# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Joseph Schmidt' _publ_contact_author_email JOSEPH.SCHMIDT@UTOLEDO.EDU _publ_section_title ; Titanium Imido Complexes Utilizing Orthometallated Acetophenone Imine Ligands: Synthesis, Isolation, and Characterization ; loop_ _publ_author_name 'Joseph Schmidt' 'Tamam I. Baiz' 'John F. Beck' 'Abdollah Neshat' # Attachment 'compiled_cifs.txt' data_(L1)2Ti(NC(CH3)3)_(1a) _database_code_depnum_ccdc_archive 'CCDC 726830' #------------------------------------------------------------------------------ _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C46 H57 N3 O4 Ti' _chemical_formula_sum 'C46 H57 N3 O4 Ti' _chemical_formula_weight 763.85 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 10.8857(8) _cell_length_b 20.8619(14) _cell_length_c 18.3463(13) _cell_angle_alpha 90.00 _cell_angle_beta 99.708(4) _cell_angle_gamma 90.00 _cell_volume 4106.7(5) _cell_formula_units_Z 4 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 4737 _cell_measurement_theta_min 1.90 _cell_measurement_theta_max 22.75 _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.235 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1632 _exptl_absorpt_coefficient_mu 0.255 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.8824 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details SADABS _exptl_special_details ; Due to poor crystal quality, the data was integrated by SAINT to a maximum 2theta of 45.5\% (a resolution of 0.92A). Due to the reduced resolution of this structure, geometric parameters are less reliable than in the other two crystal structures herein. ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART CCD' _diffrn_measurement_method \w-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 29304 _diffrn_reflns_av_R_equivalents 0.0467 _diffrn_reflns_av_sigmaI/netI 0.0341 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.90 _diffrn_reflns_theta_max 22.75 _reflns_number_total 5525 _reflns_number_gt 4486 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART v5.625' _computing_cell_refinement 'Bruker SAINT v6.22' _computing_data_reduction 'Bruker SAINT v6.22' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0507P)^2^+1.4526P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5525 _refine_ls_number_parameters 487 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0492 _refine_ls_R_factor_gt 0.0368 _refine_ls_wR_factor_ref 0.0998 _refine_ls_wR_factor_gt 0.0932 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.036 _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 0.74502(4) 0.597079(18) 1.19375(2) 0.02447(14) Uani 1 1 d . . . N1 N 0.84033(17) 0.61040(9) 1.13155(10) 0.0316(5) Uani 1 1 d . . . N2 N 0.67625(16) 0.68838(8) 1.23681(9) 0.0250(4) Uani 1 1 d . . . N3 N 0.70843(17) 0.49560(8) 1.22713(9) 0.0248(4) Uani 1 1 d . . . O1 O 1.04471(14) 0.53781(7) 1.30080(8) 0.0340(4) Uani 1 1 d . . . O2 O 1.17609(15) 0.57901(8) 1.40111(9) 0.0369(4) Uani 1 1 d . . . O3 O 0.51172(16) 0.66161(7) 1.03870(9) 0.0410(4) Uani 1 1 d . . . O4 O 0.33873(17) 0.61614(8) 0.96865(9) 0.0464(5) Uani 1 1 d . . . C1 C 0.9337(2) 0.62767(12) 1.08717(13) 0.0376(6) Uani 1 1 d . . . C2 C 0.8716(3) 0.63778(14) 1.00737(14) 0.0547(8) Uani 1 1 d . . . H2A H 0.8110 0.6715 1.0051 0.082 Uiso 1 1 calc R . . H2B H 0.8311 0.5989 0.9885 0.082 Uiso 1 1 calc R . . H2C H 0.9335 0.6493 0.9781 0.082 Uiso 1 1 calc R . . C3 C 1.0300(3) 0.57426(15) 1.09037(18) 0.0633(9) Uani 1 1 d . . . H3A H 0.9896 0.5354 1.0712 0.095 Uiso 1 1 calc R . . H3B H 1.0692 0.5677 1.1407 0.095 Uiso 1 1 calc R . . H3C H 1.0918 0.5861 1.0612 0.095 Uiso 1 1 calc R . . C4 C 0.9970(3) 0.68968(14) 1.11811(17) 0.0574(8) Uani 1 1 d . . . H4A H 0.9360 0.7232 1.1156 0.086 Uiso 1 1 calc R . . H4B H 1.0595 0.7016 1.0895 0.086 Uiso 1 1 calc R . . H4C H 1.0353 0.6831 1.1687 0.086 Uiso 1 1 calc R . . C5 C 0.8796(2) 0.61963(10) 1.29380(12) 0.0258(5) Uani 1 1 d . . . C6 C 0.9911(2) 0.59283(10) 1.32478(12) 0.0268(5) Uani 1 1 d . . . C7 C 1.0728(2) 0.61767(11) 1.38430(12) 0.0297(6) Uani 1 1 d . . . C8 C 1.0486(2) 0.67371(11) 1.41736(13) 0.0351(6) Uani 1 1 d . . . H8A H 1.1037 0.6907 1.4569 0.042 Uiso 1 1 calc R . . C9 C 0.9375(2) 0.70398(11) 1.38888(12) 0.0339(6) Uani 1 1 d . . . H9A H 0.9168 0.7422 1.4100 0.041 Uiso 1 1 calc R . . C10 C 0.8561(2) 0.67821(10) 1.32913(12) 0.0273(5) Uani 1 1 d . . . C11 C 1.1411(2) 0.52161(12) 1.35907(13) 0.0373(6) Uani 1 1 d . . . H11A H 1.2120 0.5047 1.3396 0.045 Uiso 1 1 calc R . . H11B H 1.1126 0.4892 1.3903 0.045 Uiso 1 1 calc R . . C12 C 0.7411(2) 0.71179(10) 1.29719(12) 0.0277(5) Uani 1 1 d . . . C13 C 0.7030(2) 0.77105(11) 1.33408(14) 0.0389(6) Uani 1 1 d . . . H13A H 0.6260 0.7870 1.3068 0.058 Uiso 1 1 calc R . . H13B H 0.7665 0.8032 1.3354 0.058 Uiso 1 1 calc R . . H13C H 0.6922 0.7609 1.3836 0.058 Uiso 1 1 calc R . . C14 C 0.5626(2) 0.72062(10) 1.20371(12) 0.0267(5) Uani 1 1 d . . . C15 C 0.4486(2) 0.69825(11) 1.21956(13) 0.0309(6) Uani 1 1 d . . . C16 C 0.3408(2) 0.73008(12) 1.18805(14) 0.0390(6) Uani 1 1 d . . . H16A H 0.2645 0.7165 1.1988 0.047 Uiso 1 1 calc R . . C17 C 0.3443(2) 0.78144(12) 1.14122(14) 0.0388(6) Uani 1 1 d . . . H17A H 0.2711 0.8022 1.1206 0.047 Uiso 1 1 calc R . . C18 C 0.4566(2) 0.80164(11) 1.12519(13) 0.0355(6) Uani 1 1 d . . . H18A H 0.4584 0.8361 1.0932 0.043 Uiso 1 1 calc R . . C19 C 0.5676(2) 0.77210(10) 1.15548(13) 0.0298(6) Uani 1 1 d . . . C20 C 0.4411(2) 0.64261(12) 1.27200(14) 0.0385(6) Uani 1 1 d . . . H20A H 0.5195 0.6187 1.2765 0.046 Uiso 1 1 calc R . . C21 C 0.4285(3) 0.66686(14) 1.34880(15) 0.0570(8) Uani 1 1 d . . . H21A H 0.4967 0.6950 1.3666 0.085 Uiso 1 1 