0.1180 _refine_ls_goodness_of_fit_ref 0.951 _refine_ls_restrained_S_all 0.951 _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 0.73211(4) 0.79395(5) 0.06714(3) 0.03165(16) Uani 1 1 d . . . N1 N 0.79381(19) 0.8999(2) -0.04865(15) 0.0314(5) Uani 1 1 d . . . O1 O 0.88048(19) 0.7356(2) 0.08228(16) 0.0503(6) Uani 1 1 d . . . O2 O 0.91936(16) 0.96982(17) -0.13387(13) 0.0351(4) Uani 1 1 d . . . Cl1 Cl 0.66997(6) 0.99220(6) 0.09854(5) 0.04023(19) Uani 1 1 d . . . Cl2 Cl 0.75579(8) 0.76086(8) 0.23455(5) 0.0543(2) Uani 1 1 d . . . C1 C 0.9772(2) 0.7276(3) 0.04970(19) 0.0357(6) Uani 1 1 d . . . C2 C 1.0643(3) 0.6436(3) 0.0910(2) 0.0427(7) Uani 1 1 d . . . C3 C 1.1678(3) 0.6479(3) 0.0598(2) 0.0468(7) Uani 1 1 d . . . H3 H 1.2283 0.5947 0.0882 0.056 Uiso 1 1 calc R . . C4 C 1.1842(3) 0.7274(3) -0.0111(2) 0.0464(7) Uani 1 1 d . . . H4 H 1.2547 0.7270 -0.0304 0.056 Uiso 1 1 calc R . . C5 C 1.0972(3) 0.8080(3) -0.0541(2) 0.0402(6) Uani 1 1 d . . . H5 H 1.1081 0.8615 -0.1029 0.048 Uiso 1 1 calc R . . C6 C 0.9919(2) 0.8085(2) -0.02345(18) 0.0323(6) Uani 1 1 d . . . C7 C 0.8989(2) 0.8913(2) -0.06503(18) 0.0317(6) Uani 1 1 d . . . C8 C 0.7375(2) 0.9906(2) -0.11487(18) 0.0330(6) Uani 1 1 d . . . C9 C 0.6246(3) 1.0363(3) -0.1365(2) 0.0411(7) Uani 1 1 d . . . H9 H 0.5692 1.0091 -0.1035 0.049 Uiso 1 1 calc R . . C10 C 0.5978(3) 1.1237(3) -0.2090(2) 0.0510(8) Uani 1 1 d . . . H10 H 0.5224 1.1556 -0.2258 0.061 Uiso 1 1 calc R . . C11 C 0.6811(3) 1.1656(3) -0.2581(2) 0.0535(9) Uani 1 1 d . . . H11 H 0.6600 1.2255 -0.3062 0.064 Uiso 1 1 calc R . . C12 C 0.7926(3) 1.1211(3) -0.2376(2) 0.0461(7) Uani 1 1 d . . . H12 H 0.8487 1.1488 -0.2696 0.055 Uiso 1 1 calc R . . C13 C 0.8159(3) 1.0325(3) -0.16606(18) 0.0355(6) Uani 1 1 d . . . C14 C 1.0448(3) 0.5555(4) 0.1679(3) 0.0647(10) Uani 1 1 d . . . H14A H 1.0008 0.4850 0.1382 0.097 Uiso 1 1 calc R . . H14B H 1.0023 0.5973 0.2091 0.097 Uiso 1 1 calc R . . H14C H 1.1187 0.5280 0.2057 0.097 Uiso 1 1 calc R . . C15 C 0.6709(4) 0.6422(3) -0.0501(2) 0.0564(9) Uani 1 1 d . . . H15 H 0.7226 0.6153 -0.0868 0.068 Uiso 1 1 calc R . . C16 C 0.6589(4) 0.5925(3) 0.0367(3) 0.0601(9) Uani 1 1 d . . . H16 H 0.7010 0.5259 0.0691 0.072 Uiso 1 1 calc R . . C17 C 0.5723(3) 0.6599(4) 0.0675(3) 0.0617(10) Uani 1 1 d . . . H17 H 0.5467 0.6466 0.1241 0.074 Uiso 1 1 calc R . . C18 C 0.5312(3) 0.7504(3) -0.0017(3) 0.0594(10) Uani 1 1 d . . . H18 H 0.4727 0.8081 -0.0001 0.071 Uiso 1 1 calc R . . C19 C 0.5923(3) 