# Copyright The Royal Society of Chemistry, 1999 # CCDC Number: 440/083 data_global _audit_creation_date 98-10-12 _audit_creation_method CRYSTALS _publ_contact_letter ; This CIF corresponds to the manuscript entitled Titanium imido complexes with 1,3,5-triazacyclohexane ligands: syntheses, solution dynamics and solid state structures P J Wilson, P A Cooke, A J Blake, P Mountford and M Schroeder submitted to New Journal of Chemistry ; _publ_contact_author ; Dr P Mountford Inorganic Chemistry Laboratory South Parks Road Oxford OX1 3QR ; _publ_contact_author_phone '01865 272679' _publ_contact_author_fax '01865 272690' _publ_contact_author_email Philip.Mountford@chem.ox.ac.uk _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo G., Guagliardi A., Burla M.C., Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic olution of crystal structures by direct methods. J. Appl. Cryst. (27), 435 Carruthers, J.R. and Watkin, D.J. (1979), (Chebychev Weighting) Acta Cryst, A35, 698-699 Sheldrick, G.M. (1994 or 1995). SHELXTL/PC version 5.03. Siemens Analytical Instruments Inc, Madison WI, U.S.A. Stoe & Cie (1997a). STADI4 diffractometer control program, version 1.07 for Windows. Stoe & Cie (1997b). X-RED data reduction program, version 1.09 for Windows. Watkin, D.J., Prout, C.K. Carruthers, R.J. & Betteridge, P. (1996) RYSTALS Issue 10. Chemical Crystallography Laboratory, OXFORD, UK. ; loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source 'C ' 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International_Tables_Vol_IV_Table_2.2B' 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 'International_Tables_Vol_IV_Table_2.2B' 'N ' 0.0040 0.0030 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International_Tables_Vol_IV_Table_2.2B' 'Cl ' 0.1320 0.1590 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International_Tables_Vol_IV_Table_2.2B' 'Ti ' 0.2480 0.4460 9.7595 7.8508 7.3558 0.5000 1.6991 35.6338 1.9021 116.1050 1.2807 'International_Tables_Vol_IV_Table_2.2B' _computing_data_collection 'STADI4 (Stoe & Cie, 1997a)' _computing_cell_refinement 'STADI4 (Stoe & Cie, 1997a)' _computing_data_reduction ; X-RED (Stoe & Cie, 1997b) CRYSTALS (Watkin et al, 1996) ; _computing_structure_solution 'SIR92 (Altomare, et al, 1994)' _computing_structure_refinement ; CRYSTALS Issue 10 (Watkin et al, 1996) ; _computing_publication_material ; CRYSTALS Issue 10 (Watkin et al, 1996) ; _computing_molecular_graphics 'SHELXTL/PC (Sheldrick, 1994)' data_N3TICL # [Ti(Me3tach)(NBu-t)Cl2] (Compound 2a) _chemical_name_systematic ; [Ti(Me3tach)(NBu-t)Cl2] ; _cell_length_a 7.053(2) _cell_angle_alpha 90 _cell_length_b 13.818(5) _cell_angle_beta 90 _cell_length_c 16.452(6) _cell_angle_gamma 90 _cell_volume 1603.4(7) _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21 ' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' 