calc R . . H21B H 0.4296 0.6311 1.3819 0.085 Uiso 1 1 calc R . . H21C H 0.3513 0.6897 1.3462 0.085 Uiso 1 1 calc R . . C22 C 0.3352(3) 0.59651(13) 1.24283(15) 0.0476(7) Uani 1 1 d . . . H22A H 0.3455 0.5812 1.1949 0.071 Uiso 1 1 calc R . . H22B H 0.2569 0.6185 1.2391 0.071 Uiso 1 1 calc R . . H22C H 0.3367 0.5609 1.2761 0.071 Uiso 1 1 calc R . . C23 C 0.6888(2) 0.79668(11) 1.13551(14) 0.0389(6) Uani 1 1 d . . . H23A H 0.7574 0.7713 1.1627 0.047 Uiso 1 1 calc R . . C24 C 0.6903(3) 0.78874(14) 1.05313(16) 0.0574(8) Uani 1 1 d . . . H24A H 0.6762 0.7446 1.0396 0.086 Uiso 1 1 calc R . . H24B H 0.7697 0.8020 1.0424 0.086 Uiso 1 1 calc R . . H24C H 0.6257 0.8146 1.0255 0.086 Uiso 1 1 calc R . . C25 C 0.7116(3) 0.86725(13) 1.15676(18) 0.0563(8) Uani 1 1 d . . . H25A H 0.7114 0.8724 1.2087 0.084 Uiso 1 1 calc R . . H25B H 0.6468 0.8931 1.1293 0.084 Uiso 1 1 calc R . . H25C H 0.7908 0.8804 1.1455 0.084 Uiso 1 1 calc R . . C26 C 0.5674(2) 0.57107(10) 1.12464(12) 0.0266(5) Uani 1 1 d . . . C27 C 0.4926(2) 0.60092(10) 1.06699(12) 0.0296(6) Uani 1 1 d . . . C28 C 0.3900(2) 0.57424(12) 1.02323(13) 0.0341(6) Uani 1 1 d . . . C29 C 0.3524(2) 0.51314(12) 1.03366(13) 0.0387(6) Uani 1 1 d . . . H29A H 0.2833 0.4951 1.0041 0.046 Uiso 1 1 calc R . . C30 C 0.4235(2) 0.47942(11) 1.09123(13) 0.0338(6) Uani 1 1 d . . . H30A H 0.4016 0.4375 1.1006 0.041 Uiso 1 1 calc R . . C31 C 0.5272(2) 0.50711(10) 1.13542(12) 0.0262(5) Uani 1 1 d . . . C32 C 0.4011(3) 0.67534(13) 0.98904(15) 0.0516(8) Uani 1 1 d . . . H32A H 0.4206 0.6968 0.9455 0.062 Uiso 1 1 calc R . . H32B H 0.3480 0.7033 1.0124 0.062 Uiso 1 1 calc R . . C33 C 0.6046(2) 0.46988(10) 1.19326(12) 0.0260(5) Uani 1 1 d . . . C34 C 0.5631(2) 0.40398(11) 1.21127(13) 0.0355(6) Uani 1 1 d . . . H34A H 0.6234 0.3856 1.2498 0.053 Uiso 1 1 calc R . . H34B H 0.5554 0.3775 1.1680 0.053 Uiso 1 1 calc R . . H34C H 0.4839 0.4067 1.2275 0.053 Uiso 1 1 calc R . . C35 C 0.7863(2) 0.45923(10) 1.28449(12) 0.0262(5) Uani 1 1 d . . . C36 C 0.7811(2) 0.47384(10) 1.35885(12) 0.0285(5) Uani 1 1 d . . . C37 C 0.8575(2) 0.43915(11) 1.41335(13) 0.0336(6) Uani 1 1 d . . . H37A H 0.8559 0.4482 1.4628 0.040 Uiso 1 1 calc R . . C38 C 0.9355(2) 0.39174(11) 1.39593(13) 0.0340(6) Uani 1 1 d . . . H38A H 0.9859 0.3691 1.4332 0.041 Uiso 1 1 calc R . . C39 C 0.9382(2) 0.37805(11) 1.32251(13) 0.0324(6) Uani 1 1 d . . . H39A H 0.9902 0.3456 1.3109 0.039 Uiso 1 1 calc R . . C40 C 0.8654(2) 0.41144(10) 1.26575(12) 0.0292(5) Uani 1 1 d . . . C41 C 0.6909(2) 0.52294(11) 1.37960(13) 0.0326(6) Uani 1 1 d . . . H41A H 0.6715 0.5529 1.3381 0.039 Uiso 1 1 calc R . . C42 C 0.5692(3) 0.49103(13) 1.39026(16) 0.0507(7) Uani 1 1 d . . . H42A H 0.5359 0.4672 1.3466 0.076 Uiso 1 1 calc R . . H42B H 0.5105 0.5233 1.3990 0.076 Uiso 1 1 calc R . . H42C H 0.5847 0.4625 1.4319 0.076 Uiso 1 1 calc R . . C43 C 0.7443(3) 0.56206(13) 1.44796(14) 0.0479(7) Uani 1 1 d . . . H43A H 0.8201 0.5824 1.4403 0.072 Uiso 1 1 calc R . . H43B H 0.7612 0.5342 1.4901 0.072 Uiso 1 1 calc R . . H43C H 0.6851 0.5941 1.4565 0.072 Uiso 1 1 calc R . . C44 C 0.8773(2) 0.39567(12) 1.18654(13) 0.0392(6) Uani 1 1 d . . . H44A H 0.8155 0.4211 1.1537 0.047 Uiso 1 1 calc R . . C45 C 0.8524(3) 0.32498(13) 1.16855(16) 0.0594(8) Uani 1 1 d . . . H45A H 0.7707 0.3138 1.1775 0.089 Uiso 1 1 calc R . . H45B H 0.9135 0.2993 1.1993 0.089 Uiso 1 1 calc R . . H45C H 0.8573 0.3174 1.1175 0.089 Uiso 1 1 calc R . . C46 C 1.0054(3) 0.41399(16) 1.17199(17) 0.0666(9) Uani 1 1 d . . . H46A H 1.0201 0.4586 1.1830 0.100 Uiso 1 1 calc R . . H46B H 1.0102 0.4063 1.1210 0.100 Uiso 1 1 calc R . . H46C H 1.0672 0.3887 1.2027 0.100 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.0275(3) 0.0243(2) 0.0206(2) 0.00022(16) 0.00107(18) -0.00035(18) N1 0.0304(12) 0.0376(12) 0.0251(11) -0.0016(9) -0.0001(9) -0.0020(9) N2 0.0259(11) 0.0246(10) 0.0240(11) 0.0009(8) 0.0032(9) -0.0018(8) N3 0.0289(11) 0.0261(10) 0.0192(10) -0.0017(8) 0.0033(9) 0.0024(9) O1 0.0325(10) 0.0364(10) 0.0310(9) 0.0015(7) -0.0008(8) 0.0073(7) O2 0.0298(10) 0.0438(10) 0.0338(10) 0.0075(8) -0.0041(8) -0.0012(8) O3 0.0525(12) 0.0311(10) 0.0332(10) 0.0063(7) -0.0106(8) 0.0000(8) O4 0.0534(12) 0.0385(10) 0.0378(10) 0.0009(8) -0.0193(9) 0.0045(9) C1 0.0366(15) 0.0429(15) 0.0365(15) 0.0024(12) 0.0154(12) -0.0003(12) C2 0.074(2) 0.0572(19) 0.0367(16) 0.0055(13) 0.0212(15) -0.0052(16) C3 0.052(2) 0.068(2) 0.076(2) 0.0077(17) 0.0286(17) 0.0131(16) C4 0.0438(18) 0.062(2) 0.068(2) -0.0058(16) 0.0151(16) -0.0169(15) C5 0.0307(14) 0.0259(12) 0.0211(12) 0.0016(10) 0.0053(10) -0.0051(10) C6 0.0297(14) 0.0275(13) 0.0239(13) 0.0038(10) 0.0066(11) -0.0011(11) C7 0.0273(14) 0.0348(14) 0.0261(13) 0.0095(11) 0.0013(11) -0.0050(11) C8 0.0369(15) 0.0376(15) 0.0271(13) 0.0017(11) -0.0051(11) -0.0096(12) C9 0.0425(16) 0.0292(13) 0.0288(14) -0.0023(11) 0.0022(12) -0.0052(12) C10 0.0301(14) 0.0262(13) 0.0248(13) 0.0029(10) 0.0029(10) -0.0049(10) C11 0.0320(15) 0.0399(15) 0.0376(15) 0.0073(12) -0.0015(12) 0.0020(12) C12 0.0323(14) 0.0231(12) 0.0280(13) 0.0015(10) 0.0060(11) -0.0047(10) C13 0.0411(16) 0.0338(14) 0.0391(15) -0.0082(11) -0.0009(12) 0.0026(12) C14 0.0259(14) 0.0241(13) 0.0285(13) -0.0063(10) 0.0000(10) 0.0042(10) C15 0.0292(14) 0.0300(13) 0.0330(14) -0.0051(10) 0.0038(11) -0.0001(11) C16 0.0276(15) 0.0415(16) 0.0471(16) -0.0046(13) 0.0042(12) -0.0020(12) C17 0.0338(16) 0.0343(15) 0.0451(16) -0.0058(12) -0.0031(12) 0.0082(12) C18 0.0414(16) 0.0260(13) 0.0373(15) 0.0014(11) 0.0016(12) 0.0057(12) C19 0.0331(14) 0.0248(13) 0.0307(13) -0.0015(10) 0.0035(11) 0.0039(11) C20 0.0320(15) 0.0388(15) 0.0455(16) 0.0043(12) 0.0090(12) -0.0031(12) C21 