Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 186 loop_ _publ_author_name 'I. Parkin' 'Claire J. Carmalt' 'Anne Newport' 'Andrew J. P. White' 'David J. Williams' _publ_contact_author_name 'Dr I Parkin' _publ_contact_author_address ; Department of Chemistry University College London 20 Gordon Street London WC1H 0AJ UNITED KINGDOM ; _publ_contact_author_email 'I.P.PARKIN@UCL.AC.UK' _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Titanium imido complexes as precursors to titanium nitride ; data_CC0106 _database_code_CSD 190026 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C36 H88 N8 Cl16 Ti4' _chemical_formula_weight 1391.94 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ti' 'Ti' 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.3997(12) _cell_length_b 12.952(3) _cell_length_c 13.5091(13) _cell_angle_alpha 63.134(10) _cell_angle_beta 63.229(8) _cell_angle_gamma 87.769(9) _cell_volume 1690.7(4) _cell_formula_units_Z 1 _cell_measurement_temperature 183(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 11.17 _cell_measurement_theta_max 24.95 _exptl_crystal_description prisms _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.43 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.33 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.367 _exptl_crystal_density_method ? _exptl_crystal_F_000 720 _exptl_absorpt_coefficient_mu 9.944 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.2617 _exptl_absorpt_correction_T_max 0.7152 _exptl_special_details ; ? ; _diffrn_ambient_temperature 183(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5014 _diffrn_reflns_av_R_equivalents 0.0266 _diffrn_reflns_av_sigmaI/netI 0.0454 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.91 _diffrn_reflns_theta_max 59.98 _reflns_number_total 4759 _reflns_number_observed 3879 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 229 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0635P)^2^+1.7552P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0008(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 4530 _refine_ls_number_parameters 318 _refine_ls_number_restraints 34 _refine_ls_R_factor_all 0.0617 _refine_ls_R_factor_obs 0.0466 _refine_ls_wR_factor_all 0.1221 _refine_ls_wR_factor_obs 0.1120 _refine_ls_goodness_of_fit_all 1.047 _refine_ls_goodness_of_fit_obs 1.084 _refine_ls_restrained_S_all 1.059 _refine_ls_restrained_S_obs 1.082 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti1 Ti 0.86604(6) 0.41462(6) 0.49939(7) 0.0141(2) Uani 1 d . . Ti2 Ti 1.19321(7) 0.33083(6) 0.40070(7) 0.0162(2) Uani 1 d . . Cl1 Cl 1.08012(9) 0.52751(8) 0.34598(8) 0.0166(2) Uani 1 d . . Cl2 Cl 0.96803(9) 0.24514(8) 0.55841(9) 0.0194(2) Uani 1 d . . Cl3 Cl 0.79018(9) 0.59600(9) 0.46591(9) 0.0208(3) Uani 1 d . . Cl4 Cl 1.37771(10) 0.46910(10) 0.22073(10) 0.0271(3) Uani 1 d . . N1 N 0.8276(3) 0.3990(3) 0.4025(3) 0.0180(8) Uani 1 d . . N2 N 0.7076(3) 0.3129(3) 0.6937(3) 0.0205(8) Uani 1 d D . H2A H 0.7469(36) 0.2711(34) 0.7362(37) 0.025(13) Uiso 1 d D . H2B H 0.6850(43) 0.3724(28) 0.7107(45) 0.030(14) Uiso 1 d D . N3 N 1.2461(3) 0.2094(3) 0.4614(3) 0.0192(8) Uani 1 d . . N4 N 1.1454(3) 0.3149(3) 0.2673(3) 0.0214(8) Uani 1 d D . H4A H 1.0631(6) 0.3091(37) 0.3065(34) 0.013(11) Uiso 1 d D . H4B H 1.1859(39) 0.3853(20) 0.1969(26) 0.029(13) Uiso 1 d D . C1 C 0.8021(4) 0.4121(4) 0.3013(4) 0.0233(10) Uani 1 d . . C2 C 0.7663(5) 0.2890(5) 0.3252(5) 0.0386(13) Uani 1 d . . H2C H 0.6917(5) 0.2453(5) 0.4077(5) 0.058 Uiso 1 calc R . H2D H 0.8338(5) 0.2470(5) 