# Copyright The Royal Society of Chemistry, 1999 # CCDC Number: 186/1267 data_Compound_14 _audit_creation_date 98-06-09 _audit_creation_method CRYSTALS_ver_07-07-97 _publ_contact_letter ; This CIF corresponds to the manuscript entitled "Cycloaddition Reactions of Titanium and Zirconium Imido, Oxo, and Hydrazido Complexes Supported by Tetraaza Macrcocylic Ligands" A J Blake, J. M. McInnes, P Mountford, G. I. Nikonov, D. Swallow and D. J. Watkin submitted to Dalton Transactions ; _publ_contact_author ; Dr P Mountford School of Chemistry University of Nottingham Nottingham NG7 2RD ; _publ_contact_author_phone '0115 951 3513' _publ_contact_author_fax '0115 951 3563' _publ_contact_author_email Philip.Mountford@nott.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 solution of crystal structures by direct methods. J. Appl. Cryst. (27), 435-435 Carruthers, J.R. and Watkin, D.J. (1979), Acta Cryst, A35, 698-699 Watkin, D.J., Prout, C.K. Carruthers, J.R. & Betteridge, P.W. (1996) CRYSTALS Issue 10. Chemical Crystallography Laboratory, OXFORD, UK. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. Watkin, D.J., Prout, C.K., Lilley, P.M.deQ. (1994), RC93, Chemical Crystallography Laboratory, Oxford, UK. ; _chemical_name_systematic ; [Ti{N(Tol)C(O)O}(Me4taa)] ; _chemical_melting_point 'not measured' _refine_ls_matrix_type full _atom_sites_solution_primary direct _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment riding _cell_length_a 8.920(2) _cell_angle_alpha 67.19(4) _cell_length_b 12.903(3) _cell_angle_beta 76.02(4) _cell_length_c 13.55(1) _cell_angle_gamma 73.68(2) _cell_volume 1364.5(22) _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1 ' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' '-x,-y,-z' 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 ' 0.0170 0.0090 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 ' 0.0290 0.0180 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' 'O ' 0.0470 0.0320 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International_Tables_Vol_IV_Table_2.2B' 'Cl ' 0.3480 0.7020 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 ' 0.1890 1.8070 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' _chemical_formula_sum ' C30 H28 Ti1 O2 N5 ' _chemical_formula_moiety ' C30 H28 Ti1 O2 N5 ' _chemical_compound_source ; [Ti(NTol)(Me4taa)] + CO2 ; _chemical_formula_weight 538.49 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 8 _cell_measurement_theta_max 40 _cell_measurement_temperature 173 _cell_formula_units_Z 2 _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_min 0.10 _exptl_crystal_size_mid 0.80 _exptl_crystal_size_max 0.80 _exptl_crystal_density_diffrn 1.31 _exptl_crystal_density_meas 'not measured' _exptl_crystal_F_000 562 _exptl_absorpt_coefficient_mu 2.94 _exptl_absorpt_correction_type refdelf _exptl_absorpt_process_details ; refined from delta-F (Walker & Stuart , 1983)' ; _exptl_absorpt_correction_T_min 0.40 _exptl_absorpt_correction_T_max 0.75 _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_wavelength 1.54180 _diffrn_measurement_method \w/2\q _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-nonius CAD4 ' _diffrn_standards_interval_time 60 _diffrn_standards_interval_count 0 _diffrn_standards_number 3 _diffrn_standards_decay_% 3.57 _diffrn_ambient_temperature 173 _diffrn_reflns_number 5433 _reflns_number_total 5233 _diffrn_reflns_av_R_equivalents 0.03 _diffrn_measured_fraction_theta_max 0.931 _reflns_number_observed 2677 _diffrn_reflns_theta_min 0.00 _diffrn_reflns_theta_max 75.00 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 16 _reflns_limit_h_min -10 _reflns_limit_h_max 11 _reflns_limit_k_min -14 _reflns_limit_k_max 16 _reflns_limit_l_min 0 _reflns_limit_l_max 16 _reflns_observed_criterion >2.00\s(I) _refine_diff_density_min -0.47 _refine_diff_density_max 0.46 _refine_ls_number_reflns 3045 _refine_ls_number_parameters 343 _refine_ls_R_factor_obs 0.0670 _refine_ls_wR_factor_obs 0.0736 _refine_ls_goodness_of_fit_obs 1.106 _refine_ls_shift/esd_max 0.002 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'chebychev polynomial' _refine_ls_number_restraints none _refine_ls_extinction_coef none _refine_ls_extinction_method none _refine_ls_abs_structure_flack none _computing_data_collection 'CAD-4 software (Enraf-Nonius, 1989)' _computing_data_reduction ; RC93 (Watkin, D.J., Prout, C.K., Lilley, P.M.deQ. 1994) ; _computing_cell_refinement 'CAD-4 software (Enraf-Nonius, 1989)' _computing_structure_refinement ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_publication_material ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_molecular_graphics ; CAMERON (Watkin, Prout & Pearce, 1996) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' 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 0.5889(1) 0.27369(7) 0.86322(8) 0.0405 1.0000 Uani N1 0.4665(4) 0.3051(3) 1.0035(3) 0.0432 1.0000 Uani N2 0.3702(5) 0.3216(3) 0.8200(4) 0.0516 1.0000 Uani N3 0.6899(5) 0.1369(3) 0.9824(3) 0.0411 1.0000 Uani N4 0.5853(5) 0.1482(3) 0.8052(3) 0.0429 1.0000 Uani N5 0.7764(5) 0.3100(3) 0.7478(3) 0.0447 1.0000 Uani C1 0.3150(6) 0.3463(4) 1.0333(5) 0.0477 1.0000 Uani C2 0.2026(6) 0.3680(4) 0.9679(5) 0.0579 1.0000 Uani C3 0.2262(6) 0.3578(4) 0.8671(5) 0.0571 1.0000 Uani C4 0.2586(7) 0.3631(5) 1.1409(5) 0.0661 1.0000 Uani C5 0.0820(7) 0.3817(5) 0.8160(6) 0.0748 1.0000 Uani C6 0.7259(5) 0.0232(4) 1.0029(4) 0.0403 1.0000 Uani C7 0.6977(6) -0.0246(4) 0.9357(4) 0.0432 1.0000 Uani C8 0.6328(6) 0.0347(4) 0.8390(4) 0.0423 1.0000 Uani C9 0.7903(6) -0.0576(4) 1.1049(4) 0.0513 1.0000 Uani C10 0.6135(7) -0.0370(5) 0.7801(5) 0.0587 1.0000 Uani C11 0.5928(6) 0.2855(4) 1.0592(4) 0.0443 1.0000 Uani C12 0.6101(6) 0.3524(4) 1.1126(4) 0.0503 1.0000 Uani C13 0.7463(7) 0.3258(5) 1.1569(5) 0.0598 1.0000 