'x+1/2,-y+1/2,-z' '-x,y+1/2,-z+1/2' '-x+1/2,-y,z+1/2' _publ_section_experimental ; Ti(NBu-t)Cl2(py)2] + Me3tach in CH2Cl2 ; _chemical_formula_sum ' C10 H24 Cl2 N4 Ti1 ' _chemical_formula_moiety ' C10 H24 Cl2 N4 Ti1 ' _chemical_formula_weight 319.14 _cell_measurement_reflns_used 30 _cell_measurement_theta_min 12.5 _cell_measurement_theta_max 14.0 _cell_measurement_temperature 150(2) _cell_formula_units_Z 4 _exptl_crystal_description rod _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_min 0.13 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_max 0.40 _exptl_crystal_density_diffrn 1.32 _exptl_crystal_density_meas 'not measured' _exptl_crystal_F_000 672 _exptl_absorpt_coefficient_mu 0.85 _exptl_absorpt_correction_type 'psi scans' _exptl_absorpt_correction_T_min 0.904 _exptl_absorpt_correction_T_max 0.998 _exptl_absorpt_process_details ; Psi Scan Reflections used Mu * R = 0.00 H K L 2Theta Chi Imin/Imax -1 0 1 6.3 -78.2 0.926 -2 -1 1 12.2 -83.9 0.894 2 2 -1 13.2 72.9 0.930 ; _diffrn_measurement_device 'STOE STADI4 4-circle-diffractometer' _diffrn_special_details ? _diffrn_ambient_environment ? _diffrn_radiation_collimation '0.5 mm' _diffrn_radiation_detector 'NaI(Tl) scintillation counter' _diffrn_radiation_monochromator 'planar graphite' _diffrn_radiation_polarisn_norm 90 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_standards_number 3 _diffrn_standards_interval_time 60 _diffrn_reflns_av_sigmaI/netI 0.0552 _reflns_d_resolution_high 0.841 _reflns_d_resolution_low 7.089 _diffrn_standards_decay_% 'random variation +/- 3.0' _diffrn_ambient_temperature 150(2) _diffrn_reflns_number 1803 _reflns_number_total 1659 _diffrn_reflns_av_R_equivalents 0.02 _reflns_number_observed 1435 _diffrn_reflns_theta_min 2.88 _diffrn_reflns_theta_max 25.06 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 19 _reflns_limit_h_min 0 _reflns_limit_h_max 8 _reflns_limit_k_min 0 _reflns_limit_k_max 16 _reflns_limit_l_min 0 _reflns_limit_l_max 19 _reflns_observed_criterion >2.00\s(I) _refine_diff_density_min -0.63 _refine_diff_density_max 0.36 _refine_ls_number_reflns 1435 _refine_ls_number_parameters 154 _refine_ls_R_factor_obs 0.0455 _refine_ls_wR_factor_obs 0.0475 _refine_ls_goodness_of_fit_obs 1.1198 _refine_ls_shift/esd_max 0.003 _refine_ls_structure_factor_coef F _refine_ls_extinction_method 'none required' _refine_ls_number_restraints 0 _refine_ls_abs_structure_flack 0.088(93) _refine_ls_extinction_coef 'none required' _diffrn_measurement_method 'omega\theta' _refine_ls_matrix_type full _refine_ls_weighting_scheme 'Chebychev polynomial' _refine_ls_hydrogen_treatment 'riding model' _atom_sites_solution_primary 'direct methods' _atom_sites_solution_hydrogens geometric loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_thermal_displace_type Ti1 -0.4441(1) -0.40534(7) -0.18670(5) 0.0143 1.0000 Uani N1 -0.4040(6) -0.3920(3) -0.2879(3) 0.0201 1.0000 Uani N2 -0.7211(7) -0.3269(3) -0.1758(3) 0.0204 1.0000 Uani N4 -0.7137(6) -0.4919(3) -0.1900(3) 0.0176 1.0000 Uani N6 -0.6403(6) -0.4227(3) -0.0666(3) 0.0198 1.0000 Uani C1 -0.7418(8) -0.3343(4) -0.0867(3) 0.0193 1.0000 Uani C3 -0.8243(7) -0.4076(5) -0.2147(3) 0.0220 1.0000 Uani C5 -0.7340(8) -0.5076(4) -0.1015(3) 0.0188 1.0000 Uani C10 -0.3730(9) -0.3871(4) -0.3751(3) 0.0238 1.0000 Uani C11 -0.537(1) -0.3321(6) -0.4159(4) 0.0456 1.0000 Uani C12 -0.3633(9) -0.4901(4) -0.4074(3) 0.0281 1.0000 Uani C13 -0.1862(9) -0.3356(5) -0.3917(4) 0.0338 1.0000 Uani C21 -0.7723(9) -0.2325(4) -0.2077(4) 0.0297 1.0000 Uani C41 -0.7583(9) -0.5795(5) -0.2375(3) 0.0324 1.0000 Uani C61 -0.5992(8) -0.4335(4) 0.0202(3) 0.0281 1.0000 Uani Cl1 -0.2799(2) -0.2785(1) -0.12185(8) 0.0252 1.0000 Uani Cl2 -0.2716(2) -0.5437(1) -0.14599(8) 0.0225 1.0000 Uani H11 -0.8729(8) -0.3389(4) -0.0715(3) 0.0244 1.0000 Uiso H12 -0.6854(8) -0.2795(4) -0.0601(3) 0.0244 1.0000 Uiso H31 -0.9523(7) -0.4119(5) -0.1952(3) 0.0257 1.0000 Uiso H32 -0.8250(7) -0.4008(5) -0.2727(3) 0.0257 1.0000 Uiso H51 -0.8652(8) -0.5102(4) -0.0861(3) 0.0249 1.0000 Uiso H52 -0.6718(8) -0.5661(4) -0.0846(3) 0.0249 1.0000 Uiso H111 -0.517(1) -0.3286(6) -0.4735(4) 0.0547 1.0000 Uiso H112 -0.653(1) -0.3661(6) -0.4051(4) 0.0547 1.0000 Uiso H113 -0.545(1) -0.2679(6) -0.3938(4) 0.0547 1.0000 Uiso H121 -0.3418(9) -0.4896(4) -0.4650(3) 0.0356 1.0000 Uiso H122 -0.4805(9) -0.5227(4) -0.3959(3) 0.0356 1.0000 Uiso H123 -0.2610(9) -0.5234(4) -0.3809(3) 0.0356 1.0000 Uiso H131 -0.1654(9) -0.3325(5) -0.4493(4) 0.0433 1.0000 Uiso H132 -0.0835(9) -0.3699(5) -0.3665(4) 0.0433 1.0000 Uiso H133 -0.1927(9) -0.2711(5) -0.3700(4) 0.0433 1.0000 Uiso H211 -0.7564(9) -0.2317(4) -0.2657(4) 0.0392 1.0000 Uiso H212 -0.9016(9) -0.2177(4) -0.1945(4) 0.0392 1.0000 Uiso H213 -0.6902(9) -0.1852(4) -0.1835(4) 0.0392 1.0000 Uiso H411 -0.6815(9) -0.6323(5) -0.2187(3) 0.0388 1.0000 Uiso H412 -0.8898(9) -0.5954(5) -0.2307(3) 0.0388 1.0000 Uiso H413 -0.7327(9) -0.5679(5) -0.2940(3) 0.0388 1.0000 Uiso H611 -0.5327(8) -0.4932(4) 0.0293(3) 0.0345 1.0000 Uiso H612 -0.7151(8) -0.4336(4) 0.0508(3) 0.0345 1.0000 Uiso H613 -0.5215(8) -0.3803(4) 0.0373(3) 0.0345 1.0000 Uiso 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 0.0092(4) 0.0184(4) 0.0154(4) -0.0010(4) -0.0003(4) -0.0012(4) N1 0.013(2) 0.027(3) 0.020(2) -0.001(2) -0.002(2) 0.002(2) N2 0.014(2) 0.022(2) 0.026(2) 0.005(2) -0.004(2) 0.004(2) N4 0.015(2) 0.024(2) 0.013(2) -0.000(2) -0.006(2) -0.000(2) N6 0.013(2) 0.027(3) 0.019(2) -0.001(2) 0.001(2) 0.007(2) C1 0.010(3) 0.027(3) 0.021(2) -0.001(2) 0.007(2) 0.001(2) C3 0.011(2) 0.039(3) 0.017(2) -0.002(3) -0.001(2) -0.005(3) C5 0.016(3) 0.017(2) 0.023(3) 0.003(2) 0.003(2) -0.006(2) C10 0.025(3) 0.029(3) 0.017(3) -0.001(2) 0.003(2) 0.004(3) C11 0.048(4) 0.065(5) 0.024(3) 0.015(3) 0.002(4) 0.023(4) C12 0.028(3) 0.037(3) 0.019(3) -0.009(3) 0.009(3) -0.001(3) C13 0.029(4) 0.042(4) 0.030(3) 0.004(3) 0.007(3) -0.014(3) C21 0.027(3) 0.026(3) 0.036(3) 0.007(3) -0.005(3) 0.007(3) C41 0.028(3) 0.041(3) 0.029(3) -0.009(3) 0.004(3) -0.011(3) C61 0.024(3) 0.036(3) 0.025(3) -0.000(2) -0.001(2) 0.007(3) Cl1 0.0192(7) 0.0234(7) 0.0331(7) -0.0051(6) -0.0019(6) -0.0047(6) Cl2 0.0165(7) 0.0220(6) 0.0290(6) -0.0016(5) -0.0007(6) 0.0053(6) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ti1 . N1 . 