0.3249(5) 0.058 Uiso 1 calc R . H2E H 0.7501(5) 0.2952(5) 0.2582(5) 0.058 Uiso 1 calc R . C3 C 0.9171(5) 0.4829(4) 0.1744(4) 0.0314(11) Uani 1 d . . H3A H 0.9381(5) 0.5617(4) 0.1615(4) 0.047 Uiso 1 calc R . H3B H 0.9020(5) 0.4904(4) 0.1064(4) 0.047 Uiso 1 calc R . H3C H 0.9858(5) 0.4423(4) 0.1730(4) 0.047 Uiso 1 calc R . C4 C 0.6963(5) 0.4791(5) 0.3051(5) 0.0435(14) Uani 1 d . . H4C H 0.6216(5) 0.4335(5) 0.3871(5) 0.065 Uiso 1 calc R . H4D H 0.6802(5) 0.4897(5) 0.2367(5) 0.065 Uiso 1 calc R . H4E H 0.7196(5) 0.5566(5) 0.2938(5) 0.065 Uiso 1 calc R . C5 C 0.5927(4) 0.2323(4) 0.7401(4) 0.0276(11) Uani 1 d . . C6 C 0.5224(5) 0.3056(6) 0.6755(6) 0.051(2) Uani 1 d . . H6A H 0.4997(5) 0.3675(6) 0.6995(6) 0.076 Uiso 1 calc R . H6B H 0.4475(5) 0.2546(6) 0.7021(6) 0.076 Uiso 1 calc R . H6C H 0.5746(5) 0.3422(6) 0.5833(6) 0.076 Uiso 1 calc R . C7 C 0.5155(5) 0.1813(5) 0.8827(5) 0.049(2) Uani 1 d . . H7A H 0.5614(5) 0.1340(5) 0.9239(5) 0.073 Uiso 1 calc R . H7B H 0.4381(5) 0.1311(5) 0.9135(5) 0.073 Uiso 1 calc R . H7C H 0.4971(5) 0.2459(5) 0.9027(5) 0.073 Uiso 1 calc R . C8 C 0.6298(5) 0.1352(5) 0.7057(6) 0.051(2) Uani 1 d . . H8A H 0.6750(5) 0.0893(5) 0.7487(6) 0.076 Uiso 1 calc R . H8B H 0.6827(5) 0.1706(5) 0.6136(6) 0.076 Uiso 1 calc R . H8C H 0.5556(5) 0.0830(5) 0.7325(6) 0.076 Uiso 1 calc R . C9 C 1.2927(4) 0.1168(4) 0.5339(5) 0.0301(11) Uani 1 d D . C10 C 1.2025(10) 0.0678(11) 0.6727(8) 0.053(3) Uani 0.60 d PD 1 H10A H 1.1933(10) 0.1314(11) 0.6945(8) 0.080 Uiso 0.60 calc PR 1 H10B H 1.2330(10) 0.0063(11) 0.7232(8) 0.080 Uiso 0.60 calc PR 1 H10C H 1.1222(10) 0.0336(11) 0.6910(8) 0.080 Uiso 0.60 calc PR 1 C11 C 1.3119(11) 0.0235(9) 0.4928(12) 0.046(3) Uani 0.60 d PD 1 H11A H 1.3712(11) 0.0598(9) 0.4020(12) 0.069 Uiso 0.60 calc PR 1 H11B H 1.2330(11) -0.0112(9) 0.5089(12) 0.069 Uiso 0.60 calc PR 1 H11C H 1.3438(11) -0.0385(9) 0.5410(12) 0.069 Uiso 0.60 calc PR 1 C12 C 1.4162(8) 0.1789(8) 0.5008(10) 0.034(2) Uani 0.60 d PD 1 H12A H 1.4739(8) 0.2103(8) 0.4101(10) 0.051 Uiso 0.60 calc PR 1 H12B H 1.4505(8) 0.1221(8) 0.5506(10) 0.051 Uiso 0.60 calc PR 1 H12C H 1.4033(8) 0.2439(8) 0.5205(10) 0.051 Uiso 0.60 calc PR 1 C10' C 1.1787(14) 0.0305(16) 0.6626(14) 0.049(6) Uiso 0.40 d PD 2 H10D H 1.1219(14) -0.0020(16) 0.6466(14) 0.074 Uiso 0.40 calc PR 2 H10E H 1.1363(14) 0.0732(16) 0.7084(14) 0.074 Uiso 0.40 calc PR 2 H10F H 1.2060(14) -0.0342(16) 0.7138(14) 0.074 Uiso 0.40 calc PR 2 C11' C 1.3551(16) 0.0455(18) 0.4689(18) 0.051(6) Uiso 0.40 d PD 2 H11D H 1.2986(16) 0.0151(18) 0.4512(18) 0.076 Uiso 0.40 calc PR 2 H11E H 1.3773(16) -0.0209(18) 0.5243(18) 0.076 Uiso 0.40 calc PR 2 H11F H 1.4299(16) 0.0961(18) 0.3890(18) 0.076 Uiso 0.40 calc PR 2 C12' C 1.3774(17) 0.1647(19) 0.5623(19) 0.071(7) Uiso 0.40 d PD 2 H12D H 1.3355(17) 0.2106(19) 0.6043(19) 0.106 Uiso 0.40 calc PR 2 H12E H 1.4523(17) 0.2158(19) 0.4828(19) 0.106 Uiso 0.40 calc PR 2 H12F H 1.3997(17) 0.0989(19) 0.6181(19) 0.106 Uiso 0.40 calc PR 2 C13 C 1.1707(4) 0.2223(4) 0.2260(4) 0.0260(10) Uani 1 d . . C14 C 1.1300(5) 0.2482(5) 0.1275(5) 0.0403(13) Uani 1 d . . H14A H 1.0411(5) 0.2466(5) 0.1648(5) 0.060 Uiso 1 calc R . H14B H 1.1477(5) 0.1880(5) 0.1004(5) 0.060 Uiso 1 calc R . H14C H 1.1750(5) 0.3264(5) 0.0540(5) 0.060 Uiso 1 calc R . C15 C 1.0964(5) 0.1042(4) 0.3433(5) 0.0351(12) Uani 1 d . . H15A H 1.0082(5) 0.1054(4) 0.3772(5) 0.053 Uiso 1 calc R . H15B H 1.1203(5) 0.0898(4) 0.4077(5) 0.053 Uiso 1 calc R . H15C H 1.1129(5) 0.0410(4) 0.3207(5) 0.053 Uiso 1 calc R . C16 C 1.3066(5) 0.2242(5) 0.1709(5) 