# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Alan Cowley' 'Colin D. Abernethy' 'Jennifer A. Johnson' 'Piyush Shukla' 'Dragoslav Vidovic' _publ_contact_author_name 'Prof Alan Cowley' _publ_contact_author_address ; Chemistry and Biochemistry University of Texas at Austin 1 University Station A5300 Austin TX 78712-0165 UNITED STATES OF AMERICA ; _publ_contact_author_email COWLEY@MAIL.UTEXAS.EDU _publ_requested_journal 'Chemical Communications' _publ_section_title ; Amine elimination synthesis of a titanium(IV) N-heterocyclic carbene complex with short intramolecular Cl. . .Ccarbene contacts ; _publ_section_references ; Cooper, R. I., Gould, R. O., Parsons, S. and Watkins, D. J. ROTAX. (2002). J. Appl. Cryst. 35, 168-174. Farrugia, L. J. (1999). WinGX. J. Appl. Cryst. 32, 837-838. Sheldrick, G. M. (1998). SHELXTL/PC. Release 5.10. Siemens Analytical X-ray Instruments, Inc., Madison, WI, USA. Siemens (1994). XSCANS 2.10b. Siemens Analytical X-ray Instruments, Inc., Madison, WI, USA. ; data_ti _database_code_depnum_ccdc_archive 'CCDC 224825' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C25 H36 Cl2 N4 Ti' _chemical_formula_weight 511.38 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 P21/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 11.492(2) _cell_length_b 14.182(3) _cell_length_c 16.649(3) _cell_angle_alpha 90.00 _cell_angle_beta 92.34(3) _cell_angle_gamma 90.00 _cell_volume 2711.2(9) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.253 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1080 _exptl_absorpt_coefficient_mu 0.532 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Siemens P4' _diffrn_measurement_method \w-scans _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8944 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0972 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.12 _diffrn_reflns_theta_max 25.05 _reflns_number_total 8944 _reflns_number_gt 6219 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'XSCANS v2.10b, Siemens Analytical' _computing_cell_refinement 'XSCANS v2.10b, Siemens Analytical' _computing_data_reduction 'XSCANS v2.10b, Siemens Analytical' _computing_structure_solution 'XS SHELXTL/PC, Siemens Analytical' _computing_structure_refinement 'XL SHELXTL/PC, Siemens Analytical' _computing_molecular_graphics 'XP SHELXTL/PC, Siemens Analytical' _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The data were corrected for twinning. The twin law was suggested by use of the routine ROTAX (Cooper, Gould, Parsons and Watkin, 2002) as setup in WinGX (Farrugia, 1999). The twinning was by rotation about the 1,0,0 direct axis. The twin law was 1,0,0; 0.18,-1,0; 0.29,0,-1. The twin fraction refined to 