1.699(4) yes Ti1 . N2 . 2.241(5) yes Ti1 . N4 . 2.247(5) yes Ti1 . N6 . 2.424(4) yes Ti1 . Cl1 . 2.356(2) yes Ti1 . Cl2 . 2.363(2) yes N1 . C10 . 1.452(7) yes N2 . C1 . 1.477(6) yes N2 . C3 . 1.477(7) yes N2 . C21 . 1.451(7) yes N4 . C3 . 1.460(7) yes N4 . C5 . 1.479(6) yes N4 . C41 . 1.475(7) yes N6 . C1 . 1.454(7) yes N6 . C5 . 1.463(7) yes N6 . C61 . 1.465(7) yes C10 . C11 . 1.538(9) yes C10 . C12 . 1.521(8) yes C10 . C13 . 1.523(8) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . Ti1 . N2 . 99.9(2) yes N1 . Ti1 . N4 . 100.1(2) yes N2 . Ti1 . N4 . 61.4(2) yes N1 . Ti1 . N6 . 154.8(2) yes N2 . Ti1 . N6 . 59.0(2) yes N4 . Ti1 . N6 . 58.9(2) yes N1 . Ti1 . Cl1 . 106.3(2) yes N2 . Ti1 . Cl1 . 91.9(1) yes N4 . Ti1 . Cl1 . 145.4(1) yes N6 . Ti1 . Cl1 . 89.2(1) yes N1 . Ti1 . Cl2 . 106.2(2) yes N2 . Ti1 . Cl2 . 144.8(1) yes N4 . Ti1 . Cl2 . 90.7(1) yes N6 . Ti1 . Cl2 . 89.0(1) yes Cl1 . Ti1 . Cl2 . 102.72(6) yes Ti1 . N1 . C10 . 176.3(4) yes Ti1 . N2 . C1 . 97.6(3) yes Ti1 . N2 . C3 . 91.7(3) yes C1 . N2 . C3 . 109.2(4) yes Ti1 . N2 . C21 . 128.5(4) yes C1 . N2 . C21 . 113.4(4) yes C3 . N2 . C21 . 113.5(4) yes Ti1 . N4 . C3 . 91.9(3) yes Ti1 . N4 . C5 . 97.8(3) yes C3 . N4 . C5 . 109.8(4) yes Ti1 . N4 . C41 . 129.1(4) yes C3 . N4 . C41 . 113.2(4) yes C5 . N4 . C41 . 112.4(4) yes Ti1 . N6 . C1 . 90.7(3) yes Ti1 . N6 . C5 . 91.0(3) yes C1 . N6 . C5 . 111.3(4) yes Ti1 . N6 . C61 . 133.8(3) yes C1 . N6 . C61 . 113.9(4) yes C5 . N6 . C61 . 112.9(4) yes N2 . C1 . N6 . 103.6(4) yes N2 . C3 . N4 . 102.6(4) yes N4 . C5 . N6 . 103.0(4) yes N1 . C10 . C11 . 109.9(5) yes N1 . C10 . C12 . 107.9(5) yes C11 . C10 . C12 . 110.1(5) yes N1 . C10 . C13 . 109.2(5) yes C11 . C10 . C13 . 110.0(5) yes C12 . C10 . C13 . 109.6(5) yes #==end data_TIBUTN # [Ti(NBu-t)(t-Bu3tach)Cl2] (Compound 3a) _chemical_name_systematic ; [Ti(N-t-Bu)(t-Bu3tach)Cl2] ; _publ_section_exptl_refinement ; One of the t-butyl substituents for the t-Bu3tach ligand was disordered. Two orientations for the methyl substituents were refined anisotropically [C(42), C(43), C(44) and C(421), C(431) and C(441)] with site occupancy factors of 0.38 and 0.62, subject to similarity restraints on the C(quat)-C(methyl) distances ; _cell_length_a 9.871(5) _cell_angle_alpha 90 _cell_length_b 16.677(11) _cell_angle_beta 103.515) _cell_length_c 15.020(110 _cell_angle_gamma 90 _cell_volume 2404.1(21) _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1 ' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' '-x,-y,-z' '-x+1/2,y+1/2,-z+1/2' 'x+1/2,-y+1/2,z+1/2' _chemical_formula_sum ' C19 H42 Cl2 N4 Ti1 ' _chemical_formula_moiety ' C19 H42 Cl2 N4 Ti1 ' _chemical_compound_source ; [Ti(N-t-Bu)Cl2(py)3] + t-Bu3tach in CH2Cl2 ; _chemical_formula_weight 445.38 _cell_measurement_reflns_used 17 _cell_measurement_theta_min 12.5 _cell_measurement_theta_max 13.5 _cell_measurement_temperature 150(2) _cell_formula_units_Z 4 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_min 0.26 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_max 0.35 _exptl_crystal_density_diffrn 1.23 _exptl_crystal_density_method none _exptl_crystal_density_meas 'not measured' _exptl_crystal_F_000 960 _exptl_absorpt_coefficient_mu 0.59 _exptl_absorpt_correction_type 'psi scans' _exptl_absorpt_correction_T_min 0.772 _exptl_absorpt_correction_T_max 0.883 _exptl_absorpt_process_details ; Psi Scan Reflections used Mu * R = 0.08 H K L 2Theta Chi Imin/Imax 0 -2 -4 12.2 -73.4 0.835 1 -6 -4 18.4 -72.4 0.824 ; _diffrn_measurement_device 'Stoe STADI4 4-circle-diffractometer' _diffrn_measurement_method \w-\q _diffrn_special_details none _diffrn_radiation_collimation '0.5 mm' _diffrn_radiation_detector 'NaI(Tl) scintillation counter' _diffrn_radiation_monochromator 'planar graphite' _diffrn_radiation_polarisn_norm 90 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_standards_number 3 _diffrn_standards_interval_time 60 _diffrn_reflns_av_sigmaI/netI 0.0929 _diffrn_standards_decay_% 8.4 _diffrn_ambient_temperature 150(2) _diffrn_reflns_number 4289 _reflns_number_total 4131 _diffrn_reflns_av_R_equivalents 0.00 _reflns_number_observed 3079 _diffrn_reflns_theta_min 2.56 _diffrn_reflns_theta_max 24.99 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 17 _reflns_limit_h_min -11 _reflns_limit_h_max 9 _reflns_limit_k_min 0 _reflns_limit_k_max 19 _reflns_limit_l_min 0 _reflns_limit_l_max 17 _reflns_observed_criterion >2.00\s(I) _refine_diff_density_min -0.63 _refine_diff_density_max 0.41 _refine_ls_number_reflns 3079 _refine_ls_number_parameters 262 _refine_ls_R_factor_obs 0.0681 _refine_ls_wR_factor_obs 0.0672 _refine_ls_goodness_of_fit_obs 0.938 _refine_ls_shift/esd_max 0.003 _refine_ls_structure_factor_coef F _refine_ls_number_restraints 6 _refine_ls_abs_structure_flack 'none required' _refine_ls_extinction_coef 'none required' _refine_ls_matrix_type full _refine_ls_weighting_scheme 'unit weights' _refine_ls_hydrogen_treatment 'riding model' _atom_sites_solution_primary 'direct methods' _atom_sites_solution_hydrogens geometric loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_thermal_displace_type Ti1 0.47175(9) 0.21783(5) 0.17530(6) 0.0262 1.0000 Uani N1 0.5541(4) 0.1286(3) 0.1778(3) 0.0305 1.0000 Uani N2 0.4611(4) 0.2639(2) 0.0301(3) 0.0290 1.0000 Uani N4 0.2691(4) 0.2016(2) 0.0657(2) 0.0246 1.0000 Uani N6 0.3217(5) 0.3354(3) 0.1103(3) 