0.0394(13) Uani 1 d . . H16A H 1.3521(5) 0.3014(5) 0.0955(5) 0.059 Uiso 1 calc R . H16B H 1.3245(5) 0.1619(5) 0.1471(5) 0.059 Uiso 1 calc R . H16C H 1.3320(5) 0.2107(5) 0.2341(5) 0.059 Uiso 1 calc R . C20 C 1.3862(5) 0.6758(5) -0.0790(6) 0.052(2) Uani 1 d . . H20A H 1.4126(5) 0.6494(5) -0.0137(6) 0.063 Uiso 1 calc R . H20B H 1.4469(5) 0.6628(5) -0.1489(6) 0.063 Uiso 1 calc R . Cl5 Cl 1.2408(2) 0.59195(15) -0.01269(14) 0.0698(6) Uani 1 d . . Cl6 Cl 1.3845(2) 0.8248(2) -0.1369(2) 0.0909(7) Uani 1 d . . C30 C 1.0661(8) 0.8162(7) 0.1313(7) 0.080(2) Uani 1 d . . H30A H 1.1059(8) 0.7473(7) 0.1374(7) 0.096 Uiso 1 calc R . H30B H 0.9996(8) 0.7947(7) 0.2178(7) 0.096 Uiso 1 calc R . Cl7 Cl 1.1746(2) 0.9328(2) 0.0825(2) 0.0852(6) Uani 1 d . . Cl8 Cl 1.0011(3) 0.8378(2) 0.0404(3) 0.1230(11) Uani 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 0.0134(4) 0.0150(4) 0.0145(4) -0.0079(3) -0.0066(3) 0.0024(3) Ti2 0.0169(4) 0.0166(4) 0.0177(4) -0.0103(3) -0.0085(3) 0.0057(3) Cl1 0.0169(5) 0.0176(5) 0.0139(5) -0.0065(4) -0.0073(4) 0.0019(4) Cl2 0.0191(5) 0.0161(5) 0.0186(5) -0.0069(4) -0.0074(4) 0.0049(4) Cl3 0.0278(6) 0.0212(5) 0.0251(5) -0.0147(4) -0.0187(5) 0.0109(4) Cl4 0.0201(5) 0.0278(6) 0.0261(6) -0.0153(5) -0.0033(5) 0.0011(4) N1 0.017(2) 0.019(2) 0.021(2) -0.0118(15) -0.009(2) 0.0039(15) N2 0.019(2) 0.020(2) 0.025(2) -0.013(2) -0.010(2) 0.003(2) N3 0.021(2) 0.017(2) 0.026(2) -0.013(2) -0.014(2) 0.0104(15) N4 0.019(2) 0.022(2) 0.020(2) -0.011(2) -0.006(2) 0.003(2) C1 0.025(2) 0.029(3) 0.021(2) -0.011(2) -0.016(2) 0.002(2) C2 0.053(3) 0.037(3) 0.040(3) -0.019(2) -0.031(3) 0.000(3) C3 0.038(3) 0.033(3) 0.020(2) -0.008(2) -0.015(2) 0.002(2) C4 0.043(3) 0.067(4) 0.045(3) -0.033(3) -0.035(3) 0.029(3) C5 0.018(2) 0.031(3) 0.024(2) -0.012(2) -0.002(2) -0.007(2) C6 0.023(3) 0.072(4) 0.052(4) -0.026(3) -0.017(3) 0.003(3) C7 0.031(3) 0.055(4) 0.033(3) -0.015(3) 0.001(3) -0.015(3) C8 0.048(4) 0.038(3) 0.053(4) -0.027(3) -0.009(3) -0.013(3) C9 0.028(3) 0.029(3) 0.040(3) -0.017(2) -0.022(2) 0.014(2) C10 0.056(7) 0.055(7) 0.030(6) -0.008(5) -0.021(5) 0.016(6) C11 0.038(6) 0.017(5) 0.082(9) -0.014(5) -0.039(6) 0.010(5) C12 0.029(5) 0.038(5) 0.056(7) -0.023(5) -0.038(5) 0.018(4) C13 0.033(3) 0.025(2) 0.026(2) -0.018(2) -0.013(2) 0.005(2) C14 0.055(4) 0.048(3) 0.036(3) -0.030(3) -0.027(3) 0.011(3) C15 0.045(3) 0.023(3) 0.039(3) -0.018(2) -0.018(3) 0.001(2) C16 0.034(3) 0.050(3) 0.038(3) -0.033(3) -0.009(3) 0.012(3) C20 0.040(3) 0.047(4) 0.046(4) -0.013(3) -0.012(3) -0.002(3) Cl5 0.0681(11) 0.0697(11) 0.0438(9) 0.0041(7) -0.0347(8) -0.0288(9) Cl6 0.0584(11) 0.0519(10) 0.136(2) -0.0400(12) -0.0333(12) 0.0102(9) C30 0.093(6) 0.083(5) 0.051(4) -0.015(4) -0.042(4) 0.011(5) Cl7 0.0810(14) 0.0901(14) 0.0728(13) -0.0327(11) -0.0345(11) 0.0066(11) Cl8 0.203(3) 0.0745(14) 0.130(2) -0.0242(14) -0.134(2) 0.013(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 N1 1.671(3) . ? Ti1 N2 2.217(4) . ? Ti1 Cl3 2.4205(13) . ? Ti1 Cl1 2.4672(12) . ? Ti1 Cl2 2.4828(12) . ? Ti1 Cl1 2.8429(12) 2_766 ? Ti2 N3 1.677(3) . ? Ti2 N4 2.226(4) . ? Ti2 Cl4 2.3927(14) . ? Ti2 Cl3 2.4659(12) 2_766 ? Ti2 Cl2 2.5125(13) . ? Ti2 Cl1 2.8206(13) . ? Cl1 Ti1 2.8429(12) 2_766 ? Cl3 Ti2 2.4659(12) 2_766 ? N1 C1 1.474(5) . ? N2 C5 1.495(5) . ? N3 C9 1.458(5) . ? N4 C13 1.504(6) . ? C1 C3 1.514(6) . ? C1 C2 1.519(7) . ? C1 C4 1.539(6) . ? C5 C6 1.514(7) . ? C5 C8 1.516(7) . ? C5 C7 1.517(7) . ? C9 C10 1.504(9) . ? C9 C12' 1.504(14) . ? C9 C11' 1.513(14) . ? C9 C11 1.514(10) . ? C9 C12 1.531(8) . ? C9 C10' 1.557(14) . ? C13 C16 1.501(7) . ? C13 C15 1.518(6) . ? C13 C14 1.526(6) . ? C20 Cl6 1.727(6) . ? C20 Cl5 1.747(6) . ? C30 Cl8 1.673(7) . ? C30 Cl7 1.728(8) . ? 