0.353(3). ; _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^)+(0.1011P)^2^+9.9114P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8944 _refine_ls_number_parameters 290 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1367 _refine_ls_R_factor_gt 0.0942 _refine_ls_wR_factor_ref 0.2500 _refine_ls_wR_factor_gt 0.2235 _refine_ls_goodness_of_fit_ref 1.024 _refine_ls_restrained_S_all 1.024 _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 0.44945(8) 0.31900(6) 0.22044(5) 0.0275(3) Uani 1 1 d . . . Cl1 Cl 0.24565(11) 0.29345(9) 0.21385(9) 0.0435(4) Uani 1 1 d . . . Cl2 Cl 0.65279(11) 0.30216(10) 0.24362(9) 0.0433(4) Uani 1 1 d . . . N1 N 0.4575(4) 0.0875(3) 0.2536(2) 0.0318(10) Uani 1 1 d . . . N2 N 0.4635(4) 0.1118(3) 0.1268(2) 0.0307(10) Uani 1 1 d . . . N3 N 0.4450(4) 0.4020(3) 0.3078(3) 0.0365(10) Uani 1 1 d . . . N4 N 0.4606(4) 0.3886(3) 0.1251(2) 0.0331(10) Uani 1 1 d . . . C1 C 0.4577(4) 0.1582(3) 0.1984(3) 0.0278(11) Uani 1 1 d . . . C2 C 0.4627(6) 0.0001(3) 0.2164(3) 0.0463(15) Uani 1 1 d . . . H2 H 0.4624 -0.0600 0.2429 0.056 Uiso 1 1 d R . . C3 C 0.4677(6) 0.0145(3) 0.1383(3) 0.0469(15) Uani 1 1 d . . . H3 H 0.4731 -0.0330 0.0975 0.056 Uiso 1 1 d R . . C4 C 0.4533(4) 0.1010(3) 0.3394(3) 0.0294(11) Uani 1 1 d . . . C5 C 0.5582(5) 0.1083(3) 0.3840(3) 0.0340(12) Uani 1 1 d . . . C6 C 0.5504(5) 0.1263(4) 0.4665(3) 0.0385(13) Uani 1 1 d . . . H6 H 0.6213 0.1328 0.4986 0.046 Uiso 1 1 d R . . C7 C 0.4454(5) 0.1337(3) 0.5029(3) 0.0379(13) Uani 1 1 d . . . C8 C 0.3440(5) 0.1187(3) 0.4556(3) 0.0340(12) Uani 1 1 d . . . H8 H 0.2702 0.1203 0.4804 0.041 Uiso 1 1 d R . . C9 C 0.3463(4) 0.1010(3) 0.3740(3) 0.0303(11) Uani 1 1 d . . . C10 C 0.6744(5) 0.0929(4) 0.3480(4) 0.0482(15) Uani 1 1 d . . . H10A H 0.6640 0.0822 0.2912 0.072 Uiso 1 1 d R . . H10B H 0.7223 0.1475 0.3573 0.072 Uiso 1 1 d R . . H10C H 0.7114 0.0389 0.3728 0.072 Uiso 1 1 d R . . C11 C 0.4409(6) 0.1578(4) 0.5909(3) 0.0526(16) Uani 1 1 d . . . H11C H 0.4705 0.2207 0.5975 0.079 Uiso 1 1 d R . . H11A H 0.4898 0.1165 0.6231 0.079 Uiso 1 1 d R . . H11B H 0.3633 0.1568 0.6101 0.079 Uiso 1 1 d R . . C12 C 0.2352(5) 0.0802(4) 0.3258(3) 0.0381(13) Uani 1 1 d . . . H12A H 0.1699 0.0832 0.3598 0.057 Uiso 1 1 d R . . H12B H 0.2252 0.1256 0.2833 0.057 Uiso 1 1 d R . . H12C H 0.2404 0.0182 0.3032 0.057 Uiso 1 1 d R . . C13 C 0.4619(5) 0.1526(3) 0.0466(3) 0.0302(11) Uani 1 1 d . . . C14 C 0.3571(4) 0.1560(3) 0.0031(3) 0.0329(12) Uani 1 1 d . . . C15 C 0.3576(4) 0.1912(4) -0.0753(3) 0.0333(12) Uani 1 1 d . . . H15 H 0.2858 0.1933 -0.1069 0.040 Uiso 1 1 d R . . C16 C 0.4591(4) 0.2208(3) -0.1086(3) 0.0294(11) Uani 1 1 d . . . C17 C 0.5630(5) 0.2145(3) -0.0636(3) 0.0324(11) Uani 1 1 d . . . H17 H 0.6339 0.2355 -0.0863 0.039 Uiso 1 1 d