0.0351 1.0000 Uani C1 0.4024(6) 0.3442(3) 0.0403(4) 0.0380 1.0000 Uani C3 0.3428(5) 0.2099(3) -0.0094(3) 0.0288 1.0000 Uani C5 0.2053(6) 0.2806(3) 0.0757(3) 0.0347 1.0000 Uani C10 0.6403(6) 0.0592(4) 0.2058(4) 0.0490 1.0000 Uani C11 0.5793(9) -0.0163(4) 0.1543(5) 0.0708 1.0000 Uani C12 0.6537(9) 0.0473(5) 0.3085(4) 0.0798 1.0000 Uani C13 0.7844(7) 0.0743(6) 0.1876(5) 0.0957 1.0000 Uani C21 0.5719(6) 0.2658(4) -0.0263(3) 0.0372 1.0000 Uani C22 0.5117(7) 0.2950(7) -0.1222(4) 0.0992 1.0000 Uani C23 0.628(1) 0.1832(5) -0.0305(7) 0.1064 1.0000 Uani C24 0.6898(7) 0.3202(5) 0.0174(5) 0.0683 1.0000 Uani C41 0.1643(5) 0.1335(3) 0.0495(3) 0.0306 1.0000 Uani C42 0.036(1) 0.164(1) -0.021(1) 0.0412 0.3800 Uani C43 0.225(2) 0.0618(8) 0.011(1) 0.0455 0.3800 Uani C44 0.129(2) 0.118(1) 0.1410(8) 0.0377 0.3800 Uani C421 0.077(1) 0.1261(7) -0.0482(5) 0.0436 0.6200 Uani C431 0.2466(9) 0.0541(5) 0.0728(7) 0.0376 0.6200 Uani C441 0.067(1) 0.1363(7) 0.1150(7) 0.0458 0.6200 Uani C61 0.2768(8) 0.4143(3) 0.1433(4) 0.0514 1.0000 Uani C62 0.1717(9) 0.4588(4) 0.0701(5) 0.0758 1.0000 Uani C63 0.4032(9) 0.4678(4) 0.1764(6) 0.0875 1.0000 Uani C64 0.215(1) 0.3965(5) 0.2260(5) 0.0921 1.0000 Uani Cl1 0.6571(2) 0.3032(1) 0.2424(1) 0.0568 1.0000 Uani Cl2 0..3678(2) 0.2028(1) 0.30005(9) 0.0472 1.0000 Uani H11 0.4759(6) 0.3825(3) 0.0598(4) 0.0520 1.0000 Uiso H12 0.3432(6) 0.3613(3) -0.0167(4) 0.0520 1.0000 Uiso H31 0.2831(5) 0.2333(3) -0.0628(3) 0.0396 1.0000 Uiso H32 0.3757(5) 0.1588(3) -0.0251(3) 0.0396 1.0000 Uiso H51 0.1514(6) 0.2987(3) 0.0175(3) 0.0457 1.0000 Uiso H52 0.1466(6) 0.2769(3) 0.1182(3) 0.0457 1.0000 Uiso H111 0.6393(9) -0.0612(4) 0.1749(5) 0.0836 1.0000 Uiso H112 0.5702(9) -0.0087(4) 0.0899(5) 0.0836 1.0000 Uiso H113 0.4892(9) -0.0264(4) 0.1659(5) 0.0836 1.0000 Uiso H121 0.7103(9) 0.0012(5) 0.3294(4) 0.0899 1.0000 Uiso H122 0.6962(9) 0.0940(5) 0.3406(4) 0.0899 1.0000 Uiso H123 0.5628(9) 0.0398(5) 0.3199(4) 0.0899 1.0000 Uiso H131 0.8428(7) 0.0283(6) 0.2059(5) 0.0971 1.0000 Uiso H132 0.8258(7) 0.1203(6) 0.2218(5) 0.0971 1.0000 Uiso H133 0.7749(7) 0.0839(6) 0.1234(5) 0.0971 1.0000 Uiso H221 0.5826(7) 0.2959(7) -0.1563(4) 0.0919 1.0000 Uiso H222 0.4757(7) 0.3482(7) -0.1193(4) 0.0919 1.0000 Uiso H223 0.4376(7) 0.2599(7) -0.1518(4) 0.0919 1.0000 Uiso H231 0.698(1) 0.1835(5) -0.0655(7) 0.1411 1.0000 Uiso H232 0.669(1) 0.1648(5) 0.0305(7) 0.1411 1.0000 Uiso H233 0.554(1) 0.1480(5) -0.0590(7) 0.1411 1.0000 Uiso H241 0.7585(7) 0.3209(5) -0.0184(5) 0.0842 1.0000 Uiso H242 0.6547(7) 0.3734(5) 0.0211(5) 0.0842 1.0000 Uiso H243 0.7312(7) 0.3010(5) 0.0779(5) 0.0842 1.0000 Uiso H421 -0.034(1) 0.123(1) -0.034(1) 0.0490 0.3800 Uiso H422 -0.000(1) 0.211(1) 0.002(1) 0.0490 0.3800 Uiso H423 0.065(1) 0.177(1) -0.076(1) 0.0490 0.3800 Uiso H431 0.160(2) 0.0183(8) 0.000(1) 0.0662 0.3800 Uiso H432 0.309(2) 0.0454(8) 0.054(1) 0.0662 0.3800 Uiso H433 0.248(2) 0.0766(8) -0.046(1) 