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 N1 Ti1 N2 106.6(2) . . ? N1 Ti1 Cl3 92.40(12) . . ? N2 Ti1 Cl3 92.38(10) . . ? N1 Ti1 Cl1 99.66(12) . . ? N2 Ti1 Cl1 153.32(10) . . ? Cl3 Ti1 Cl1 90.93(4) . . ? N1 Ti1 Cl2 101.99(12) . . ? N2 Ti1 Cl2 86.71(10) . . ? Cl3 Ti1 Cl2 165.24(4) . . ? Cl1 Ti1 Cl2 83.48(4) . . ? N1 Ti1 Cl1 171.79(12) . 2_766 ? N2 Ti1 Cl1 74.54(9) . 2_766 ? Cl3 Ti1 Cl1 79.40(4) . 2_766 ? Cl1 Ti1 Cl1 80.09(4) . 2_766 ? Cl2 Ti1 Cl1 86.17(4) . 2_766 ? N3 Ti2 N4 106.5(2) . . ? N3 Ti2 Cl4 102.76(13) . . ? N4 Ti2 Cl4 88.32(10) . . ? N3 Ti2 Cl3 92.57(12) . 2_766 ? N4 Ti2 Cl3 160.67(11) . 2_766 ? Cl4 Ti2 Cl3 90.64(4) . 2_766 ? N3 Ti2 Cl2 97.13(13) . . ? N4 Ti2 Cl2 84.91(10) . . ? Cl4 Ti2 Cl2 160.08(5) . . ? Cl3 Ti2 Cl2 89.63(4) 2_766 . ? N3 Ti2 Cl1 169.18(13) . . ? N4 Ti2 Cl1 81.57(10) . . ? Cl4 Ti2 Cl1 84.41(4) . . ? Cl3 Ti2 Cl1 79.12(4) 2_766 . ? Cl2 Ti2 Cl1 76.08(4) . . ? Ti1 Cl1 Ti2 96.03(4) . . ? Ti1 Cl1 Ti1 99.91(4) . 2_766 ? Ti2 Cl1 Ti1 90.48(3) . 2_766 ? Ti1 Cl2 Ti2 104.05(4) . . ? Ti1 Cl3 Ti2 110.76(4) . 2_766 ? C1 N1 Ti1 168.1(3) . . ? C5 N2 Ti1 129.8(3) . . ? C9 N3 Ti2 165.2(3) . . ? C13 N4 Ti2 127.0(3) . . ? N1 C1 C3 108.7(3) . . ? N1 C1 C2 107.7(4) . . ? C3 C1 C2 111.3(4) . . ? N1 C1 C4 109.1(4) . . ? C3 C1 C4 109.2(4) . . ? C2 C1 C4 110.7(4) . . ? N2 C5 C6 107.5(4) . . ? N2 C5 C8 108.2(4) . . ? C6 C5 C8 111.3(5) . . ? N2 C5 C7 108.9(4) . . ? C6 C5 C7 109.8(4) . . ? C8 C5 C7 111.1(4) . . ? N3 C9 C10 108.2(5) . . ? N3 C9 C12' 112.3(9) . . ? N3 C9 C11' 111.8(9) . . ? C12' C9 C11' 110.7(10) . . ? N3 C9 C11 109.4(5) . . ? C10 C9 C11 112.6(7) . . ? N3 C9 C12 105.2(5) . . ? C10 C9 C12 110.5(7) . . ? C11 C9 C12 110.5(6) . . ? N3 C9 C10' 106.9(8) . . ? C12' C9 C10' 107.9(9) . . ? C11' C9 C10' 107.0(9) . . ? C16 C13 N4 108.2(4) . . ? C16 C13 C15 111.3(4) . . ? N4 C13 C15 107.0(4) . . ? C16 C13 C14 110.4(4) . . ? N4 C13 C14 110.0(4) . . ? C15 C13 C14 109.9(4) . . ? Cl6 C20 Cl5 111.4(4) . . ? Cl8 C30 Cl7 117.0(4) . . ? _refine_diff_density_max 0.582 _refine_diff_density_min -0.600 _refine_diff_density_rms 0.081 data_CC0109 _database_code_CSD 190027 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C19.50 H25 N4 Cl3 Ti' _chemical_formula_weight 469.69 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ti' 'Ti' 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pna2(1) 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' _cell_length_a 16.8801(9) _cell_length_b 9.2147(3) _cell_length_c 29.0003(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4510.9(3) _cell_formula_units_Z 8 _cell_measurement_temperature 183(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 11.01 _cell_measurement_theta_max 26.39 _exptl_crystal_description prisms _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.383 _exptl_crystal_density_method ? _exptl_crystal_F_000 1944 _exptl_absorpt_coefficient_mu 6.576 _exptl_absorpt_correction_type Ellipsoidal _exptl_absorpt_correction_T_min 0.2147 _exptl_absorpt_correction_T_max 0.2998 _exptl_special_details ; ? ; _diffrn_ambient_temperature 183(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3421 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0494 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 3.05 _diffrn_reflns_theta_max 59.99 _reflns_number_total 3421 _reflns_number_observed 3063 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 77 