R . . C18 C 0.5677(4) 0.1779(3) 0.0143(3) 0.0312(11) Uani 1 1 d . . . C19 C 0.2444(5) 0.1237(4) 0.0384(3) 0.0455(14) Uani 1 1 d . . . H19C H 0.1846 0.1314 -0.0030 0.068 Uiso 1 1 d R . . H19A H 0.2218 0.1617 0.0829 0.068 Uiso 1 1 d R . . H19B H 0.2448 0.0582 0.0528 0.068 Uiso 1 1 d R . . C20 C 0.4565(5) 0.2599(4) -0.1938(3) 0.0373(12) Uani 1 1 d . . . H20A H 0.3775 0.2590 -0.2148 0.056 Uiso 1 1 d R . . H20B H 0.4855 0.3233 -0.1940 0.056 Uiso 1 1 d R . . H20C H 0.5037 0.2210 -0.2266 0.056 Uiso 1 1 d R . . C21 C 0.6813(5) 0.1659(4) 0.0609(3) 0.0453(14) Uani 1 1 d . . . H21A H 0.7441 0.1872 0.0293 0.068 Uiso 1 1 d R . . H21B H 0.6804 0.2018 0.1098 0.068 Uiso 1 1 d R . . H21C H 0.6918 0.1003 0.0736 0.068 Uiso 1 1 d R . . C22 C 0.4147(7) 0.3603(4) 0.3832(4) 0.0610(19) Uani 1 1 d . . . H22C H 0.3387 0.3827 0.3956 0.092 Uiso 1 1 d R . . H22A H 0.4677 0.3783 0.4265 0.092 Uiso 1 1 d R . . H22B H 0.4109 0.2928 0.3797 0.092 Uiso 1 1 d R . . C23 C 0.4919(6) 0.4970(4) 0.3174(4) 0.0537(16) Uani 1 1 d . . . H23C H 0.5203 0.5182 0.2671 0.081 Uiso 1 1 d R . . H23A H 0.5548 0.4969 0.3572 0.081 Uiso 1 1 d R . . H23B H 0.4329 0.5396 0.3345 0.081 Uiso 1 1 d R . . C24 C 0.3773(5) 0.3868(4) 0.0578(3) 0.0398(13) Uani 1 1 d . . . H24C H 0.4173 0.3739 0.0095 0.060 Uiso 1 1 d R . . H24A H 0.3376 0.4461 0.0519 0.060 Uiso 1 1 d R . . H24B H 0.3208 0.3381 0.0653 0.060 Uiso 1 1 d R . . C25 C 0.5560(5) 0.4544(4) 0.1093(4) 0.0468(14) Uani 1 1 d . . . H25A H 0.5441 0.4822 0.0570 0.070 Uiso 1 1 d R . . H25B H 0.5572 0.5030 0.1494 0.070 Uiso 1 1 d R . . H25C H 0.6288 0.4212 0.1118 0.070 Uiso 1 1 d 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 0.0294(5) 0.0211(4) 0.0323(5) 0.0017(4) 0.0045(4) 0.0012(4) Cl1 0.0293(7) 0.0343(7) 0.0676(9) 0.0057(6) 0.0098(6) 0.0020(5) Cl2 0.0314(7) 0.0409(8) 0.0567(9) -0.0043(6) -0.0110(6) 0.0004(6) N1 0.044(3) 0.023(2) 0.028(2) 0.0037(17) -0.0002(18) -0.0012(18) N2 0.044(3) 0.0193(19) 0.029(2) 0.0011(17) 0.0033(18) 0.0029(18) N3 0.043(3) 0.026(2) 0.041(2) -0.0006(19) 0.006(2) -0.0006(19) N4 0.034(2) 0.025(2) 0.041(2) 0.0025(18) 0.0012(19) -0.0007(18) C1 0.027(3) 0.024(2) 0.032(3) 0.003(2) 0.002(2) -0.001(2) C2 0.089(5) 0.016(2) 0.034(3) 0.002(2) 0.000(3) 0.005(3) C3 0.084(5) 0.016(2) 0.041(3) -0.003(2) 0.004(3) 0.005(3) C4 0.040(3) 0.017(2) 0.031(3) 0.0073(19) 0.001(2) 0.002(2) C5 0.035(3) 0.026(2) 0.041(3) 0.003(2) 0.000(2) 0.004(2) C6 0.048(4) 0.031(3) 0.035(3) 0.004(2) -0.012(2) 0.001(2) C7 0.056(4) 0.026(3) 0.032(3) 0.008(2) 0.000(3) 0.000(2) C8 0.039(3) 0.028(3) 0.035(3) 0.006(2) 0.006(2) 0.001(2) C9 0.041(3) 0.018(2) 0.032(3) 0.009(2) -0.002(2) -0.002(2) C10 0.040(3) 0.046(4) 0.059(4) 0.006(3) 0.002(3) 0.005(3) C11 0.074(5) 0.052(4) 0.030(3) 0.002(3) -0.007(3) 0.005(3) C12 