0.7393(3) -0.0729(2) 0.0526(9) Uani 1 1 d . . . H19 H 0.5826 0.7890 -0.1278 0.063 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 0.0320(3) 0.0317(3) 0.0319(3) 0.00288(19) 0.00850(19) 0.0039(2) N1 0.0337(12) 0.0310(12) 0.0300(11) 0.0006(9) 0.0082(9) 0.0048(9) O1 0.0410(12) 0.0636(14) 0.0495(12) 0.0249(10) 0.0170(9) 0.0199(11) O2 0.0373(10) 0.0350(10) 0.0344(10) 0.0018(8) 0.0108(8) 0.0016(8) Cl1 0.0431(4) 0.0348(4) 0.0447(4) -0.0019(3) 0.0138(3) 0.0044(3) Cl2 0.0689(6) 0.0591(5) 0.0356(4) 0.0108(3) 0.0132(4) 0.0067(4) C1 0.0325(14) 0.0401(16) 0.0338(14) -0.0024(11) 0.0058(11) 0.0045(12) C2 0.0429(17) 0.0392(17) 0.0440(16) -0.0004(13) 0.0059(13) 0.0099(13) C3 0.0392(16) 0.0427(17) 0.0556(18) -0.0066(14) 0.0048(14) 0.0154(14) C4 0.0353(15) 0.0474(18) 0.0587(19) -0.0066(15) 0.0150(14) 0.0043(14) C5 0.0355(15) 0.0410(16) 0.0450(16) -0.0018(13) 0.0109(12) 0.0000(13) C6 0.0320(14) 0.0320(14) 0.0323(13) -0.0060(11) 0.0055(11) 0.0023(11) C7 0.0375(14) 0.0293(14) 0.0283(12) -0.0032(10) 0.0073(11) -0.0011(11) C8 0.0384(15) 0.0308(14) 0.0279(12) -0.0004(10) 0.0032(11) 0.0036(11) C9 0.0386(16) 0.0460(17) 0.0372(15) 0.0034(12) 0.0050(12) 0.0089(14) C10 0.0476(18) 0.058(2) 0.0431(17) 0.0070(14) 0.0010(14) 0.0178(16) C11 0.068(2) 0.051(2) 0.0384(16) 0.0138(14) 0.0041(15) 0.0154(17) C12 0.061(2) 0.0400(17) 0.0381(15) 0.0075(12) 0.0137(14) 0.0042(15) C13 0.0410(15) 0.0338(15) 0.0302(13) -0.0016(11) 0.0049(11) 0.0050(12) C14 0.062(2) 0.067(2) 0.066(2) 0.0258(19) 0.0157(18) 0.023(2) C15 0.076(2) 0.0427(19) 0.0527(19) -0.0140(15) 0.0188(17) -0.0005(17) C16 0.079(3) 0.0295(17) 0.067(2) 0.0010(15) 0.0063(19) -0.0010(17) C17 0.067(2) 0.061(2) 0.064(2) -0.0115(18) 0.0277(18) -0.033(2) C18 0.0370(18) 0.051(2) 0.084(3) -0.0232(19) 0.0009(18) -0.0077(16) C19 0.063(2) 0.0381(17) 0.0475(18) -0.0033(14) -0.0063(16) -0.0114(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 1.820(2) . ? Ti1 N1 2.248(2) . ? Ti1 C15 2.324(3) . ? Ti1 Cl1 2.3263(12) . ? Ti1 C16 2.333(3) . ? Ti1 C19 2.350(3) . ? Ti1 Cl2 2.3545(13) . ? Ti1 C17 2.368(3) . ? Ti1 C18 2.391(3) . ? N1 C7 1.310(3) . ? N1 C8 1.411(3) . ? O1 C1 1.323(3) . ? O2 C7 1.352(3) . ? O2 C13 1.376(3) . ? C1 C2 1.392(4) . ? C1 C6 1.393(4) . ? C2 C3 1.386(4) . ? C2 C14 1.499(4) . ? C3 C4 1.366(5) . ? C4 C5 1.373(4) . ? C5 C6 1.402(4) . ? C6 C7 1.430(4) . ? C8 C13 1.371(4) . ? C8 C9 1.383(4) . ? C9 C10 1.376(4) . ? C10 C11 1.398(5) . ? C11 C12 1.363(5) . ? C12 C13 1.373(4) . ? C15 C16 1.378(5) . ? C15 C19 1.382(5) . ? C16 C17 1.397(5) . ? C17 C18 1.389(5) . ? C18 C19 1.370(5) . ? 