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0356P)^2^+1.8048P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00010(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.004(11) _refine_ls_number_reflns 3344 _refine_ls_number_parameters 497 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0473 _refine_ls_R_factor_obs 0.0374 _refine_ls_wR_factor_all 0.0867 _refine_ls_wR_factor_obs 0.0805 _refine_ls_goodness_of_fit_all 1.041 _refine_ls_goodness_of_fit_obs 1.053 _refine_ls_restrained_S_all 1.064 _refine_ls_restrained_S_obs 1.053 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti Ti 0.54169(6) 0.82504(10) 0.15201(4) 0.0229(2) Uani 1 d . . Cl1 Cl 0.60557(9) 0.6762(2) 0.09388(5) 0.0306(3) Uani 1 d . . Cl2 Cl 0.49871(9) 0.9432(2) 0.22330(6) 0.0306(3) Uani 1 d . . N1 N 0.4618(3) 0.8666(6) 0.1190(2) 0.0263(11) Uani 1 d . . N2 N 0.6072(3) 1.0251(5) 0.1289(2) 0.0263(12) Uani 1 d . . N3 N 0.6674(3) 0.7953(5) 0.1927(2) 0.0287(11) Uani 1 d . . N4 N 0.5010(3) 0.6181(6) 0.1839(2) 0.0303(12) Uani 1 d . . C1 C 0.4068(4) 0.9118(8) 0.0839(2) 0.0325(15) Uani 1 d . . C2 C 0.3681(5) 1.0557(8) 0.0981(3) 0.049(2) Uani 1 d . . H2A H 0.4092(5) 1.1294(8) 0.1027(3) 0.073 Uiso 1 calc R . H2B H 0.3387(5) 1.0420(8) 0.1269(3) 0.073 Uiso 1 calc R . H2C H 0.3316(5) 1.0876(8) 0.0739(3) 0.073 Uiso 1 calc R . C3 C 0.3421(5) 0.7966(10) 0.0768(3) 0.054(2) Uani 1 d . . H3A H 0.3666(5) 0.7045(10) 0.0677(3) 0.081 Uiso 1 calc R . H3B H 0.3057(5) 0.8287(10) 0.0525(3) 0.081 Uiso 1 calc R . H3C H 0.3127(5) 0.7831(10) 0.1056(3) 0.081 Uiso 1 calc R . C4 C 0.4535(5) 0.9368(10) 0.0390(3) 0.053(2) Uani 1 d . . H4A H 0.4786(5) 0.8458(10) 0.0294(3) 0.080 Uiso 1 calc R . H4B H 0.4943(5) 1.0106(10) 0.0442(3) 0.080 Uiso 1 calc R . H4C H 0.4172(5) 0.9699(10) 0.0148(3) 0.080 Uiso 1 calc R . C5 C 0.6738(4) 1.0192(7) 0.1030(3) 0.037(2) Uani 1 d . . H5A H 0.6978(4) 0.9278(7) 0.0971(3) 0.044 Uiso 1 calc R . C6 C 0.7079(4) 1.1446(8) 0.0848(3) 0.045(2) Uani 1 d . . H6A H 0.7551(4) 1.1383(8) 0.0670(3) 0.054 Uiso 1 calc R . C7 C 0.6734(4) 1.2762(7) 0.0924(3) 0.040(2) Uani 1 d . . H7A H 0.6948(4) 1.3616(7) 0.0789(3) 0.048 Uiso 1 calc R . C8 C 0.6064(4) 1.2834(7) 0.1202(3) 0.038(2) Uani 1 d . . H8A H 0.5822(4) 1.3739(7) 0.1272(3) 0.045 Uiso 1 calc R . C9 C 0.5761(4) 1.1544(7) 0.1374(2) 0.0336(15) Uani 1 d . . H9A H 0.5303(4) 1.1590(7) 0.1564(2) 0.040 Uiso 1 calc R . C10 C 0.7170(4) 0.6846(7) 0.1856(2) 0.0338(14) Uani 1 d . . H10A H 0.6990(4) 0.6059(7) 0.1672(2) 0.041 Uiso 1 calc R . C11 C 0.7924(4) 0.6777(8) 0.2033(2) 0.0357(14) Uani 1 d . . H11A H 0.8264(4) 0.5989(8) 0.1959(2) 0.043 Uiso 1 calc R . C12 C 0.8177(4) 0.7891(8) 0.2323(2) 0.037(2) Uani 1 d . . H12A H 0.8689(4) 0.7870(8) 0.2459(2) 0.044 Uiso 1 calc R . C13 C 0.7671(4) 0.9008(8) 0.2405(2) 0.036(2) Uani 1 d . . H13A H 0.7830(4) 0.9783(8) 0.2599(2) 0.043 Uiso 1 calc R . C14 C 0.6925(4) 0.9025(7) 0.2207(3) 0.0352(15) Uani 1 d . . H14A H 0.6580(4) 0.9814(7) 0.2271(3) 0.042 Uiso 1 calc R . C15 C 0.5286(4) 0.5689(7) 0.2240(2) 0.0317(14) Uani 1 d . . H15A H 0.5649(4) 0.6276(7) 0.2407(2) 0.038 Uiso 1 calc R . C16 C 0.5071(5) 0.4371(8) 0.2423(3) 0.046(2) Uani 1 d . . H16A H 0.5292(5) 0.4049(8) 0.2706(3) 0.055 Uiso 1 calc R . C17 C 0.4527(5) 0.3518(7) 0.2189(3) 0.050(2) Uani 1 d . . H17A H 0.4371(5) 0.2600(7) 0.2308(3) 0.060 Uiso 1 calc R . C18 C 0.4220(5) 0.4031(8) 0.1782(3) 0.046(2) Uani 1 d . . H18A H 0.3836(5) 0.3484(8) 0.1617(3) 0.056 Uiso 1 calc R . C19 C 0.4478(4) 0.5360(6) 0.1615(3) 0.034(2) Uani 1 d . . H19A H 0.4270(4) 0.5702(6) 0.1330(3) 