0.0662 0.3800 Uiso H441 0.063(2) 0.075(1) 0.1358(8) 0.0479 0.3800 Uiso H442 0.091(2) 0.166(1) 0.1608(8) 0.0479 0.3800 Uiso H443 0.213(2) 0.103(1) 0.1850(8) 0.0479 0.3800 Uiso H4211 0.013(1) 0.0819(7) -0.0523(5) 0.0574 0.6200 Uiso H4212 0.025(1) 0.1748(7) -0.0648(5) 0.0574 0.6200 Uiso H4213 0.137(1) 0.1174(7) -0.0891(5) 0.0574 0.6200 Uiso H4311 0.1831(9) 0.0097(5) 0.0633(7) 0.0473 0.6200 Uiso H4312 0.2980(9) 0.0549(5) 0.1355(7) 0.0473 0.6200 Uiso H4313 0.3100(9) 0.0488(5) 0.0335(7) 0.0473 0.6200 Uiso H4411 0.002(1) 0.0925(7) 0.1026(7) 0.0622 0.6200 Uiso H4412 0.016(1) 0.1861(7) 0.1075(7) 0.0622 0.6200 Uiso H4413 0.121(1) 0.1322(7) 0.1766(7) 0.0622 0.6200 Uiso H621 0.1466(9) 0.5085(4) 0.0943(5) 0.0946 1.0000 Uiso H622 0.2113(9) 0.4694(4) 0.0187(5) 0.0946 1.0000 Uiso H623 0.0902(9) 0.4260(4) 0.0509(5) 0.0946 1.0000 Uiso H631 0.3752(9) 0.5181(4) 0.1974(6) 0.1017 1.0000 Uiso H632 0.4468(9) 0.4770(4) 0.1265(6) 0.1017 1.0000 Uiso H633 0.4680(9) 0.4418(4) 0.2255(6) 0.1017 1.0000 Uiso H641 0.185(1) 0.4455(5) 0.2491(5) 0.1126 1.0000 Uiso H642 0.284(1) 0.3711(5) 0.2733(5) 0.1126 1.0000 Uiso H643 0.136(1) 0.3614(5) 0.2070(5) 0.1126 1.0000 Uiso 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 0.0286(5) 0.0322(5) 0.0198(4) 0.0002(4) 0.0095(3) -0.0050(4) N1 0.026(2) 0.044(3) 0.023(2) -0.004(2) 0.011(2) -0.002(2) N2 0.036(3) 0.032(2) 0.022(2) -0.001(2) 0.013(2) -0.008(2) N4 0.032(2) 0.025(2) 0.020(2) -0.002(2) 0.012(2) -0.005(2) N6 0.048(3) 0.028(2) 0.031(2) -0.003(2) 0.013(2) 0.004(2) C1 0.057(4) 0.029(3) 0.032(3) 0.002(2) 0.019(3) -0.006(3) C3 0.031(3) 0.033(3) 0.024(2) -0.001(2) 0.010(2) -0.005(2) C5 0.042(3) 0.039(3) 0.026(3) 0.004(2) 0.013(2) 0.009(3) C10 0.037(3) 0.072(4) 0.034(3) -0.008(3) -0.000(3) 0.029(3) C11 0.097(6) 0.055(4) 0.054(4) -0.009(3) 0.005(4) 0.042(4) C12 0.107(7) 0.080(6) 0.043(4) 0.005(4) 0.001(4) 0.052(5) C13 0.042(4) 0.17(1) 0.067(5) -0.034(6) 0.003(4) 0.038(5) C21 0.037(3) 0.052(3) 0.027(3) 0.004(2) 0.017(2) -0.014(3) C22 0.046(4) 0.22(1) 0.036(4) 0.039(5) 0.012(3) -0.040(6) C23 0.158(9) 0.060(5) 0.156(9) -0.007(5) 0.148(8) 0.000(5) C24 0.040(4) 0.091(6) 0.077(5) -0.032(4) 0.020(4) -0.014(4) C41 0.024(3) 0.043(3) 0.027(3) 0.001(2) 0.010(2) -0.009(2) C42 0.024(9) 0.06(1) 0.039(9) 0.002(8) 0.013(7) -0.020(8) C43 0.03(1) 0.040(9) 0.07(1) -0.017(9) 0.03(1) -0.015(7) C44 0.05(1) 0.04(1) 0.019(8) 0.012(7) 0.006(8) -0.002(9) C421 0.040(6) 0.048(7) 0.042(6) 0.011(5) 0.006(5) -0.020(5) C431 0.035(6) 0.032(5) 0.045(6) -0.001(5) 0.008(5) -0.016(4) C441 0.044(8) 0.050(7) 0.044(7) 0.024(5) 0.012(6) -0.008(6) C61 0.085(5) 0.030(3) 0.039(3) -0.006(3) 0.013(3) 0.018(3) C62 0.107(7) 0.059(5) 0.056(4) -0.007(4) 0.006(4) 0.040(5) C63 0.119(7) 0.040(4) 0.096(6) -0.032(4) 0.009(6) 0.002(4) C64 0.17(1) 0.059(5) 0.063(5) -0.008(4) 0.061(6) 0.037(6) Cl1 0.071(1) 0.055(1) 0.0330(7) 0.0057(7) -0.0114(7) -0.0342(8) Cl2 0.0564(9) 0.065(1) 0.0275(7) 0.0063(7) 0.0255(6) 0.0149(8) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ti1 . N1 . 