0.070(2) 0.0554(19) 0.0451(18) 0.0057(14) 0.0072(15) -0.0139(16) C22 0.0461(17) 0.0441(16) 0.0558(18) 0.0017(13) 0.0175(14) -0.0080(13) C23 0.0384(15) 0.0331(14) 0.0464(16) 0.0126(12) 0.0103(12) 0.0069(12) C24 0.071(2) 0.0507(18) 0.0563(19) 0.0088(14) 0.0267(16) -0.0060(15) C25 0.0389(17) 0.0510(18) 0.079(2) -0.0030(16) 0.0099(15) -0.0091(14) C26 0.0290(14) 0.0285(13) 0.0220(13) -0.0029(10) 0.0036(10) 0.0026(10) C27 0.0386(15) 0.0249(13) 0.0241(13) -0.0028(10) 0.0015(11) 0.0016(11) C28 0.0370(15) 0.0348(15) 0.0266(13) -0.0028(11) -0.0056(11) 0.0080(12) C29 0.0316(15) 0.0410(16) 0.0380(15) -0.0080(12) -0.0096(12) -0.0027(12) C30 0.0355(15) 0.0287(13) 0.0353(14) -0.0022(11) 0.0010(12) -0.0056(11) C31 0.0258(13) 0.0297(13) 0.0229(12) -0.0030(10) 0.0033(10) -0.0002(10) C32 0.066(2) 0.0373(16) 0.0412(16) 0.0001(12) -0.0221(15) 0.0067(14) C33 0.0314(14) 0.0254(12) 0.0219(12) -0.0032(10) 0.0065(11) -0.0003(11) C34 0.0407(15) 0.0288(13) 0.0354(14) 0.0021(11) 0.0019(12) -0.0040(11) C35 0.0305(14) 0.0226(12) 0.0238(13) 0.0025(9) -0.0006(10) -0.0052(10) C36 0.0345(14) 0.0243(12) 0.0260(13) 0.0017(10) 0.0036(11) -0.0072(10) C37 0.0431(16) 0.0363(14) 0.0202(13) 0.0031(10) 0.0023(11) -0.0058(12) C38 0.0330(14) 0.0360(15) 0.0300(14) 0.0102(11) -0.0034(11) -0.0026(12) C39 0.0325(14) 0.0292(13) 0.0344(15) 0.0027(11) 0.0025(11) 0.0025(11) C40 0.0326(14) 0.0263(13) 0.0279(13) 0.0017(10) 0.0028(11) 0.0011(11) C41 0.0427(15) 0.0299(13) 0.0260(13) 0.0008(10) 0.0085(11) -0.0010(11) C42 0.0537(19) 0.0433(17) 0.0593(19) -0.0092(14) 0.0218(15) -0.0031(14) C43 0.069(2) 0.0426(16) 0.0330(15) -0.0068(12) 0.0105(14) 0.0001(14) C44 0.0504(17) 0.0404(15) 0.0254(14) -0.0018(11) 0.0026(12) 0.0176(12) C45 0.076(2) 0.0487(18) 0.0477(18) -0.0157(14) -0.0052(16) 0.0181(16) C46 0.086(3) 0.079(2) 0.0421(18) -0.0092(16) 0.0303(17) 0.0025(19) _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 1.6897(19) . ? Ti1 C26 2.194(2) . ? Ti1 C5 2.198(2) . ? Ti1 N2 2.2387(18) . ? Ti1 N3 2.2579(18) . ? N1 C1 1.451(3) . ? N2 C12 1.304(3) . ? N2 C14 1.449(3) . ? N3 C33 1.309(3) . ? N3 C35 1.450(3) . ? O1 C6 1.392(3) . ? O1 C11 1.407(3) . ? O2 C7 1.376(3) . ? O2 C11 1.441(3) . ? O3 C27 1.397(3) . ? O3 C32 1.412(3) . ? O4 C28 1.375(3) . ? O4 C32 1.428(3) . ? C1 C2 1.520(4) . ? C1 C3 1.524(4) . ? C1 C4 1.529(4) . ? C5 C6 1.370(3) . ? C5 C10 1.427(3) . ? C6 C7 1.387(3) . ? C7 C8 1.363(3) . ? C8 C9 1.386(3) . ? C9 C10 1.396(3) . ? C10 C12 1.467(3) . ? C12 C13 1.501(3) . ? C14 C19 1.398(3) . ? C14 C15 1.401(3) . ? C15 C16 1.387(3) . ? C15 C20 1.518(3) . ? C16 C17 1.378(4) . ? C17 C18 1.371(3) . ? C18 C19 1.387(3) . ? C19 C23 1.517(3) . ? C20 C21 1.525(4) . ? C20 C22 1.527(3) . ? C23 C24 1.523(4) . ? C23 C25 1.533(4) . ? C26 C27 1.371(3) . ? C26 C31 1.429(3) . ? C27 C28 1.378(3) . ? C28 C29 1.362(3) . ? C29 C30 1.391(3) . ? C30 C31 1.399(3) . ? C31 C33 1.462(3) . ? C33 C34 1.501(3) . ? C35 C40 1.398(3) . ? C35 C36 1.409(3) . ? C36 C37 1.391(3) . ? C36 C41 1.511(3) . ? C37 C38 1.375(3) . ? C38 C39 1.382(3) . ? C39 C40 1.385(3) . ? C40 C44 1.516(3) . ? C41 C42 1.524(3) . ? C41 C43 1.527(3) . ? C44 C46 1.513(4) . ? C44 C45 1.525(4) . ? 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 C26 103.42(9) . . ? N1 Ti1 C5 97.48(9) . . ? C26 Ti1 C5 159.06(8) . . ? N1 Ti1 N2 112.23(8) . . ? C26 Ti1 N2 95.73(7) . . ? C5 Ti1 N2 74.84(7) . . ? N1 Ti1 N3 119.60(8) . . ? C26 Ti1 N3 75.30(7) . . ? C5 Ti1 N3 95.59(7) . . ? N2 Ti1 N3 128.11(6) . . ? C1 N1 Ti1 171.08(17) . . ? C12 N2 C14 118.94(18) . . ? C12 N2 Ti1 116.95(15) . . ? C14 N2 Ti1 124.05(13) . . ? C33 N3 C35 118.85(18) . . ? C33 N3 Ti1 115.67(14) . . ? C35 N3 Ti1 125.40(13) . . ? C6 O1 C11 104.86(17) . . ? C7 O2 C11 103.59(17) . . ? C27 O3 C32 105.01(19) . . ? C28 O4 C32 104.04(18) . . ? N1 C1 C2 109.6(2) . . ? N1 C1 C3 109.8(2) . . ? C2 C1 C3 109.2(2) . . ? N1 C1 C4 108.4(2) . . ? C2 C1 C4 109.8(2) . . ? C3 C1 C4 109.9(2) . . ? C6 C5 C10 112.1(2) . . ? C6 C5 Ti1 132.72(17) . . ? C10 C5 Ti1 114.67(16) . . ? C5 C6 C7 125.4(2) . . ? C5 C6 O1 126.5(2) . . ? C7 C6 O1 108.02(19) . . ? C8 C7 O2 128.0(2) . . ? C8 C7 C6 121.6(2) . . ? O2 C7 C6 110.4(2) . . ? C7 C8 C9 116.4(2) . . ? C8 C9 C10 121.2(2) . . ? C9 C10 C5 123.2(2) . . ? C9 C10 C12 121.0(2) . . ? C5 C10 C12 115.72(19) . . ? O1 C11 O2 107.64(18) . . ? N2 C12 C10 117.6(2) . . ? N2 C12 C13 122.7(2) . . ? C10 C12 C13 119.7(2) . . ? C19 C14 C15 121.2(2) . . ? C19 C14 N2 120.0(2) . . ? C15 C14 N2 118.81(19) . . ? C16 C15 C14 118.1(2) . . ? C16 C15 C20 119.9(2) . . ? C14 C15 C20 122.0(2) . . ? C17 C16 C15 121.5(2) . . ? C18 C17 C16 119.5(2) . . ? C17 C18 C19 121.7(2) . . ? C18 C19 C14 118.1(2) . . ? C18 C19 C23 119.2(2) . . ? C14 C19 C23 122.7(2) . . ? C15 C20 C21 110.8(2) . . ? C15 C20 C22 112.2(2) . . ? C21 C20 C22 110.6(2) . . ? C19 C23 C24 111.0(2) . . ? C19 C23 C25 111.9(2) . . ? C24 C23 C25 109.2(2) . . ? C27 C26 C31 112.0(2) . . ? C27 C26 Ti1 133.22(17) . . ? C31 C26 Ti1 114.33(15) . . ? C26 C27 C28 125.7(2) . . ? C26 C27 O3 126.3(2) . . ? C28 C27 O3 107.86(19) . . ? C29 C28 O4 127.1(2) . . ? C29 C28 C27 122.0(2) . . ? O4 C28 C27 110.9(2) . . ? C28 C29 C30 116.0(2) . . ? C29 C30 C31 121.5(2) . . ? C30 C31 C26 122.8(2) . . ? C30 C31 C33 120.8(2) . . ? C26 C31 C33 116.35(19) . . ? O3 C32 O4 108.04(19) . . ? N3 C33 C31 118.20(19) . . ? N3 C33 C34 122.6(2) . . ? C31 C33 C34 119.2(2) . . ? C40 C35 C36 121.3(2) . . ? C40 C35 N3 120.27(19) . . ? C36 C35 N3 118.40(19) . . ? C37 C36 C35 117.8(2) . . ? C37 C36 C41 120.5(2) . . ? C35 C36 C41 121.7(2) . . ? C38 C37 C36 121.7(2) . . ? C37 C38 C39 119.4(2) . . ? C38 C39 C40 121.7(2) . . ? C39 C40 C35 118.1(2) . . ? C39 C40 C44 