0.041 Uiso 1 calc R . Ti' Ti 0.66090(6) 0.69182(11) 0.41531(4) 0.0253(2) Uani 1 d . . Cl1' Cl 0.72017(9) 0.8429(2) 0.47405(6) 0.0328(3) Uani 1 d . . Cl2' Cl 0.63330(9) 0.5721(2) 0.34201(6) 0.0345(3) Uani 1 d . . N1' N 0.5808(3) 0.6418(5) 0.4469(2) 0.0267(11) Uani 1 d . . N2' N 0.7293(3) 0.4965(6) 0.4384(2) 0.0285(12) Uani 1 d . . N3' N 0.7855(3) 0.7487(6) 0.3775(2) 0.0312(12) Uani 1 d . . N4' N 0.6090(3) 0.8944(6) 0.3855(2) 0.0311(12) Uani 1 d . . C1' C 0.5232(4) 0.5914(7) 0.4803(2) 0.0317(14) Uani 1 d . . C2' C 0.4978(5) 0.4374(8) 0.4682(3) 0.046(2) Uani 1 d . . H2'A H 0.4721(5) 0.4372(8) 0.4379(3) 0.069 Uiso 1 calc R . H2'B H 0.4604(5) 0.4018(8) 0.4915(3) 0.069 Uiso 1 calc R . H2'C H 0.5444(5) 0.3741(8) 0.4674(3) 0.069 Uiso 1 calc R . C3' C 0.4515(4) 0.6919(9) 0.4807(3) 0.047(2) Uani 1 d . . H3'A H 0.4263(4) 0.6912(9) 0.4503(3) 0.071 Uiso 1 calc R . H3'B H 0.4686(4) 0.7908(9) 0.4882(3) 0.071 Uiso 1 calc R . H3'C H 0.4135(4) 0.6584(9) 0.5040(3) 0.071 Uiso 1 calc R . C4' C 0.5630(5) 0.5914(9) 0.5273(3) 0.050(2) Uani 1 d . . H4'A H 0.5794(5) 0.6904(9) 0.5352(3) 0.075 Uiso 1 calc R . H4'B H 0.6096(5) 0.5281(9) 0.5265(3) 0.075 Uiso 1 calc R . H4'C H 0.5257(5) 0.5558(9) 0.5506(3) 0.075 Uiso 1 calc R . C5' C 0.7932(4) 0.5002(7) 0.4661(3) 0.036(2) Uani 1 d . . H5'A H 0.8158(4) 0.5920(7) 0.4732(3) 0.043 Uiso 1 calc R . C6' C 0.8273(5) 0.3789(8) 0.4847(3) 0.046(2) Uani 1 d . . H6'A H 0.8724(5) 0.3874(8) 0.5041(3) 0.055 Uiso 1 calc R . C7' C 0.7959(5) 0.2449(8) 0.4750(3) 0.045(2) Uani 1 d . . H7'A H 0.8185(5) 0.1596(8) 0.4879(3) 0.053 Uiso 1 calc R . C8' C 0.7314(4) 0.2363(8) 0.4466(3) 0.043(2) Uani 1 d . . H8'A H 0.7091(4) 0.1449(8) 0.4388(3) 0.052 Uiso 1 calc R . C9' C 0.6995(4) 0.3628(7) 0.4293(2) 0.0324(14) Uani 1 d . . H9'A H 0.6542(4) 0.3560(7) 0.4101(2) 0.039 Uiso 1 calc R . C10' C 0.8164(4) 0.8826(8) 0.3750(3) 0.040(2) Uani 1 d . . H10B H 0.7867(4) 0.9614(8) 0.3871(3) 0.048 Uiso 1 calc R . C11' C 0.8896(5) 0.9110(10) 0.3557(3) 0.052(2) Uani 1 d . . H11B H 0.9101(5) 1.0070(10) 0.3550(3) 0.062 Uiso 1 calc R . C12' C 0.9325(4) 0.7968(10) 0.3375(3) 0.051(2) Uani 1 d . . H12B H 0.9833(4) 0.8131(10) 0.3244(3) 0.061 Uiso 1 calc R . C13' C 0.9015(4) 0.6621(10) 0.3387(3) 0.046(2) Uani 1 d . . H13B H 0.9301(4) 0.5824(10) 0.3262(3) 0.055 Uiso 1 calc R . C14' C 0.8274(4) 0.6410(8) 0.3582(2) 0.0360(15) Uani 1 d . . H14B H 0.8054(4) 0.5461(8) 0.3579(2) 0.043 Uiso 1 calc R . C15' C 0.6239(4) 0.9470(7) 0.3432(3) 0.0348(15) Uani 1 d . . H15B H 0.6557(4) 0.8908(7) 0.3229(3) 0.042 Uiso 1 calc R . C16' C 0.5953(5) 1.0791(8) 0.3278(3) 0.045(2) Uani 1 d . . H16B H 0.6089(5) 1.1148(8) 0.2981(3) 0.054 Uiso 1 calc R . C17' C 0.5467(5) 1.1572(8) 0.3565(3) 0.044(2) Uani 1 d . . H17B H 0.5259(5) 1.2480(8) 0.3468(3) 0.053 Uiso 1 calc R . C18' C 0.5284(5) 1.1031(7) 0.3992(3) 0.042(2) Uani 1 d . . H18B H 0.4940(5) 1.1547(7) 0.4193(3) 0.050 Uiso 1 calc R . C19' C 0.5610(4) 0.9725(7) 0.4126(2) 0.0333(14) Uani 1 d . . H19B H 0.5487(4) 0.9362(7) 0.4424(2) 0.040 Uiso 1 calc R . C20 C 0.7775(7) 0.3850(9) 0.2724(3) 0.063(2) Uani 1 d . . H20A H 0.7401(7) 0.4548(9) 0.2865(3) 0.076 Uiso 1 calc R . H20B H 0.8244(7) 0.4400(9) 0.2616(3) 0.076 Uiso 1 calc R . Cl3 Cl 0.7319(2) 0.3008(2) 0.22514(9) 0.0689(6) Uani 1 d . . Cl4 Cl 0.8074(2) 0.2586(2) 0.31442(8) 0.0698(6) Uani 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 Ti 0.0192(5) 0.0221(5) 0.0273(5) 0.0006(5) -0.0009(4) -0.0001(4) Cl1 0.0309(7) 0.0304(7) 0.0305(8) -0.0038(6) 0.0011(6) 0.0013(6) Cl2 0.0266(7) 0.0328(7) 0.0322(8) -0.0038(6) 