Uani C14 0.8674(7) 0.2351(5) 1.1451(5) 0.0573 1.0000 Uani C15 0.8544(6) 0.1694(5) 1.0891(4) 0.0501 1.0000 Uani C16 0.7162(6) 0.1919(4) 1.0472(4) 0.0411 1.0000 Uani C17 0.4061(7) 0.3125(5) 0.7146(5) 0.0562 1.0000 Uani C18 0.3486(8) 0.3925(6) 0.6230(6) 0.0758 1.0000 Uani C19 0.405(1) 0.3776(7) 0.5236(6) 0.0905 1.0000 Uani C20 0.5259(9) 0.2842(7) 0.5155(5) 0.0832 1.0000 Uani C21 0.5868(8) 0.2043(5) 0.6063(4) 0.0620 1.0000 Uani C22 0.5263(6) 0.2166(5) 0.7064(4) 0.0511 1.0000 Uani C23 0.7431(6) 0.4232(4) 0.7419(4) 0.0468 1.0000 Uani C24 0.8948(6) 0.2631(4) 0.6761(4) 0.0457 1.0000 Uani C25 0.9515(6) 0.1457(4) 0.7104(4) 0.0472 1.0000 Uani C26 1.0639(8) 0.0932(5) 0.6454(5) 0.0661 1.0000 Uani C27 1.1270(9) 0.1588(6) 0.5433(6) 0.0814 1.0000 Uani C28 1.0707(9) 0.2760(6) 0.5099(5) 0.0809 1.0000 Uani C29 0.9554(7) 0.3285(5) 0.5745(4) 0.0623 1.0000 Uani C30 1.257(1) 0.1009(8) 0.4744(7) 0.1388 1.0000 Uani O1 0.6240(4) 0.4313(3) 0.8202(3) 0.0548 1.0000 Uani O2 0.8080(4) 0.5015(3) 0.6804(3) 0.0540 1.0000 Uani H21 0.0949(6) 0.3927(4) 0.9970(5) 0.0690 1.0000 Uiso H41 0.1468(7) 0.3937(5) 1.1480(5) 0.0885 1.0000 Uiso H42 0.3120(7) 0.4155(5) 1.1459(5) 0.0885 1.0000 Uiso H43 0.2808(7) 0.2903(5) 1.1976(5) 0.0885 1.0000 Uiso H51 -0.0105(7) 0.4066(5) 0.8614(6) 0.0916 1.0000 Uiso H52 0.0909(7) 0.4408(5) 0.7462(6) 0.0916 1.0000 Uiso H53 0.0737(7) 0.3129(5) 0.8079(6) 0.0916 1.0000 Uiso H71 0.7257(6) -0.1069(4) 0.9570(4) 0.0545 1.0000 Uiso H91 0.8098(6) -0.1354(4) 1.1068(4) 0.0646 1.0000 Uiso H92 0.8872(6) -0.0402(4) 1.1067(4) 0.0646 1.0000 Uiso H93 0.7147(6) -0.0487(4) 1.1664(4) 0.0646 1.0000 Uiso H101 0.6552(7) -0.1166(5) 0.8174(5) 0.0790 1.0000 Uiso H102 0.6693(7) -0.0139(5) 0.7077(5) 0.0790 1.0000 Uiso H103 0.5033(7) -0.0265(5) 0.7778(5) 0.0790 1.0000 Uiso H121 0.5278(6) 0.4170(4) 1.1190(4) 0.0641 1.0000 Uiso H131 0.7569(7) 0.3708(5) 1.1961(5) 0.0785 1.0000 Uiso H141 0.9612(7) 0.2177(5) 1.1763(5) 0.0773 1.0000 Uiso H151 0.9408(6) 0.1086(5) 1.0790(4) 0.0630 1.0000 Uiso H181 0.2695(8) 0.4593(6) 0.6274(6) 0.0932 1.0000 Uiso H191 0.360(1) 0.4313(7) 0.4605(6) 0.1124 1.0000 Uiso H201 0.5670(9) 0.2755(7) 0.4462(5) 0.1010 1.0000 Uiso H211 0.6710(8) 0.1407(5) 0.6002(4) 0.0838 1.0000 Uiso H251 0.9109(6) 0.0992(4) 0.7813(4) 0.0580 1.0000 Uiso H261 1.0991(8) 0.0112(5) 0.6709(5) 0.0837 1.0000 Uiso H281 1.1123(9) 0.3229(6) 0.4396(5) 0.1000 1.0000 Uiso H291 0.9180(7) 0.4104(5) 0.5484(4) 0.0806 1.0000 Uiso H301 1.287(1) 0.1576(8) 0.4067(7) 0.1624 1.0000 Uiso H302 1.347(1) 0.0627(8) 0.5119(7) 0.1624 1.0000 Uiso H303 1.219(1) 0.0457(8) 0.4611(7) 0.1624 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 0.0338(5) 0.0389(4) 0.0460(5) -0.0146(4) -0.0089(4) -0.0008(4) N1 0.029(2) 0.045(2) 0.054(3) -0.017(2) -0.007(2) -0.005(2) N2 0.041(3) 0.044(2) 0.070(3) -0.020(2) -0.022(2) 0.004(2) N3 0.035(2) 0.039(2) 0.045(2) -0.015(2) -0.006(2) -0.001(2) N4 0.040(2) 0.040(2) 