118.8(2) . . ? C35 C40 C44 123.1(2) . . ? C36 C41 C42 110.6(2) . . ? C36 C41 C43 113.3(2) . . ? C42 C41 C43 110.3(2) . . ? C46 C44 C40 110.1(2) . . ? C46 C44 C45 109.9(2) . . ? C40 C44 C45 112.1(2) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 22.75 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.308 _refine_diff_density_min -0.308 _refine_diff_density_rms 0.039 data_(L3)2Ti(N-2,6-Me2C6H3)_(3b) _database_code_depnum_ccdc_archive 'CCDC 726831' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety C45.5H45N3O4Ti _chemical_formula_sum 'C45.50 H45 N3 O4 Ti' _chemical_formula_weight 745.75 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.9994(11) _cell_length_b 12.6959(12) _cell_length_c 14.6241(14) _cell_angle_alpha 73.494(2) _cell_angle_beta 81.949(2) _cell_angle_gamma 88.826(2) _cell_volume 1938.4(3) _cell_formula_units_Z 2 _cell_measurement_temperature 140(2) _cell_measurement_reflns_used 3472 _cell_measurement_theta_min 2.21 _cell_measurement_theta_max 28.8 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.278 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 786 _exptl_absorpt_coefficient_mu 0.268 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.932 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 140(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART CCD' _diffrn_measurement_method \w-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 21835 _diffrn_reflns_av_R_equivalents 0.0581 _diffrn_reflns_av_sigmaI/netI 0.0905 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _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 1.67 _diffrn_reflns_theta_max 28.31 _reflns_number_total 9596 _reflns_number_gt 6124 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART v5.625' _computing_cell_refinement 'Bruker SAINT v6.22' _computing_data_reduction 'Bruker SAINT v6.22' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Hydrogen atoms were included in constrained positions for the titanium complex, but were omitted from the toluene solvate. ; _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^)+(0.0736P)^2^+1.2019P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 9596 _refine_ls_number_parameters 487 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1132 _refine_ls_R_factor_gt 0.0702 _refine_ls_wR_factor_ref 0.1843 _refine_ls_wR_factor_gt 0.1668 _refine_ls_goodness_of_fit_ref 1.040 _refine_ls_restrained_S_all 1.040 _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 0.69813(4) 0.67703(4) 0.68382(4) 0.02519(15) Uani 1 1 d . . . O1 O 0.4755(2) 0.6194(2) 0.91243(15) 0.0437(6) Uani 1 1 d . . . O2 O 0.2638(2) 0.6121(2) 0.93829(17) 0.0542(7) Uani 1 1 d . . . O3 O 0.95249(18) 0.62662(17) 0.50084(14) 0.0331(5) Uani 1 1 d . . . O4 O 1.13323(18) 0.72266(18) 0.43039(16) 0.0397(5) Uani 1 1 d . . . N1 N 0.7264(2) 0.5409(2) 0.73285(17) 0.0314(5) Uani 1 1 d . . . N2 N 0.6128(2) 0.71423(18) 0.55217(16) 0.0264(5) Uani 1 1 d . . . N3 N 0.7475(2) 0.80013(19) 0.75261(17) 0.0310(5) Uani 1 1 d . . . C1 C 0.7449(3) 0.4294(3) 0.7655(2) 0.0388(8) Uani 1 1 d . . . C2 C 0.6530(4) 0.3553(3) 0.7639(2) 0.0552(11) Uani 1 1 d . . . C3 C 0.6775(7) 0.2428(3) 0.7940(3) 0.092(2) Uani 1 1 d . . . H3A H 0.6196 0.1922 0.7906 0.111 Uiso 1 1 calc R . . C4 C 0.7854(9) 0.2055(4) 0.8284(4) 0.118(3) Uani 1 1 d . . . H4A H 0.7992 0.1305 0.8494 0.142 Uiso 1 1 calc R . . C5 C 0.8717(6) 0.2793(5) 0.8314(3) 0.100(2) Uani 1 1 d . . . H5A H 0.9438 0.2528 0.8554 0.120 Uiso 1 1 calc R . . C6 C 0.8572(4) 0.3929(3) 0.8000(2) 0.0598(12) Uani 1 1 d . . . C7 C 0.5335(4) 0.3949(4) 0.7329(3) 0.0701(13) Uani 1 1 d . . . H7A H 0.4824 0.3332 0.7361 0.105 Uiso 1 1 calc R . . H7B H 0.5470 0.4417 0.6679 0.105 Uiso 1 1 calc R . . H7C H 0.4938 0.4354 0.7745 0.105 Uiso 1 1 calc R . . C8 C 0.9543(4) 0.4723(5) 0.7998(3) 0.0803(15) Uani 1 1 d . . . H8A H 0.9262 0.5458 0.7760 0.121 Uiso 1 1 calc R . . H8B H 1.0271 0.4617 0.7589 0.121 Uiso 1 1 calc R . . H8C H 0.9726 0.4607 0.8642 0.121 Uiso 1 1 calc R . . C9 C 0.5002(3) 0.6791(2) 0.7347(2) 0.0294(6) Uani 1 1 d . . . C10 C 0.4321(3) 0.6511(2) 0.8244(2) 0.0346(7) Uani 1 1 d . . . C11 C 0.3035(3) 0.6445(3) 0.8418(2) 0.0418(8) Uani 1 1 d . . . C12 C 0.2350(3) 0.6649(3) 0.7686(3) 0.0502(9) Uani 1 1 d . . . H12A H 0.1496 0.6615 0.7802 0.060 Uiso 1 1 calc R . . C13 C 0.2982(3) 0.6912(3) 0.6753(2) 0.0422(8) Uani 1 1 d . . . H13A H 0.2545 0.7047 0.6232 0.051 Uiso 1 1 calc R . . C14 C 0.4266(3) 0.6975(2) 0.6592(2) 0.0303(6) Uani 1 1 d . . . C15 C 0.3709(3) 0.6141(3) 0.9840(3) 0.0506(9) Uani 1 1 d . . . H15A H 0.3702 0.6776 1.0085 0.061 Uiso 1 1 calc R . . H15B H 0.3728 0.5483 1.0374 0.061 Uiso 1 1 calc R . . C16 C 0.4928(2) 0.7207(2) 0.5609(2) 0.0291(6) Uani 1 1 d . . . C17 C 0.4251(3) 0.7505(3) 0.4757(2) 0.0361(7) Uani 1 1 d . . . H17A H 0.4826 0.7628 0.4178 0.054 Uiso 1 1 calc R . . H17B H 0.3799 0.8162 0.4748 0.054 Uiso 1 1 calc R . . H17C H 0.3693 0.6916 0.4798 0.054 Uiso 1 1 calc R . . C18 C 0.6801(2) 0.7433(2) 0.4562(2) 0.0285(6) Uani 1 1 d . . . C19 C 0.7081(3) 0.8543(3) 0.4088(2) 0.0348(7) Uani 1 1 d . . . C20 C 0.7705(3) 0.8810(3) 0.3160(2) 0.0462(9) Uani 1 1 d . . . H20A H 0.7903 0.9542 0.2836 0.055 Uiso 1 1 calc R . . C21 C 0.8040(3) 0.8015(4) 0.2707(2) 0.0545(10) Uani 1 1 d . . . H21A H 0.8445 0.8210 0.2079 0.065 Uiso 1 1 calc R . . C22 C 0.7772(3) 0.6927(3) 0.3189(2) 0.0466(9) Uani 1 1 d . . . H22A H 0.8008 0.6392 0.2882 0.056 Uiso 1 1 calc R . . C23 C 0.7157(3) 0.6611(3) 0.4124(2) 0.0330(7) Uani 1 1 d . . . C24 C 0.6717(3) 0.9413(3) 0.4585(3) 0.0448(8) Uani 1 1 d . . . H24A H 0.6976 1.0123 0.4159 0.067 Uiso 1 1 calc R . . H24B H 0.7102 0.9278 0.5156 0.067 Uiso 1 1 calc R . . H24C H 0.5841 0.9395 0.4756 0.067 Uiso 1 1 calc R . . C25 C 0.6881(3) 0.5423(3) 0.4645(2) 0.0425(8) Uani 1 1 d . . . H25A H 0.6008 0.5307 0.4812 0.064 Uiso 1 1 calc R . . H25B H 0.7261 0.5223 0.5221 0.064 Uiso 1 1 calc R . . H25C H 0.7196 0.4978 0.4237 0.064 Uiso 1 1 calc R . . C26 C 0.8774(2) 0.7449(2) 0.60452(19) 0.0264(6) Uani 1 1 d . . . C27 C 0.9599(2) 0.7171(2) 0.53605(19) 0.0266(6) Uani 1 1 d . . . C28 C 1.0700(2) 0.7722(2) 0.4932(2) 0.0299(6) Uani 1 1 d . . . C29 C 1.1063(3) 0.8622(2) 0.5170(2) 0.0353(7) Uani 1 1 d . . . H29A H 1.1786 0.9010 0.4867 0.042 Uiso 1 1 calc R . . C30 C 1.0299(3) 0.8929(2) 0.5888(2) 0.0323(6) Uani 1 1 d . . . H30A H 1.0522 0.9523 0.6087 0.039 Uiso 1 1 calc R . . C31 C 0.9200(2) 0.8355(2) 0.63126(19) 0.0268(6) Uani 1 1 d . . . C32 C 1.0467(3) 0.6445(3) 0.4203(2) 0.0385(7) Uani 1 1 d . . . H32A H 1.0122 0.6731 0.3607 0.046 Uiso 1 1 calc R . . H32B H 1.0869 0.5761 0.4191 0.046 Uiso 1 1 calc R . . C33 C 0.8440(3) 0.8624(2) 0.7123(2) 0.0306(6) Uani 1 1 d . . . C34 C 0.8800(3) 0.9572(3) 0.7463(2) 0.0427(8) Uani 1 1 d . . . H34A H 0.8208 0.9635 0.7993 0.064 Uiso 1 1 calc R . . H34B H 0.8825 1.0239 0.6945 0.064 Uiso 1 1 calc R . . H34C H 0.9596 0.9448 0.7668 0.064 Uiso 1 1 calc R . . C35 C 0.6723(3) 0.8217(3) 0.8341(2) 0.0434(8) Uani 1 1 d . . . C36 C 0.6906(4) 0.7617(3) 0.9249(3) 0.0591(11) Uani 1 1 d . . . C37 C 0.6154(6) 0.7843(4) 1.0039(3) 0.0891(19) Uani 1 1 d . . . H37A H 0.6254 0.7463 1.0668 0.107 Uiso 1 1 calc R . . C38 C 0.5270(6) 0.8637(5) 0.9858(5) 0.103(2) Uani 1 1 d . . . H38A H 0.4783 0.8787 1.0377 0.123 Uiso 1 1 calc R . . C39 C 0.5085(5) 0.9207(4) 0.8949(5) 0.0891(19) Uani 1 1 d . . . H39A H 0.4472 0.9726 0.8861 0.107 Uiso 1 1 calc R . . C40 C 0.5799(3) 0.9021(3) 0.8153(3) 0.0599(12) Uani 1 1 d . . . C41 C 0.7857(5) 0.6741(4) 0.9395(3) 0.0788(15) Uani 1 1 d . . . H41A H 0.8632 0.7042 0.9038 0.118 Uiso 1 1 calc R . . H41B H 0.7611 0.6145 0.9173 0.118 Uiso 1 1 calc R . . H41C H 0.7934 0.6475 1.0067 0.118 Uiso 1 1 calc R . . C42 C 0.5603(4) 0.9645(3) 0.7164(4) 0.0708(13) Uani 1 1 d . . . H42A H 0.4946 1.0148 0.7195 0.106 Uiso 1 1 calc R . . H42B H 0.5394 0.9143 0.6825 0.106 Uiso 1 1 calc R . . H42C H 0.6341 1.0046 0.6831 0.106 Uiso 1 1 calc R . . C96 C 1.1498(12) 0.8782(17) 0.9254(9) 0.147(8) Uani 0.50 1 d P . . C97 C 1.0748(11) 0.9240(7) 0.9588(5) 0.139(3) Uani 1 1 d . . . C98 C 0.9381(6) 0.9177(5) 0.9922(4) 0.0906(19) Uani 1 1 d . . . H98A H 0.8982 0.8570 0.9855 0.109 Uiso 1 1 calc R . . C99 C 0.8640(9) 0.9850(6) 1.0303(5) 0.140(3) Uani 1 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 0.0200(3) 0.0258(3) 0.0297(3) -0.0090(2) -0.00027(19) -0.00375(19) O1 0.0340(12) 0.0585(15) 0.0325(12) -0.0063(11) 0.0033(9) -0.0076(11) O2 0.0363(13) 0.0749(18) 0.0428(14) -0.0100(13) 0.0118(11) -0.0114(12) O3 0.0270(10) 0.0379(12) 0.0366(11) -0.0178(9) 0.0032(9) -0.0020(9) O4 0.0252(11) 0.0469(13) 0.0469(13) -0.0185(11) 0.0063(9) -0.0007(9) N1 0.0274(12) 0.0331(13) 0.0335(13) -0.0104(11) -0.0019(10) -0.0005(10) N2 0.0223(11) 0.0239(12) 0.0328(12) -0.0083(10) -0.0017(10) -0.0018(9) N3 0.0312(13) 0.0293(13) 0.0320(13) -0.0114(11) 0.0034(10) -0.0054(10) C1 0.058(2) 0.0306(16) 0.0239(14) -0.0064(12) 0.0044(14) 0.0100(15) C2 0.105(3) 0.0323(18) 0.0243(16) -0.0101(14) 0.0115(19) -0.014(2) C3 0.203(7) 0.027(2) 0.034(2) -0.0072(17) 0.026(3) -0.016(3) C4 0.246(9) 0.039(3) 0.041(3) 0.003(2) 0.037(4) 0.056(4) C5 0.145(5) 0.086(4) 0.040(2) 0.009(3) 0.016(3) 0.080(4) C6 0.077(3) 0.062(2) 0.0298(17) -0.0044(17) 0.0054(18) 0.038(2) C7 0.095(3) 0.065(3) 0.047(2) -0.009(2) -0.002(2) -0.051(3) C8 0.045(2) 0.121(4) 0.072(3) -0.022(3) -0.015(2) 0.036(3) C9 0.0239(14) 0.0273(15) 0.0353(15) -0.0081(12) 0.0009(12) -0.0029(11) C10 0.0307(16) 0.0338(16) 0.0366(16) -0.0078(13) 0.0005(13) -0.0027(13) C11 0.0305(16) 0.047(2) 0.0420(18) -0.0091(15) 0.0081(14) -0.0061(14) C12 0.0226(16) 0.065(2) 0.058(2) -0.0141(19) 0.0041(15) -0.0009(16) C13 0.0269(16) 0.051(2) 0.0472(19) -0.0118(16) -0.0042(14) -0.0009(14) C14 0.0240(14) 0.0264(14) 0.0380(16) -0.0078(12) 0.0011(12) -0.0017(11) C15 0.0401(19) 0.063(2) 0.0399(19) -0.0077(17) 0.0107(15) -0.0116(17) C16 0.0239(14) 0.0245(14) 0.0393(16) -0.0098(12) -0.0038(12) -0.0021(11) C17 0.0246(15) 0.0406(18) 0.0424(17) -0.0100(14) -0.0058(13) -0.0016(13) C18 0.0195(13) 0.0346(16) 0.0292(14) -0.0054(12) -0.0034(11) -0.0008(11) C19 0.0208(14) 0.0375(17) 0.0413(17) -0.0034(14) -0.0041(12) -0.0031(12) C20 0.0337(17) 0.049(2) 0.0427(19) 0.0083(16) -0.0048(15) -0.0033(15) C21 0.040(2) 0.079(3) 0.0310(18) 0.0013(18) 0.0036(15) 0.0087(19) C22 0.0392(19) 0.065(2) 0.0380(18) -0.0189(18) -0.0059(15) 0.0136(17) C23 0.0248(14) 0.0409(17) 0.0348(16) -0.0121(14) -0.0071(12) 0.0042(13) C24 0.0422(19) 0.0283(16) 0.061(2) -0.0069(15) -0.0089(16) -0.0055(14) C25 0.0432(19) 0.0378(18) 0.053(2) -0.0232(16) -0.0073(16) 0.0032(15) C26 0.0203(13) 0.0284(14) 0.0305(14) -0.0077(12) -0.0052(11) -0.0005(11) C27 0.0236(14) 0.0268(14) 0.0280(14) -0.0050(12) -0.0047(11) -0.0016(11) C28 0.0209(13) 0.0347(16) 0.0316(15) -0.0064(13) -0.0019(11) 0.0041(12) C29 0.0238(15) 0.0326(16) 0.0447(18) -0.0058(14) 0.0014(13) -0.0065(12) C30 0.0269(15) 0.0274(15) 0.0415(17) -0.0087(13) -0.0025(13) -0.0040(12) C31 0.0250(14) 0.0256(14) 0.0278(14) -0.0045(11) -0.0035(11) 0.0002(11) C32 0.0283(16) 0.0490(19) 0.0392(17) -0.0183(15) 0.0042(13) -0.0006(14) C33 0.0327(16) 0.0265(14) 0.0318(15) -0.0071(12) -0.0046(12) -0.0021(12) C34 0.050(2) 0.0376(18) 0.0420(18) -0.0170(15) 0.0018(15) -0.0156(15) C35 0.048(2) 0.0378(18) 0.046(2) -0.0239(16) 0.0177(15) -0.0210(15) C36 0.090(3) 0.046(2) 0.041(2) -0.0209(18) 