1.692(5) yes Ti1 . N2 . 2.292(4) yes Ti1 . N4 . 2.290(4) yes Ti1 . N6 . 2.513(5) yes Ti1 . Cl1 . 2.351(2) yes Ti1 . Cl2 . 2.351(2) yes N1 . C10 . 1.440(7) yes N2 . C1 . 1.481(7) yes N2 . C3 . 1.485(6) yes N2 . C21 . 1.533(6) yes N4 . C3 . 1.485(6) yes N4 . C5 . 1.482(6) yes N4 . C41 . 1.517(6) yes N6 . C1 . 1.467(6) yes N6 . C5 . 1.465(7) yes N6 . C61 . 1.510(7) yes C10 . C11 . 1.526(9) yes C10 . C12 . 1.529(8) yes C10 . C13 . 1.53(1) yes C21 . C22 . 1.504(8) yes C21 . C23 . 1.493(9) yes C21 . C24 . 1.500(8) yes C41 . C42 . 1.536(9) yes C41 . C43 . 1.516(9) yes C41 . C44 . 1.517(9) yes C41 . C421 . 1.524(7) yes C41 . C431 . 1.550(7) yes C41 . C441 . 1.530(8) yes C61 . C62 . 1.517(9) yes C61 . C63 . 1.52(1) yes C61 . C64 . 1.54(1) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . Ti1 . N2 . 103.3(2) yes N1 . Ti1 . N4 . 104.3(2) yes N2 . Ti1 . N4 . 61.2(1) yes N1 . Ti1 . N6 . 158.6(2) yes N2 . Ti1 . N6 . 58.5(1) yes N4 . Ti1 . N6 . 58.4(1) yes N1 . Ti1 . Cl1 . 101.6(2) yes N2 . Ti1 . Cl1 . 93.6(1) yes N4 . Ti1 . Cl1 . 147.3(1) yes N6 . Ti1 . Cl1 . 91.3(1) yes N1 . Ti1 . Cl2 . 100.7(2) yes N2 . Ti1 . Cl2 . 149.6(1) yes N4 . Ti1 . Cl2 . 95.1(1) yes N6 . Ti1 . Cl2 . 93.7(1) yes Cl1 . Ti1 . Cl2 . 99.44(8) yes Ti1 . N1 . C10 . 164.1(4) yes Ti1 . N2 . C1 . 97.8(3) yes Ti1 . N2 . C3 . 91.9(3) yes C1 . N2 . C3 . 107.4(4) yes Ti1 . N2 . C21 . 130.8(3) yes C1 . N2 . C21 . 112.7(4) yes C3 . N2 . C21 . 112.8(4) yes Ti1 . N4 . C3 . 92.0(3) yes Ti1 . N4 . C5 . 98.2(3) yes C3 . N4 . C5 . 106.8(4) yes Ti1 . N4 . C41 . 130.7(3) yes C3 . N4 . C41 . 112.6(3) yes C5 . N4 . C41 . 113.0(4) yes Ti1 . N6 . C1 . 89.3(3) yes Ti1 . N6 . C5 . 89.6(3) yes C1 . N6 . C5 . 108.6(4) yes Ti1 . N6 . C61 . 138.1(3) yes C1 . N6 . C61 . 113.5(4) yes C5 . N6 . C61 . 113.2(5) yes N2 . C1 . N6 . 106.0(4) yes N2 . C3 . N4 . 103.4(4) yes N4 . C5 . N6 . 105.9(4) yes N1 . C10 . C11 . 112.3(5) yes N1 . C10 . C12 . 107.7(5) yes C11 . C10 . C12 . 109.6(6) yes N1 . C10 . C13 . 109.0(6) yes C11 . C10 . C13 . 108.6(6) yes C12 . C10 . C13 . 109.6(6) yes N2 . C21 . C22 . 111.2(5) yes N2 . C21 . C23 . 109.0(4) yes C22 . C21 . C23 . 109.0(7) yes N2 . C21 . C24 . 110.5(5) yes C22 . C21 . C24 . 108.5(6) yes C23 . C21 . C24 . 108.5(6) yes N4 . C41 . C42 . 106.3(7) yes N4 . C41 . C43 . 109.5(7) yes N4 . C41 . C44 . 106.1(8) yes C42 . C41 . C43 . 109.4(11) yes C42 . C41 . C44 . 111.3(9) yes C43 . C41 . C44 . 113.9(11) yes N4 . C41 . C421 . 115.2(5) yes N4 . C41 . C431 . 107.5(5) yes N4 . C41 . C441 . 112.5(6) yes C421 . C41 . C431 . 107.3(7) yes C421 . C41 . C441 . 108.7(7) yes C431 . C41 . C441 . 104.9(7) yes N6 . C61 . C62 . 113.0(5) yes N6 . C61 . C63 . 109.7(6) yes C62 . C61 . C63 . 108.7(6) yes N6 . C61 . C64 . 107.5(5) yes C62 . C61 . C64 . 110.2(6) yes C63 . C61 . C64 . 107.6(6) yes #==end