0.036(3) 0.034(3) 0.045(3) 0.010(2) 0.001(2) -0.002(2) C13 0.045(3) 0.020(2) 0.026(3) -0.0041(19) 0.002(2) 0.002(2) C14 0.037(3) 0.027(3) 0.035(3) -0.003(2) 0.007(2) 0.001(2) C15 0.031(3) 0.037(3) 0.031(3) -0.001(2) -0.002(2) 0.000(2) C16 0.040(3) 0.023(2) 0.026(2) -0.002(2) 0.002(2) 0.003(2) C17 0.037(3) 0.027(3) 0.034(3) -0.005(2) 0.005(2) -0.004(2) C18 0.037(3) 0.025(2) 0.032(3) -0.006(2) -0.001(2) 0.001(2) C19 0.039(3) 0.054(4) 0.044(3) 0.009(3) 0.003(3) -0.012(3) C20 0.037(3) 0.042(3) 0.032(3) 0.001(2) 0.000(2) 0.001(2) C21 0.035(3) 0.053(4) 0.047(3) 0.001(3) 0.001(3) 0.004(3) C22 0.102(6) 0.041(3) 0.040(3) 0.004(3) 0.011(3) -0.003(4) C23 0.068(4) 0.039(3) 0.055(4) -0.009(3) 0.009(3) -0.011(3) C24 0.048(3) 0.033(3) 0.038(3) 0.003(2) -0.004(3) -0.002(2) C25 0.043(3) 0.048(3) 0.050(3) 0.011(3) 0.007(3) -0.008(3) _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 N3 1.874(4) . ? Ti1 N4 1.878(4) . ? Ti1 C1 2.313(5) . ? Ti1 Cl2 2.3649(17) . ? Ti1 Cl1 2.3680(16) . ? N1 C1 1.360(6) . ? N1 C2 1.387(6) . ? N1 C4 1.444(6) . ? N2 C1 1.366(6) . ? N2 C3 1.394(6) . ? N2 C13 1.455(6) . ? N3 C22 1.443(7) . ? N3 C23 1.457(7) . ? N4 C24 1.445(7) . ? N4 C25 1.471(7) . ? C2 C3 1.321(8) . ? C2 H2 0.9599 . ? C3 H3 0.9598 . ? C4 C9 1.379(7) . ? C4 C5 1.393(7) . ? C5 C6 1.403(7) . ? C5 C10 1.503(7) . ? C6 C7 1.377(8) . ? C6 H6 0.9600 . ? C7 C8 1.396(8) . ? C7 C11 1.506(7) . ? C8 C9 1.383(7) . ? C8 H8 0.9599 . ? C9 C12 1.509(7) . ? C10 H10A 0.9601 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C11 H11C 0.9599 . ? C11 H11A 0.9600 . ? C11 H11B 0.9601 . ? C12 H12A 0.9600 . ? C12 H12B 0.9601 . ? C12 H12C 0.9599 . ? C13 C14 1.381(7) . ? C13 C18 1.396(7) . ? C14 C15 1.397(7) . ? C14 C19 1.516(7) . ? C15 C16 1.377(7) . ? C15 H15 0.9600 . ? C16 C17 1.387(7) . ? C16 C20 1.521(7) . ? C17 C18 1.395(7) . ? C17 H17 0.9600 . ? C18 C21 1.501(7) . ? C19 H19C 0.9600 . ? C19 H19A 0.9601 . ? C19 H19B 0.9599 . ? C20 H20A 0.9601 . ? C20 H20B 0.9599 . ? C20 H20C 0.9600 . ? C21 H21A 0.9600 . ? C21 H21B 0.9600 . ? C21 H21C 0.9599 . ? C22 H22C 0.9600 . ? C22 H22A 0.9601 . ? C22 H22B 0.9600 . ? C23 H23C 0.9599 . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C24 H24C 0.9600 . ? C24 H24A 0.9599 . ? C24 H24B 0.9600 . ? C25 H25A 0.9600 . ? C25 H25B 0.9599 . ? C25 H25C 0.9599 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N3 Ti1 N4 109.30(18) . . ? N3 Ti1 C1 138.20(17) . . ? N4 Ti1 C1 112.33(17) . . ? N3 Ti1 Cl2 89.71(15) . . ? N4 Ti1 Cl2 95.17(14) . . ? C1 Ti1 Cl2 83.09(12) . . ? N3 Ti1 Cl1 94.23(15) . . ? N4 Ti1 Cl1 98.20(14) . . ? C1 Ti1 Cl1 83.60(12) . . ? Cl2 Ti1 Cl1 163.93(6) . . ? C1 N1 C2 110.8(4) . . ? C1 N1 C4 124.9(4) . . ? C2 N1 C4 124.3(4) . . ? C1 N2 C3 111.1(4) . . ? C1 N2 C13 127.7(4) . . ? C3 