0.014(2) -0.035(2) C37 0.134(5) 0.082(4) 0.050(3) -0.033(3) 0.033(3) -0.065(4) C38 0.116(5) 0.088(4) 0.109(5) -0.073(4) 0.069(4) -0.056(4) C39 0.073(3) 0.073(3) 0.125(5) -0.064(3) 0.054(3) -0.026(3) C40 0.045(2) 0.049(2) 0.094(3) -0.048(2) 0.023(2) -0.0149(17) C41 0.140(5) 0.056(3) 0.037(2) 0.0001(19) -0.022(2) -0.030(3) C42 0.053(2) 0.048(2) 0.111(4) -0.027(3) -0.004(2) 0.0134(19) C96 0.080(8) 0.25(2) 0.065(7) 0.018(9) 0.017(6) 0.081(11) C97 0.225(11) 0.117(6) 0.059(4) 0.020(4) -0.063(6) -0.002(7) C98 0.109(5) 0.095(4) 0.056(3) 0.013(3) -0.036(3) -0.050(4) C99 0.280(11) 0.073(4) 0.068(4) 0.003(3) -0.080(5) -0.003(6) _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 1.713(2) . ? Ti1 N2 2.186(2) . ? Ti1 N3 2.198(2) . ? Ti1 C26 2.200(3) . ? Ti1 C9 2.202(3) . ? O1 C10 1.385(4) . ? O1 C15 1.432(4) . ? O2 C11 1.362(4) . ? O2 C15 1.437(4) . ? O3 C27 1.393(3) . ? O3 C32 1.424(3) . ? O4 C28 1.361(3) . ? O4 C32 1.441(4) . ? N1 C1 1.379(4) . ? N2 C16 1.312(3) . ? N2 C18 1.442(4) . ? N3 C33 1.302(4) . ? N3 C35 1.442(4) . ? C1 C2 1.401(5) . ? C1 C6 1.420(5) . ? C2 C3 1.403(6) . ? C2 C7 1.482(6) . ? C3 C4 1.376(9) . ? C4 C5 1.360(10) . ? C5 C6 1.396(6) . ? C6 C8 1.483(7) . ? C9 C10 1.371(4) . ? C9 C14 1.424(4) . ? C10 C11 1.401(4) . ? C11 C12 1.357(5) . ? C12 C13 1.393(5) . ? C13 C14 1.399(4) . ? C14 C16 1.469(4) . ? C16 C17 1.493(4) . ? C18 C23 1.395(4) . ? C18 C19 1.402(4) . ? C19 C20 1.383(4) . ? C19 C24 1.506(4) . ? C20 C21 1.374(5) . ? C21 C22 1.377(5) . ? C22 C23 1.388(4) . ? C23 C25 1.500(4) . ? C26 C27 1.372(4) . ? C26 C31 1.422(4) . ? C27 C28 1.387(4) . ? C28 C29 1.368(4) . ? C29 C30 1.390(4) . ? C30 C31 1.395(4) . ? C31 C33 1.470(4) . ? C33 C34 1.506(4) . ? C35 C36 1.371(5) . ? C35 C40 1.423(5) . ? C36 C37 1.418(6) . ? C36 C41 1.502(7) . ? C37 C38 1.383(9) . ? C38 C39 1.362(9) . ? C39 C40 1.385(6) . ? C40 C42 1.482(6) . ? C96 C97 1.134(14) . ? C97 C99 1.407(11) 2_777 ? C97 C98 1.511(11) . ? C98 C99 1.349(10) . ? C99 C97 1.407(11) 2_777 ? 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 115.09(10) . . ? N1 Ti1 N3 120.27(10) . . ? N2 Ti1 N3 124.64(9) . . ? N1 Ti1 C26 103.50(11) . . ? N2 Ti1 C26 92.56(9) . . ? N3 Ti1 C26 75.07(9) . . ? N1 Ti1 C9 100.06(11) . . ? N2 Ti1 C9 75.86(10) . . ? N3 Ti1 C9 94.43(10) . . ? C26 Ti1 C9 156.39(11) . . ? C10 O1 C15 106.2(2) . . ? C11 O2 C15 105.8(2) . . ? C27 O3 C32 105.4(2) . . ? C28 O4 C32 104.5(2) . . ? C1 N1 Ti1 174.8(2) . . ? C16 N2 C18 117.7(2) . . ? C16 N2 Ti1 117.62(19) . . ? C18 N2 Ti1 124.33(17) . . ? C33 N3 C35 118.8(2) . . ? C33 N3 Ti1 117.72(19) . . ? C35 N3 Ti1 123.20(18) . . ? N1 C1 C2 119.5(3) . . ? N1 C1 C6 118.8(3) . . ? C2 C1 C6 121.7(3) . . ? C1 C2 C3 117.7(5) . . ? C1 C2 C7 120.9(3) . . ? C3 C2 C7 121.3(4) . . ? C4 C3 C2 121.5(5) . . ? C5 C4 C3 119.5(5) . . ? C4 C5 C6 123.1(6) . . ? C5 C6 C1 116.4(5) . . ? C5 C6 C8 122.5(5) . . ? C1 C6 C8 121.0(3) . . ? C10 C9 C14 112.8(3) . . ? C10 C9 Ti1 133.3(2) . . ? C14 C9 Ti1 113.11(19) . . ? C9 C10 O1 127.3(3) . . ? C9 C10 C11 124.6(3) . . ? O1 C10 C11 108.0(3) . . ? C12 C11 O2 128.0(3) . . ? C12 C11 C10 121.5(3) . . ? O2 C11 C10 110.4(3) . . ? C11 C12 C13 117.0(3) . . ? C12 C13 C14 120.7(3) . . ? C13 C14 C9 123.2(3) . . ? C13 C14 C16 120.4(3) . . ? C9 C14 C16 116.3(2) . . ? O1 C15 O2 106.9(3) . . ? N2 C16 C14 116.9(3) . . ? N2 C16 C17 122.3(3) . . ? C14 C16 C17 120.8(2) . . ? C23 C18 C19 121.4(3) . . ? C23 C18 N2 119.7(3) . . ? C19 C18 N2 118.9(3) . . ? C20 C19 C18 118.2(3) . . ? C20 C19 C24 121.4(3) . . ? C18 C19 C24 120.4(3) . . ? C21 C20 C19 121.3(3) . . ? C20 C21 C22 119.6(3) . . ? C21 C22 C23 121.5(3) . . ? C22 C23 C18 117.9(3) . . ? C22 C23 C25 121.0(3) . . ? C18 C23 C25 121.0(3) . . ? C27 C26 C31 112.2(2) . . ? C27 C26 Ti1 133.9(2) . . ? C31 C26 Ti1 113.84(19) . . ? C26 C27 C28 125.2(3) . . ? C26 C27 O3 127.0(2) . . ? C28 C27 O3 107.7(2) . . ? O4 C28 C29 127.3(3) . . ? O4 C28 C27 111.2(3) . . ? C29 C28 C27 121.4(3) . . ? C28 C29 C30 116.8(3) . . ? C29 C30 C31 120.6(3) . . ? C30 C31 C26 123.7(3) . . ? C30 C31 C33 120.5(3) . . ? C26 C31 C33 115.7(2) . . ? O3 C32 O4 107.1(2) . . ? N3 C33 C31 117.0(2) . . ? N3 C33 C34 122.8(3) . . ? C31 C33 C34 120.2(3) . . ? C36 C35 C40 123.6(3) . . ? C36 C35 N3 118.6(3) . . ? C40 C35 N3 117.8(3) . . ? C35 C36 C37 117.6(5) . . ? C35 C36 C41 120.8(3) . . ? C37 C36 C41 121.6(4) . . ? C38 C37 C36 118.9(5) . . ? C39 C38 C37 122.6(4) . . ? C38 C39 C40 120.8(5) . . ? C39 C40 C35 116.6(5) . . ? C39 C40 C42 120.8(5) . . ? C35 C40 C42 122.6(3) . . ? C97 C96 C99 42.5(11) . 2_777 ? C96 C97 C99 104.4(16) . 2_777 ? C96 C97 C98 140.7(15) . . ? C99 C97 C98 114.9(8) 2_777 . ? C99 C98 C97 131.0(7) . . ? C98 C99 C97 114.1(10) . 2_777 ? C98 C99 C96 147.2(8) . 2_777 ? C97 C99 C96 33.0(6) 2_777 2_777 ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 28.31 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.482 _refine_diff_density_min -0.608 _refine_diff_density_rms 0.065 data_(L5)2Ti(NC(CH3)3)_(5a) _database_code_depnum_ccdc_archive 'CCDC 726832' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C44 H53 N3 O4 Ti' _chemical_formula_sum 'C44 H53 N3 O4 Ti' _chemical_formula_weight 735.79 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1)/n _symmetry_Int_Tables_number 14 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 12.288(4) _cell_length_b 24.290(8) _cell_length_c 13.775(4) _cell_angle_alpha 90.00 _cell_angle_beta 97.284(10) _cell_angle_gamma 90.00 _cell_volume 4078(2) _cell_formula_units_Z 4 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 5029 _cell_measurement_theta_min 2.3 _cell_measurement_theta_max 28.13 _exptl_crystal_description tablet _exptl_crystal_colour