0.0038(7) -0.0007(6) N1 0.022(2) 0.030(3) 0.026(3) 0.003(2) -0.002(2) -0.001(2) N2 0.026(3) 0.024(3) 0.030(3) 0.005(2) 0.000(2) -0.005(2) N3 0.026(3) 0.027(3) 0.033(3) 0.001(2) -0.002(2) 0.001(2) N4 0.028(3) 0.030(2) 0.033(3) 0.000(2) 0.008(2) 0.000(2) C1 0.024(3) 0.049(4) 0.024(3) 0.005(3) 0.003(3) 0.003(3) C2 0.053(5) 0.047(4) 0.046(4) 0.005(4) -0.001(4) 0.019(4) C3 0.037(4) 0.077(6) 0.049(5) -0.013(4) -0.017(4) -0.008(4) C4 0.050(5) 0.083(6) 0.027(4) 0.016(4) 0.004(4) 0.016(4) C5 0.029(4) 0.034(3) 0.047(4) 0.001(3) 0.015(3) -0.001(3) C6 0.036(4) 0.052(4) 0.047(4) -0.002(4) 0.006(3) -0.010(3) C7 0.031(4) 0.033(3) 0.056(5) 0.010(3) -0.003(3) -0.009(3) C8 0.032(3) 0.029(3) 0.052(4) 0.003(3) 0.001(3) 0.002(3) C9 0.027(3) 0.028(3) 0.045(4) 0.004(3) 0.009(3) 0.003(3) C10 0.032(3) 0.036(3) 0.033(4) -0.002(3) -0.005(3) 0.004(3) C11 0.028(3) 0.044(4) 0.035(3) 0.006(3) 0.000(3) 0.010(3) C12 0.026(3) 0.056(4) 0.029(3) 0.008(3) -0.003(3) -0.002(3) C13 0.032(4) 0.046(4) 0.030(4) 0.000(3) -0.006(3) -0.009(3) C14 0.033(4) 0.034(3) 0.039(4) -0.006(3) 0.000(3) -0.002(3) C15 0.032(3) 0.034(3) 0.029(3) 0.007(3) 0.002(3) -0.001(3) C16 0.051(4) 0.046(4) 0.040(4) 0.016(3) 0.012(4) 0.003(3) C17 0.061(5) 0.028(3) 0.061(5) 0.005(4) 0.022(4) -0.006(3) C18 0.042(4) 0.043(4) 0.055(5) -0.018(4) 0.015(4) -0.009(3) C19 0.028(3) 0.030(3) 0.044(4) -0.003(3) 0.007(3) 0.000(3) Ti' 0.0227(5) 0.0248(5) 0.0285(5) -0.0003(5) 0.0005(5) 0.0013(4) Cl1' 0.0324(8) 0.0318(7) 0.0342(8) -0.0051(7) -0.0005(7) -0.0010(6) Cl2' 0.0302(7) 0.0382(8) 0.0350(9) -0.0072(7) -0.0061(7) 0.0046(6) N1' 0.020(2) 0.029(3) 0.031(3) -0.002(2) 0.000(2) 0.001(2) N2' 0.020(3) 0.030(3) 0.035(3) -0.001(2) 0.007(2) 0.001(2) N3' 0.025(3) 0.036(3) 0.033(3) 0.001(2) 0.000(2) 0.001(2) N4' 0.031(3) 0.032(3) 0.031(3) 0.005(2) 0.002(2) 0.001(2) C1' 0.025(3) 0.037(3) 0.033(4) -0.004(3) 0.004(3) -0.003(3) C2' 0.042(4) 0.042(4) 0.055(5) -0.001(4) 0.005(4) -0.013(3) C3' 0.029(4) 0.060(5) 0.052(5) -0.005(4) 0.011(3) -0.002(3) C4' 0.055(5) 0.064(5) 0.032(4) 0.002(4) -0.001(4) -0.001(4) C5' 0.025(3) 0.038(3) 0.044(4) 0.003(3) -0.001(3) 0.001(3) C6' 0.041(4) 0.044(4) 0.053(5) 0.006(3) -0.008(4) 0.004(3) C7' 0.045(4) 0.040(4) 0.049(4) 0.011(4) 0.010(4) 0.017(3) C8' 0.036(4) 0.032(3) 0.061(5) 0.001(4) 0.010(4) 0.006(3) C9' 0.034(3) 0.025(3) 0.039(4) 0.004(3) -0.002(3) 0.003(3) C10' 0.035(4) 0.041(4) 0.044(4) 0.004(3) -0.001(3) -0.007(3) C11' 0.041(4) 0.072(5) 0.042(4) 0.019(4) -0.004(3) -0.027(4) C12' 0.020(3) 0.085(6) 0.047(4) 0.015(4) 0.003(3) -0.003(4) C13' 0.031(4) 0.068(5) 0.037(4) 0.008(4) 0.000(3) 0.012(3) C14' 0.029(3) 0.042(4) 0.037(4) 0.000(3) 0.004(3) 0.003(3) C15' 0.032(3) 0.042(4) 0.030(4) 0.006(3) -0.001(3) 0.002(3) C16' 0.060(5) 0.037(4) 0.037(4) 0.017(3) -0.001(4) 0.000(3) C17' 0.052(4) 0.031(3) 0.050(4) 0.006(3) -0.010(4) 0.002(3) C18' 0.054(5) 0.031(3) 0.040(4) -0.002(3) -0.002(3) 0.012(3) C19' 0.039(4) 0.033(3) 0.028(3) -0.006(3) 0.001(3) 0.006(3) C20 0.090(7) 0.048(5) 0.051(5) -0.004(4) -0.006(5) 0.009(4) Cl3 0.087(2) 0.0537(11) 0.0663(13) -0.0061(11) -0.0153(13) 0.0038(11) Cl4 0.100(2) 0.0529(11) 0.0565(13) 0.0035(10) -0.0016(13) 0.0121(11) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti N1 1.697(5) . ? Ti N4 2.228(5) . ? Ti N2 2.252(5) . ? Ti Cl1 2.426(2) . ? Ti N3 2.444(5) . ? Ti Cl2 2.447(2) . ? N1 C1 1.440(8) . ? N2 C9 1.325(8) . ? N2 C5 1.353(9) . ? N3 C10 1.335(8) . ? N3 C14 1.347(9) . ? N4 C15 1.331(9) . ? N4 C19 1.343(9) . ? C1 C2 1.535(10) . ? C1 C3 1.537(10) . ? C1 C4 1.539(10) . ? C5 C6 