0.047(2) -0.013(2) -0.008(2) -0.007(2) N5 0.042(2) 0.041(2) 0.047(2) -0.013(2) -0.005(2) -0.007(2) C1 0.036(3) 0.039(2) 0.072(4) -0.030(2) -0.005(2) -0.002(2) C2 0.034(3) 0.042(3) 0.102(5) -0.035(3) -0.011(3) 0.002(2) C3 0.038(3) 0.039(3) 0.098(5) -0.025(3) -0.026(3) 0.003(2) C4 0.047(3) 0.066(4) 0.101(5) -0.058(4) 0.011(3) -0.011(3) C5 0.049(4) 0.060(4) 0.113(6) -0.024(4) -0.042(4) 0.010(3) C6 0.027(2) 0.044(3) 0.044(3) -0.020(2) -0.000(2) 0.003(2) C7 0.037(3) 0.039(2) 0.047(3) -0.018(2) -0.001(2) 0.001(2) C8 0.037(3) 0.048(3) 0.045(3) -0.022(2) 0.001(2) -0.011(2) C9 0.047(3) 0.045(3) 0.054(3) -0.012(2) -0.011(2) -0.002(2) C10 0.067(4) 0.057(3) 0.057(3) -0.031(3) -0.003(3) -0.010(3) C11 0.036(3) 0.046(3) 0.047(3) -0.017(2) 0.001(2) -0.006(2) C12 0.047(3) 0.043(3) 0.059(3) -0.023(2) -0.004(3) -0.004(2) C13 0.061(4) 0.061(3) 0.063(4) -0.026(3) -0.008(3) -0.016(3) C14 0.051(3) 0.061(3) 0.061(4) -0.017(3) -0.014(3) -0.015(3) C15 0.038(3) 0.050(3) 0.059(3) -0.018(2) -0.007(2) -0.005(2) C16 0.033(3) 0.042(2) 0.043(3) -0.014(2) -0.000(2) -0.004(2) C17 0.051(3) 0.051(3) 0.066(4) -0.007(3) -0.029(3) -0.010(3) C18 0.074(5) 0.066(4) 0.077(5) -0.004(3) -0.039(4) -0.004(3) C19 0.093(6) 0.097(6) 0.071(5) -0.004(4) -0.045(4) -0.012(5) C20 0.089(6) 0.111(6) 0.048(4) -0.008(4) -0.021(3) -0.036(5) C21 0.071(4) 0.075(4) 0.045(3) -0.015(3) -0.017(3) -0.024(3) C22 0.052(3) 0.055(3) 0.048(3) -0.012(2) -0.013(2) -0.017(3) C23 0.043(3) 0.047(3) 0.047(3) -0.009(2) -0.017(2) -0.005(2) C24 0.043(3) 0.054(3) 0.042(3) -0.020(2) -0.006(2) -0.007(2) C25 0.044(3) 0.052(3) 0.038(3) -0.013(2) -0.002(2) -0.005(2) C26 0.072(4) 0.062(3) 0.058(4) -0.027(3) 0.006(3) -0.008(3) C27 0.089(5) 0.087(5) 0.064(4) -0.042(4) 0.024(4) -0.019(4) C28 0.105(6) 0.080(5) 0.049(4) -0.021(3) 0.019(4) -0.034(4) C29 0.071(4) 0.064(3) 0.048(3) -0.016(3) 0.004(3) -0.024(3) C30 0.18(1) 0.106(7) 0.100(7) -0.054(6) 0.063(7) -0.026(7) O1 0.051(2) 0.044(2) 0.066(2) -0.020(2) -0.002(2) -0.009(2) O2 0.063(2) 0.048(2) 0.049(2) -0.008(2) -0.014(2) -0.016(2) 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 . 2.078(5) yes Ti1 . N2 . 2.031(4) yes Ti1 . N3 . 2.033(4) yes Ti1 . N4 . 2.066(4) yes Ti1 . N5 . 2.018(4) yes Ti1 . C23 . 2.502(5) yes Ti1 . O1 . 1.981(4) yes N1 . C1 . 1.331(6) yes N1 . C11 . 1.416(6) yes N2 . C3 . 1.332(7) yes N2 . C17 . 1.430(7) yes N3 . C6 . 1.340(6) yes N3 . C16 . 1.416(6) yes N4 . C8 . 1.326(6) yes N4 . C22 . 1.419(6) yes N5 . C23 . 1.381(6) yes N5 . C24 . 1.424(6) yes C1 . C2 . 1.396(8) yes C1 . C4 . 1.502(8) yes C2 . C3 . 1.384(9) yes C3 . C5 . 1.507(7) yes C6 . C7 . 1.380(7) yes C6 . C9 . 1.502(7) yes C7 . C8 . 1.406(7) yes C8 . C10 . 1.501(7) yes C11 . C12 . 1.381(7) yes C11 . C16 . 1.420(7) yes C12 . C13 . 1.383(8) yes C13 . C14 . 1.383(8) yes C14 . C15 . 1.380(8) yes C15 . C16 . 1.391(7) yes C17 . C18 . 1.374(8) yes C17 . C22 . 1.413(8) yes C18 . C19 . 1.39(1) yes C19 . C20 . 