orange _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.198 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1568 _exptl_absorpt_coefficient_mu 0.254 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.834 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART CCD' _diffrn_measurement_method \w-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 45289 _diffrn_reflns_av_R_equivalents 0.0806 _diffrn_reflns_av_sigmaI/netI 0.0677 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.68 _diffrn_reflns_theta_max 28.49 _reflns_number_total 10246 _reflns_number_gt 6761 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART v5.625' _computing_cell_refinement 'Bruker SAINT v6.22' _computing_data_reduction 'Bruker SAINT v6.22' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0601P)^2^+1.0904P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0087(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 10246 _refine_ls_number_parameters 470 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0971 _refine_ls_R_factor_gt 0.0564 _refine_ls_wR_factor_ref 0.1420 _refine_ls_wR_factor_gt 0.1247 _refine_ls_goodness_of_fit_ref 1.018 _refine_ls_restrained_S_all 1.018 _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 0.66631(3) 0.400584(15) 0.82840(2) 0.02886(11) Uani 1 1 d . . . O1 O 0.69668(15) 0.34130(7) 1.22144(11) 0.0529(5) Uani 1 1 d . . . N1 N 0.53667(15) 0.42217(8) 0.82868(13) 0.0420(4) Uani 1 1 d . . . C1 C 0.4255(2) 0.44193(13) 0.82298(19) 0.0597(7) Uani 1 1 d . . . N2 N 0.79871(14) 0.46351(7) 0.84738(12) 0.0312(4) Uani 1 1 d . . . O2 O 0.61035(13) 0.33236(7) 1.06438(11) 0.0461(4) Uani 1 1 d . . . C2 C 0.3787(3) 0.4281(2) 0.9162(2) 0.1125(16) Uani 1 1 d . . . H2A H 0.3808 0.3890 0.9260 0.169 Uiso 1 1 calc R . . H2B H 0.3041 0.4407 0.9113 0.169 Uiso 1 1 calc R . . H2C H 0.4213 0.4459 0.9705 0.169 Uiso 1 1 calc R . . N3 N 0.68506(14) 0.31076(7) 0.80747(11) 0.0322(4) Uani 1 1 d . . . O3 O 0.6612(2) 0.45540(11) 0.43489(14) 0.0912(8) Uani 1 1 d . . . C3 C 0.3595(2) 0.41275(18) 0.7354(2) 0.0967(13) Uani 1 1 d . . . H3A H 0.3585 0.3739 0.7476 0.145 Uiso 1 1 calc R . . H3B H 0.3931 0.4196 0.6773 0.145 Uiso 1 1 calc R . . H3C H 0.2857 0.4266 0.7266 0.145 Uiso 1 1 calc R . . O4 O 0.64507(18) 0.48312(8) 0.59263(13) 0.0686(6) Uani 1 1 d . . . C4 C 0.4244(3) 0.50367(17) 0.8014(3) 0.1072(14) Uani 1 1 d . . . H4A H 0.4653 0.5228 0.8551 0.161 Uiso 1 1 calc R . . H4B H 0.3500 0.5167 0.7928 0.161 Uiso 1 1 calc R . . H4C H 0.4570 0.5103 0.7428 0.161 Uiso 1 1 calc R . . C5 C 0.84738(17) 0.46708(8) 0.93560(15) 0.0338(5) Uani 1 1 d . . . H5A H 0.9052 0.4917 0.9495 0.041 Uiso 1 1 calc R . . C6 C 0.86537(19) 0.44040(9) 1.10908(16) 0.0413(5) Uani 1 1 d . . . H6A H 0.9226 0.4655 1.1220 0.050 Uiso 1 1 calc R . . C7 C 0.8317(2) 0.40995(10) 1.18514(15) 0.0443(6) Uani 1 1 d . . . H7A H 0.8651 0.4134 1.2493 0.053 Uiso 1 1 calc R . . C8 C 0.74687(19) 0.37468(9) 1.15994(15) 0.0386(5) Uani 1 1 d . . . C9 C 0.6225(2) 0.30800(11) 1.15806(17) 0.0536(7) Uani 1 1 d . . . H9A H 0.6514 0.2710 1.1548 0.064 Uiso 1 1 calc R . . H9B H 0.5521 0.3060 1.1826 0.064 Uiso 1 1 calc R . . C10 C 0.69704(17) 0.36883(8) 1.06445(14) 0.0322(4) Uani 1 1 d . . . C11 C 0.72744(16) 0.39650(8) 0.98541(14) 0.0301(4) Uani 1 1 d . . . C12 C 0.81421(16) 0.43372(8) 1.01348(14) 0.0314(4) Uani 1 1 d . . . C13 C 0.84231(17) 0.49585(9) 0.77315(15) 0.0354(5) Uani 1 1 d . . . C14 C 0.91784(18) 0.47098(9) 0.71900(15) 0.0388(5) Uani 1 1 d . . . C15 C 0.95534(18) 0.41211(9) 0.73875(16) 0.0408(5) Uani 1 1 d . . . H15A H 0.8961 0.3927 0.7659 0.049 Uiso 1 1 calc R . . C16 C 1.0566(2) 0.41021(11) 0.8158(2) 0.0574(7) Uani 1 1 d . . . H16A H 1.0415 0.4296 0.8733 0.086 Uiso 1 1 calc R . . H16B H 1.1174 0.4272 0.7901 0.086 Uiso 1 1 calc R . . H16C H 1.0743 0.3726 0.8323 0.086 Uiso 1 1 calc R . . C17 C 0.9771(2) 0.38128(12) 0.6469(2) 0.0588(7) Uani 1 1 d . . . H17A H 0.9128 0.3826 0.5994 0.088 Uiso 1 1 calc R . . H17B H 0.9948 0.3436 0.6631 0.088 Uiso 1 1 calc R . . H17C H 1.0374 0.3982 0.6202 0.088 Uiso 1 1 calc R . . C18 C 0.9593(2) 0.50277(11) 0.64829(17) 0.0522(6) Uani 1 1 d . . . H18A H 1.0100 0.4874 0.6115 0.063 Uiso 1 1 calc R . . C19 C 0.9271(2) 0.55651(11) 0.63154(19) 0.0593(7) Uani 1 1 d . . . H19A H 0.9566 0.5771 0.5843 0.071 Uiso 1 1 calc R . . C20 C 0.8518(2) 0.57973(11) 0.68398(19) 0.0561(7) Uani 1 1 d . . . H20A H 0.8301 0.6160 0.6716 0.067 Uiso 1 1 calc R . . C21 C 0.7227(2) 0.57680(11) 0.8122(2) 0.0634(8) Uani 1 1 d . . . H21A H 0.6896 0.5479 0.8484 0.076 Uiso 1 1 calc R . . C22 C 0.6312(3) 0.60413(16) 0.7430(3) 0.1106(15) Uani 1 1 d . . . H22A H 0.5973 0.5773 0.6977 0.166 Uiso 1 1 calc R . . H22B H 0.6615 0.6332 0.7075 0.166 Uiso 1 1 calc R . . H22C H 0.5773 0.6191 0.7803 0.166 Uiso 1 1 calc R . . C23 C 0.7774(4) 0.61790(15) 0.8860(3) 0.1027(14) Uani 1 1 d . . . H23A H 0.8333 0.5996 0.9294 0.154 Uiso 1 1 calc R . . H23B H 0.7236 0.6331 0.9231 0.154 Uiso 1 1 calc R . . H23C H 0.8100 0.6469 0.8522 0.154 Uiso 1 1 calc R . . C24 C 0.8069(2) 0.55001(9) 0.75559(17) 0.0459(6) Uani 1 1 d . . . C25 C 0.69660(18) 0.29650(9) 0.71916(15) 0.0373(5) Uani 1 1 d . . . H25A H 0.7089 0.2597 0.7052 0.045 Uiso 1 1 calc R . . C26 C 0.69070(18) 0.33669(9) 0.64178(15) 0.0381(5) Uani 1 1 d . . . C27 C 0.67579(17) 0.39233(9) 0.67016(15) 0.0369(5) Uani 1 1 d . . . C28 C 0.6659(2) 0.42691(11) 0.59170(17) 0.0467(6) Uani 1 1 d . . . C29 C 0.6561(3) 0.50228(15) 0.4968(2) 0.0818(10) Uani 1 1 d . . . H29A H 0.7224 0.5241 0.4978 0.098 Uiso 1 1 calc R . . H29B H 0.5939 0.5252 0.4725 0.098 Uiso 1 1 calc R . . C30 C 0.6735(2) 0.41100(13) 0.49570(17) 0.0599(7) Uani 1 1 d . . . C31 C 0.6893(2) 