1.395(10) . ? C6 C7 1.363(11) . ? C7 C8 1.391(11) . ? C8 C9 1.388(10) . ? C10 C11 1.374(9) . ? C11 C12 1.394(10) . ? C12 C13 1.359(10) . ? C13 C14 1.384(10) . ? C15 C16 1.374(10) . ? C16 C17 1.385(12) . ? C17 C18 1.375(12) . ? C18 C19 1.387(10) . ? Ti' N1' 1.696(5) . ? Ti' N4' 2.235(5) . ? Ti' N2' 2.240(5) . ? Ti' Cl1' 2.417(2) . ? Ti' N3' 2.429(5) . ? Ti' Cl2' 2.440(2) . ? N1' C1' 1.450(8) . ? N2' C5' 1.346(9) . ? N2' C9' 1.356(8) . ? N3' C10' 1.342(9) . ? N3' C14' 1.342(9) . ? N4' C19' 1.339(9) . ? N4' C15' 1.344(9) . ? C1' C4' 1.521(10) . ? C1' C2' 1.524(9) . ? C1' C3' 1.524(10) . ? C5' C6' 1.369(10) . ? C6' C7' 1.373(11) . ? C7' C8' 1.369(12) . ? C8' C9' 1.377(10) . ? C10' C11' 1.381(11) . ? C11' C12' 1.382(13) . ? C12' C13' 1.348(12) . ? C13' C14' 1.387(10) . ? C15' C16' 1.384(10) . ? C16' C17' 1.372(11) . ? C17' C18' 1.371(11) . ? C18' C19' 1.378(10) . ? C20 Cl3 1.754(9) . ? C20 Cl4 1.759(9) . ? 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 N1 Ti N4 100.5(2) . . ? N1 Ti N2 92.2(2) . . ? N4 Ti N2 167.3(2) . . ? N1 Ti Cl1 95.1(2) . . ? N4 Ti Cl1 86.66(14) . . ? N2 Ti Cl1 92.18(15) . . ? N1 Ti N3 171.0(2) . . ? N4 Ti N3 88.3(2) . . ? N2 Ti N3 79.0(2) . . ? Cl1 Ti N3 83.46(13) . . ? N1 Ti Cl2 98.1(2) . . ? N4 Ti Cl2 86.47(15) . . ? N2 Ti Cl2 91.86(15) . . ? Cl1 Ti Cl2 166.06(7) . . ? N3 Ti Cl2 84.24(13) . . ? C1 N1 Ti 167.5(5) . . ? C9 N2 C5 117.9(5) . . ? C9 N2 Ti 119.1(4) . . ? C5 N2 Ti 122.7(4) . . ? C10 N3 C14 117.2(6) . . ? C10 N3 Ti 123.7(4) . . ? C14 N3 Ti 118.8(4) . . ? C15 N4 C19 117.7(6) . . ? C15 N4 Ti 123.1(5) . . ? C19 N4 Ti 119.1(5) . . ? N1 C1 C2 109.5(6) . . ? N1 C1 C3 110.7(6) . . ? C2 C1 C3 109.3(6) . . ? N1 C1 C4 108.2(5) . . ? C2 C1 C4 108.4(7) . . ? C3 C1 C4 110.7(7) . . ? N2 C5 C6 121.3(6) . . ? C7 C6 C5 119.9(7) . . ? C6 C7 C8 119.0(6) . . ? C9 C8 C7 117.9(6) . . ? N2 C9 C8 123.9(6) . . ? N3 C10 C11 123.9(6) . . ? C10 C11 C12 118.4(6) . . ? C13 C12 C11 118.0(6) . . ? C12 C13 C14 120.6(7) . . ? N3 C14 C13 121.8(6) . . ? N4 C15 C16 123.0(7) . . ? C15 C16 C17 119.3(7) . . ? C18 C17 C16 118.3(7) . . ? C17 C18 C19 119.0(7) . . ? N4 C19 C18 122.6(7) . . ? N1' Ti' N4' 97.1(2) . . ? N1' Ti' N2' 91.8(2) . . ? N4' Ti' N2' 171.1(2) . . ? N1' Ti' Cl1' 96.1(2) . . ? N4' Ti' Cl1' 87.3(2) . . ? N2' Ti' Cl1' 92.24(15) . . ? N1' Ti' N3' 172.8(2) . . ? N4' Ti' N3' 89.1(2) . . ? N2' Ti' N3' 82.1(2) . . ? Cl1' Ti' N3' 80.55(14) . . ? N1' Ti' Cl2' 101.3(2) . . ? N4' Ti' Cl2' 88.1(2) . . ? N2' Ti' Cl2' 89.7(2) . . ? Cl1' Ti' Cl2' 162.48(7) . . ? N3' Ti' Cl2' 82.49(14) . . ? C1' N1' Ti' 169.3(5) . . ? C5' N2' C9' 115.8(6) . . ? C5' N2' Ti' 124.8(4) . . ? C9' N2' Ti' 118.8(4) . . ? C10' N3' C14' 116.9(6) . . ? C10' N3' Ti' 124.0(5) . . ? C14' N3' Ti' 119.0(4) . . ? C19' N4' C15' 117.1(6) . . ? C19' N4' Ti' 117.4(4) . . ? C15' N4' Ti' 125.5(5) . . ? N1' C1' C4' 107.6(5) . . ? N1' C1' C2' 109.5(5) . . ? C4' C1' C2' 109.4(6) . . ? N1' C1' C3' 110.1(6) . . ? C4' C1' C3' 110.1(6) . . ? C2' C1' C3' 110.1(6) . . ? N2' C5' C6' 123.5(7) . . ? C5' C6' C7' 119.5(7) . . ? C8' C7' C6' 118.8(7) . . ? C7' C8' C9' 118.7(7) . . ? N2' C9' C8' 123.7(7) . . ? N3' C10' C11' 123.0(7) . . ? C12' C11' C10' 118.6(7) . . ? C13' C12' C11' 119.2(7) . . ? C12' C13' C14' 119.3(7) . . ? N3' C14' C13' 122.9(7) . . ? N4' C15' C16' 123.2(7) . . ? C17' C16' C15' 118.3(7) . . ? C18' C17' C16' 119.5(7) . . ? C17' C18' C19' 118.8(7) . . ? N4' C19' C18' 123.1(7) . . ? Cl3 C20 Cl4 112.0(5) . . ? _refine_diff_density_max 0.243 _refine_diff_density_min -0.287 _refine_diff_density_rms 0.058