1.39(1) yes C20 . C21 . 1.377(8) yes C21 . C22 . 1.387(8) yes C23 . O1 . 1.321(6) yes C23 . O2 . 1.221(6) yes C24 . C25 . 1.379(7) yes C24 . C29 . 1.377(7) yes C25 . C26 . 1.377(7) yes C26 . C27 . 1.389(9) yes C27 . C28 . 1.38(1) yes C27 . C30 . 1.518(9) yes C28 . C29 . 1.384(9) 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 . 83.5(2) yes N1 . Ti1 . N3 . 76.9(2) yes N2 . Ti1 . N3 . 132.1(2) yes N1 . Ti1 . N4 . 129.8(2) yes N2 . Ti1 . N4 . 76.8(2) yes N3 . Ti1 . N4 . 83.1(2) yes N1 . Ti1 . N5 . 141.6(2) yes N2 . Ti1 . N5 . 119.3(2) yes N3 . Ti1 . N5 . 102.4(2) yes N4 . Ti1 . N5 . 87.4(2) yes N1 . Ti1 . C23 . 113.3(2) yes N2 . Ti1 . C23 . 108.3(2) yes N3 . Ti1 . C23 . 119.5(2) yes N4 . Ti1 . C23 . 116.7(2) yes N5 . Ti1 . C23 . 33.4(2) yes N1 . Ti1 . O1 . 83.1(2) yes N2 . Ti1 . O1 . 96.3(2) yes N3 . Ti1 . O1 . 123.5(2) yes N4 . Ti1 . O1 . 144.1(2) yes N5 . Ti1 . O1 . 65.0(2) yes C23 . Ti1 . O1 . 31.7(2) yes Ti1 . N1 . C1 . 132.5(4) yes Ti1 . N1 . C11 . 101.0(3) yes C1 . N1 . C11 . 126.1(4) yes Ti1 . N2 . C3 . 133.7(4) yes Ti1 . N2 . C17 . 101.3(3) yes C3 . N2 . C17 . 124.9(5) yes Ti1 . N3 . C6 . 133.4(3) yes Ti1 . N3 . C16 . 101.4(3) yes C6 . N3 . C16 . 125.2(4) yes Ti1 . N4 . C8 . 133.7(3) yes Ti1 . N4 . C22 . 100.9(3) yes C8 . N4 . C22 . 125.2(4) yes Ti1 . N5 . C23 . 92.9(3) yes Ti1 . N5 . C24 . 141.8(3) yes C23 . N5 . C24 . 124.7(4) yes N1 . C1 . C2 . 120.5(5) yes N1 . C1 . C4 . 121.2(5) yes C2 . C1 . C4 . 118.2(5) yes C1 . C2 . C3 . 128.4(5) yes N2 . C3 . C2 . 121.1(5) yes N2 . C3 . C5 . 121.3(6) yes C2 . C3 . C5 . 117.5(5) yes N3 . C6 . C7 . 122.1(4) yes N3 . C6 . C9 . 120.2(4) yes C7 . C6 . C9 . 117.6(4) yes C6 . C7 . C8 . 126.8(4) yes N4 . C8 . C7 . 120.8(4) yes N4 . C8 . C10 . 122.4(5) yes C7 . C8 . C10 . 116.7(4) yes N1 . C11 . C12 . 126.8(5) yes N1 . C11 . C16 . 112.9(4) yes C12 . C11 . C16 . 120.1(5) yes C11 . C12 . C13 . 119.6(5) yes C12 . C13 . C14 . 120.6(5) yes C13 . C14 . C15 . 120.6(5) yes C14 . C15 . C16 . 119.9(5) yes N3 . C16 . C11 . 114.5(4) yes N3 . C16 . C15 . 126.1(4) yes C11 . C16 . C15 . 119.1(5) yes N2 . C17 . C18 . 126.3(6) yes N2 . C17 . C22 . 113.7(4) yes C18 . C17 . C22 . 119.5(6) yes C17 . C18 . C19 . 120.2(7) yes C18 . C19 . C20 . 120.0(6) yes C19 . C20 . C21 . 120.4(7) yes C20 . C21 . C22 . 119.7(7) yes N4 . C22 . C17 . 113.1(5) yes N4 . C22 . C21 . 126.3(5) yes C17 . C22 . C21 . 120.1(5) yes Ti1 . C23 . N5 . 53.7(2) yes Ti1 . C23 . O1 . 51.9(2) yes N5 . C23 . O1 . 105.3(4) yes Ti1 . C23 . O2 . 175.2(4) yes N5 . C23 . O2 . 129.3(5) yes O1 . C23 . O2 . 125.4(5) yes N5 . C24 . C25 . 118.1(4) yes N5 . C24 . C29 . 123.5(5) yes C25 . C24 . C29 . 118.4(5) yes C24 . C25 . C26 . 121.8(5) yes C25 . C26 . C27 . 120.2(6) yes C26 . C27 . C28 . 117.7(6) yes C26 . C27 . C30 . 119.9(7) yes C28 . C27 . C30 . 122.4(7) yes C27 . C28 . C29 . 122.1(6) yes C24 . C29 . C28 . 119.9(6) yes Ti1 . O1 . C23 . 96.4(3) yes