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 78.62(9) . . ? O1 Ti1 C15 88.72(13) . . ? N1 Ti1 C15 86.07(11) . . ? O1 Ti1 Cl1 128.78(9) . . ? N1 Ti1 Cl1 80.97(6) . . ? C15 Ti1 Cl1 135.94(10) . . ? O1 Ti1 C16 90.37(13) . . ? N1 Ti1 C16 120.06(11) . . ? C15 Ti1 C16 34.43(13) . . ? Cl1 Ti1 C16 139.97(11) . . ? O1 Ti1 C19 118.91(13) . . ? N1 Ti1 C19 77.79(11) . . ? C15 Ti1 C19 34.39(12) . . ? Cl1 Ti1 C19 101.56(9) . . ? C16 Ti1 C19 56.85(12) . . ? O1 Ti1 Cl2 86.32(7) . . ? N1 Ti1 Cl2 145.94(6) . . ? C15 Ti1 Cl2 124.27(10) . . ? Cl1 Ti1 Cl2 85.20(3) . . ? C16 Ti1 Cl2 90.09(10) . . ? C19 Ti1 Cl2 135.74(10) . . ? O1 Ti1 C17 122.02(14) . . ? N1 Ti1 C17 134.08(11) . . ? C15 Ti1 C17 57.08(13) . . ? Cl1 Ti1 C17 105.82(11) . . ? C16 Ti1 C17 34.56(14) . . ? C19 Ti1 C17 56.29(13) . . ? Cl2 Ti1 C17 79.66(10) . . ? O1 Ti1 C18 144.45(12) . . ? N1 Ti1 C18 104.59(12) . . ? C15 Ti1 C18 56.75(13) . . ? Cl1 Ti1 C18 86.17(9) . . ? C16 Ti1 C18 56.87(14) . . ? C19 Ti1 C18 33.56(13) . . ? Cl2 Ti1 C18 105.35(11) . . ? C17 Ti1 C18 33.93(14) . . ? C7 N1 C8 104.6(2) . . ? C7 N1 Ti1 124.44(17) . . ? C8 N1 Ti1 130.95(18) . . ? C1 O1 Ti1 149.02(19) . . ? C7 O2 C13 104.9(2) . . ? O1 C1 C2 120.3(3) . . ? O1 C1 C6 118.6(2) . . ? C2 C1 C6 121.0(3) . . ? C3 C2 C1 117.4(3) . . ? C3 C2 C14 122.8(3) . . ? C1 C2 C14 119.8(3) . . ? C4 C3 C2 122.3(3) . . ? C3 C4 C5 120.5(3) . . ? C4 C5 C6 119.1(3) . . ? C1 C6 C5 119.6(3) . . ? C1 C6 C7 119.0(2) . . ? C5 C6 C7 121.4(3) . . ? N1 C7 O2 114.3(2) . . ? N1 C7 C6 129.4(2) . . ? O2 C7 C6 116.2(2) . . ? C13 C8 C9 119.5(3) . . ? C13 C8 N1 107.9(2) . . ? C9 C8 N1 132.6(3) . . ? C10 C9 C8 117.1(3) . . ? C9 C10 C11 121.6(3) . . ? C12 C11 C10 121.9(3) . . ? C11 C12 C13 115.1(3) . . ? C8 C13 C12 124.9(3) . . ? C8 C13 O2 108.3(2) . . ? C12 C13 O2 126.8(3) . . ? C16 C15 C19 107.7(3) . . ? C16 C15 Ti1 73.1(2) . . ? C19 C15 Ti1 73.86(18) . . ? C15 C16 C17 107.8(3) . . ? C15 C16 Ti1 72.4(2) . . ? C17 C16 Ti1 74.1(2) . . ? C18 C17 C16 107.8(3) . . ? C18 C17 Ti1 73.95(19) . . ? C16 C17 Ti1 71.3(2) . . ? C19 C18 C17 107.6(3) . . ? C19 C18 Ti1 71.6(2) . . ? C17 C18 Ti1 72.12(19) . . ? C18 C19 C15 109.1(3) . . ? C18 C19 Ti1 74.86(19) . . ? C15 C19 Ti1 71.75(19) . . ? _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 27.16 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 0.836 _refine_diff_density_min -0.285 _refine_diff_density_rms 0.101