N2 C13 121.3(4) . . ? C22 N3 C23 112.6(5) . . ? C22 N3 Ti1 115.6(4) . . ? C23 N3 Ti1 130.1(4) . . ? C24 N4 C25 110.3(4) . . ? C24 N4 Ti1 125.5(3) . . ? C25 N4 Ti1 124.2(4) . . ? N1 C1 N2 103.7(4) . . ? N1 C1 Ti1 128.2(3) . . ? N2 C1 Ti1 128.1(3) . . ? C3 C2 N1 107.9(4) . . ? C3 C2 H2 126.1 . . ? N1 C2 H2 126.0 . . ? C2 C3 N2 106.6(4) . . ? C2 C3 H3 126.5 . . ? N2 C3 H3 126.9 . . ? C9 C4 C5 123.0(4) . . ? C9 C4 N1 118.6(4) . . ? C5 C4 N1 118.3(5) . . ? C4 C5 C6 116.6(5) . . ? C4 C5 C10 122.7(5) . . ? C6 C5 C10 120.7(5) . . ? C7 C6 C5 122.5(5) . . ? C7 C6 H6 119.1 . . ? C5 C6 H6 118.4 . . ? C6 C7 C8 117.7(5) . . ? C6 C7 C11 120.7(5) . . ? C8 C7 C11 121.5(5) . . ? C9 C8 C7 122.3(5) . . ? C9 C8 H8 118.7 . . ? C7 C8 H8 119.0 . . ? C4 C9 C8 117.5(5) . . ? C4 C9 C12 121.9(4) . . ? C8 C9 C12 120.6(5) . . ? C5 C10 H10A 109.8 . . ? C5 C10 H10B 109.3 . . ? H10A C10 H10B 109.5 . . ? C5 C10 H10C 109.3 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C7 C11 H11C 107.3 . . ? C7 C11 H11A 111.3 . . ? H11C C11 H11A 107.8 . . ? C7 C11 H11B 112.9 . . ? H11C C11 H11B 107.8 . . ? H11A C11 H11B 109.6 . . ? C9 C12 H12A 110.0 . . ? C9 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C9 C12 H12C 108.8 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C14 C13 C18 122.9(4) . . ? C14 C13 N2 118.3(4) . . ? C18 C13 N2 118.5(4) . . ? C13 C14 C15 117.8(5) . . ? C13 C14 C19 121.8(5) . . ? C15 C14 C19 120.4(5) . . ? C16 C15 C14 121.4(5) . . ? C16 C15 H15 119.5 . . ? C14 C15 H15 119.1 . . ? C15 C16 C17 119.2(4) . . ? C15 C16 C20 120.1(4) . . ? C17 C16 C20 120.7(5) . . ? C16 C17 C18 121.8(5) . . ? C16 C17 H17 119.5 . . ? C18 C17 H17 118.7 . . ? C17 C18 C13 116.9(5) . . ? C17 C18 C21 121.6(5) . . ? C13 C18 C21 121.6(4) . . ? C14 C19 H19C 106.5 . . ? C14 C19 H19A 113.1 . . ? H19C C19 H19A 106.5 . . ? C14 C19 H19B 113.2 . . ? H19C C19 H19B 106.5 . . ? H19A C19 H19B 110.5 . . ? C16 C20 H20A 108.5 . . ? C16 C20 H20B 110.6 . . ? H20A C20 H20B 109.5 . . ? C16 C20 H20C 109.4 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C18 C21 H21A 109.7 . . ? C18 C21 H21B 109.9 . . ? H21A C21 H21B 109.5 . . ? C18 C21 H21C 108.8 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N3 C22 H22C 107.8 . . ? N3 C22 H22A 112.1 . . ? H22C C22 H22A 107.7 . . ? N3 C22 H22B 111.7 . . ? H22C C22 H22B 107.7 . . ? H22A C22 H22B 109.6 . . ? N3 C23 H23C 109.4 . . ? N3 C23 H23A 109.8 . . ? H23C C23 H23A 109.2 . . ? N3 C23 H23B 110.6 . . ? H23C C23 H23B 109.2 . . ? H23A C23 H23B 108.5 . . ? N4 C24 H24C 109.2 . . ? N4 C24 H24A 111.1 . . ? H24C C24 H24A 108.9 . . ? N4 C24 H24B 110.0 . . ? H24C C24 H24B 108.9 . . ? H24A C24 H24B 108.8 . . ? N4 C25 H25A 110.1 . . ? N4 C25 H25B 108.7 . . ? H25A C25 H25B 109.5 . . ? N4 C25 H25C 109.6 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N4 Ti1 N3 C22 168.8(4) . . . . ? C1 Ti1 N3 C22 -16.5(6) . . . . ? Cl2 Ti1 N3 C22 -95.8(4) . . . . ? Cl1 Ti1 N3 C22 68.6(4) . . . . ? N4 Ti1 N3 C23 -26.9(6) . . . . ? C1 Ti1 N3 C23 147.8(5) . . . . ? Cl2 Ti1 N3 C23 68.5(5) . . . . ? Cl1 Ti1 N3 C23 -127.1(5) . . . . ? N3 Ti1 N4 C24 -120.0(4) . . . . ? C1 Ti1 N4 C24 63.9(4) . . . . ? Cl2 Ti1 N4 C24 148.5(4) . . . . ? Cl1 Ti1 N4 C24 -22.6(4) . . . . ? N3 Ti1 N4 C25 59.1(4) . . . . ? C1 Ti1 N4 C25 -117.0(4) . . . . ? Cl2 Ti1 N4 C25 -32.4(4) . . . . ? Cl1 Ti1 N4 C25 156.6(4) . . . . ? C2 N1 C1 N2 -0.3(6) . . . . ? C4 N1 C1 N2 179.4(4) . . . . ? C2 N1 C1 Ti1 179.6(4) . . . . ? C4 N1 C1 Ti1 -0.8(7) . . . . ? C3 N2 C1 N1 -0.4(6) . . . . ? C13 N2 C1 N1 177.5(5) . . . . ? C3 N2 C1 Ti1 179.8(4) . . . . ? C13 N2 C1 Ti1 -2.3(7) . . . . ? N3 Ti1 C1 N1 2.2(6) . . . . ? N4 Ti1 C1 N1 176.8(4) . . . . ? Cl2 Ti1 C1 N1 84.0(4) . . . . ? Cl1 Ti1 C1 N1 -87.0(4) . . . . ? N3 Ti1 C1 N2 -178.0(4) . . . . ? N4 Ti1 C1 N2 -3.4(5) . . . . ? Cl2 Ti1 C1 N2 -96.2(4) . . . . ? Cl1 Ti1 C1 N2 92.8(4) . . . . ? C1 N1 C2 C3 0.8(7) . . . . ? C4 N1 C2 C3 -178.8(5) . . . . ? N1 C2 C3 N2 -1.0(7) . . . . ? C1 N2 C3 C2 0.9(7) . . . . ? C13 N2 C3 C2 -177.1(5) . . . . ? C1 N1 C4 C9 92.7(6) . . . . ? C2 N1 C4 C9 -87.7(6) . . . . ? C1 N1 C4 C5 -90.7(6) . . . . ? C2 N1 C4 C5 88.9(6) . . . . ? C9 C4 C5 C6 -6.8(7) . . . . ? N1 C4 C5 C6 176.8(4) . . . . ? C9 C4 C5 C10 170.0(5) . . . . ? N1 C4 C5 C10 -6.5(7) . . . . ? C4 C5 C6 C7 1.9(7) . . . . ? C10 C5 C6 C7 -174.9(5) . . . . ? C5 C6 C7 C8 2.7(7) . . . . ? C5 C6 C7 C11 -177.0(5) . . . . ? C6 C7 C8 C9 -2.8(7) . . . . ? C11 C7 C8 C9 176.8(5) . . . . ? C5 C4 C9 C8 6.7(7) . . . . ? N1 C4 C9 C8 -176.9(4) . . . . ? C5 C4 C9 C12 -171.8(5) . . . . ? N1 C4 C9 C12 4.6(7) . . . . ? C7 C8 C9 C4 -1.7(7) . . . . ? C7 C8 C9 C12 176.8(5) . . . . ? C1 N2 C13 C14 -96.4(6) . . . . ? C3 N2 C13 C14 81.3(6) . . . . ? C1 N2 C13 C18 89.6(6) . . . . ? C3 N2 C13 C18 -92.7(6) . . . . ? C18 C13 C14 C15 -3.4(7) . . . . ? N2 C13 C14 C15 -177.0(4) . . . . ? C18 C13 C14 C19 177.1(5) . . . . ? N2 C13 C14 C19 3.4(7) . . . . ? C13 C14 C15 C16 0.6(7) . . . . ? C19 C14 C15 C16 -179.9(5) . . . . ? C14 C15 C16 C17 0.7(7) . . . . ? C14 C15 C16 C20 -179.2(5) . . . . ? C15 C16 C17 C18 0.8(7) . . . . ? C20 C16 C17 C18 -179.3(4) . . . . ? C16 C17 C18 C13 -3.3(7) . . . . ? C16 C17 C18 C21 176.3(5) . . . . ? C14 C13 C18 C17 4.7(7) . . . . ? N2 C13 C18 C17 178.3(4) . . . . ? C14 C13 C18 C21 -174.9(5) . . . . ? N2 C13 C18 C21 -1.3(7) . . . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 25.05 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.838 _refine_diff_density_min -0.629 _refine_diff_density_rms 0.111 #===END