0.35751(14) 0.47002(18) 0.0648(8) Uani 1 1 d . . . H31A H 0.6942 0.3472 0.4057 0.078 Uiso 1 1 calc R . . C32 C 0.6977(2) 0.31946(12) 0.54578(16) 0.0514(6) Uani 1 1 d . . . H32A H 0.7080 0.2824 0.5327 0.062 Uiso 1 1 calc R . . C33 C 0.9628(2) 0.25030(12) 0.8377(2) 0.0594(7) Uani 1 1 d . . . H33A H 0.9145 0.2412 0.7796 0.089 Uiso 1 1 calc R . . H33B H 0.9903 0.2171 0.8697 0.089 Uiso 1 1 calc R . . H33C H 1.0230 0.2718 0.8205 0.089 Uiso 1 1 calc R . . C34 C 0.5982(2) 0.24299(9) 0.90385(16) 0.0430(6) Uani 1 1 d . . . C35 C 0.4877(2) 0.26144(12) 0.85586(19) 0.0566(7) Uani 1 1 d . . . H35A H 0.4948 0.3001 0.8373 0.068 Uiso 1 1 calc R . . C36 C 0.3979(3) 0.25861(17) 0.9225(3) 0.0898(11) Uani 1 1 d . . . H36A H 0.4198 0.2795 0.9809 0.135 Uiso 1 1 calc R . . H36B H 0.3860 0.2209 0.9395 0.135 Uiso 1 1 calc R . . H36C H 0.3312 0.2736 0.8890 0.135 Uiso 1 1 calc R . . C37 C 0.4535(3) 0.22932(18) 0.7622(2) 0.0977(12) Uani 1 1 d . . . H37A H 0.5096 0.2323 0.7199 0.147 Uiso 1 1 calc R . . H37B H 0.3860 0.2441 0.7297 0.147 Uiso 1 1 calc R . . H37C H 0.4433 0.1913 0.7778 0.147 Uiso 1 1 calc R . . C38 C 0.6096(3) 0.20038(10) 0.97220(18) 0.0545(7) Uani 1 1 d . . . H38A H 0.5473 0.1825 0.9882 0.065 Uiso 1 1 calc R . . C39 C 0.7107(3) 0.18429(10) 1.01614(19) 0.0596(7) Uani 1 1 d . . . H39A H 0.7165 0.1552 1.0604 0.071 Uiso 1 1 calc R . . C40 C 0.8036(2) 0.21078(10) 0.99540(18) 0.0535(6) Uani 1 1 d . . . H40A H 0.8716 0.1999 1.0270 0.064 Uiso 1 1 calc R . . C41 C 0.79787(19) 0.25377(9) 0.92756(16) 0.0398(5) Uani 1 1 d . . . C42 C 0.89991(19) 0.28345(10) 0.90688(16) 0.0425(5) Uani 1 1 d . . . H42A H 0.8768 0.3180 0.8736 0.051 Uiso 1 1 calc R . . C43 C 0.9748(2) 0.29835(11) 0.99984(19) 0.0553(7) Uani 1 1 d . . . H43A H 0.9345 0.3195 1.0421 0.083 Uiso 1 1 calc R . . H43B H 1.0356 0.3196 0.9832 0.083 Uiso 1 1 calc R . . H43C H 1.0015 0.2653 1.0328 0.083 Uiso 1 1 calc R . . C44 C 0.69444(19) 0.26785(8) 0.88087(14) 0.0359(5) Uani 1 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 0.02921(19) 0.0345(2) 0.02325(18) 0.00215(15) 0.00487(13) -0.00059(15) O1 0.0789(13) 0.0557(10) 0.0271(8) 0.0047(7) 0.0178(8) -0.0079(9) N1 0.0345(10) 0.0606(12) 0.0308(9) 0.0035(9) 0.0042(7) 0.0076(9) C1 0.0364(14) 0.094(2) 0.0488(15) 0.0044(14) 0.0057(11) 0.0203(14) N2 0.0355(9) 0.0286(9) 0.0307(9) 0.0024(7) 0.0090(7) 0.0006(7) O2 0.0550(10) 0.0537(10) 0.0317(8) 0.0044(7) 0.0136(7) -0.0167(8) C2 0.056(2) 0.230(5) 0.057(2) 0.013(3) 0.0262(16) 0.032(3) N3 0.0368(10) 0.0353(9) 0.0255(9) -0.0005(7) 0.0079(7) -0.0066(7) O3 0.132(2) 0.1036(18) 0.0354(11) 0.0285(12) 0.0007(12) -0.0102(15) C3 0.0414(17) 0.183(4) 0.062(2) 0.001(2) -0.0090(14) 0.006(2) O4 0.0941(15) 0.0650(13) 0.0446(10) 0.0254(9) 0.0011(10) 0.0084(11) C4 0.092(3) 0.113(3) 0.113(3) 0.007(2) 0.000(2) 0.058(2) C5 0.0363(11) 0.0293(10) 0.0363(11) -0.0035(8) 0.0063(9) -0.0038(9) C6 0.0451(13) 0.0416(12) 0.0358(12) -0.0064(10) -0.0002(10) -0.0050(10) C7 0.0566(15) 0.0503(14) 0.0244(11) -0.0028(9) -0.0014(10) 0.0011(11) C8 0.0517(14) 0.0402(12) 0.0262(10) 0.0019(9) 0.0134(9) 0.0054(10) C9 0.0728(18) 0.0538(15) 0.0376(13) 0.0071(11) 0.0200(12) -0.0092(13) C10 0.0357(11) 0.0336(11) 0.0287(10) -0.0017(8) 0.0091(8) 0.0016(9) C11 0.0327(11) 0.0329(10) 0.0255(9) -0.0011(8) 0.0071(8) 0.0035(8) C12 0.0334(11) 0.0328(10) 0.0286(10) -0.0025(8) 0.0064(8) 0.0019(8) C13 0.0402(12) 0.0351(11) 0.0317(11) 0.0041(9) 0.0074(9) -0.0071(9) C14 0.0407(12) 0.0431(12) 0.0337(11) -0.0004(9) 0.0086(9) -0.0094(10) C15 0.0382(12) 0.0448(13) 0.0417(12) -0.0050(10) 0.0141(10) -0.0046(10) C16 0.0498(15) 0.0559(16) 0.0661(18) -0.0050(13) 0.0059(13) 0.0044(12) C17 0.0629(17) 0.0606(16) 0.0574(16) -0.0148(13) 0.0248(13) -0.0040(13) C18 0.0586(16) 0.0605(16) 0.0406(13) 0.0004(12) 0.0185(11) -0.0146(13) C19 0.079(2) 0.0576(17) 0.0438(14) 0.0177(12) 0.0153(13) -0.0193(14) C20 0.0754(19) 0.0428(13) 0.0504(15) 0.0151(12) 0.0095(13) -0.0059(13) C21 0.079(2) 0.0414(14) 0.0748(19) 0.0174(13) 0.0308(16) 0.0145(14) C22 0.114(3) 0.090(3) 0.133(4) 0.035(2) 0.036(3) 0.060(2) C23 0.158(4) 0.069(2) 0.093(3) -0.022(2) 0.061(3) -0.007(2) C24 0.0574(15) 0.0374(12) 0.0439(13) 0.0080(10) 0.0095(11) -0.0043(11) C25 0.0413(12) 0.0408(12) 0.0310(11) -0.0072(9) 0.0094(9) -0.0092(10) C26 0.0372(12) 0.0523(13) 0.0255(10) -0.0021(9) 0.0062(9) -0.0103(10) C27 0.0324(11) 0.0515(13) 0.0263(10) 0.0064(9) 0.0025(8) -0.0045(10) C28 0.0463(14) 0.0585(15) 0.0342(12) 0.0100(11) 0.0012(10) -0.0022(11) C29 0.099(3) 0.088(2) 0.0557(19) 0.0401(18) -0.0027(17) -0.001(2) C30 0.0674(18) 0.085(2) 0.0257(12) 0.0170(13) 0.0003(11) -0.0104(15) C31 0.077(2) 0.094(2) 0.0238(12) -0.0038(13) 0.0105(12) -0.0189(17) C32 0.0569(16) 0.0686(17) 0.0304(12) -0.0093(11) 0.0119(11) -0.0156(13) C33 0.0586(17) 0.0630(17) 0.0596(17) -0.0114(13) 0.0189(13) 0.0012(13) C34 0.0601(15) 0.0370(12) 0.0345(12) -0.0065(9) 0.0158(11) -0.0135(11) C35 0.0551(16) 0.0637(17) 0.0529(15) 0.0016(13) 0.0142(12) -0.0239(13) C36 0.064(2) 0.128(3) 0.083(2) -0.001(2) 0.0313(18) -0.024(2) C37 0.084(3) 0.141(3) 0.065(2) -0.021(2) -0.0030(18) -0.036(2) C38 0.084(2) 0.0401(13) 0.0439(14) -0.0027(11) 0.0268(14) -0.0218(13) C39 0.100(2) 0.0386(14) 0.0426(14) 0.0091(11) 0.0199(15) -0.0050(14) C40 0.0741(19) 0.0430(14) 0.0433(14) 0.0068(11) 0.0075(12) 0.0046(13) C41 0.0526(14) 0.0338(11) 0.0343(11) -0.0023(9) 0.0106(10) 0.0019(10) C42 0.0479(14) 0.0403(12) 0.0389(12) 0.0001(10) 0.0039(10) 0.0060(10) C43 0.0535(16) 0.0586(16) 0.0518(15) -0.0057(12) -0.0019(12) 0.0067(12) C44 0.0539(14) 0.0285(11) 0.0273(10) -0.0047(8) 0.0130(9) -0.0055(9) _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 1.6776(19) . ? Ti1 C11 2.200(2) . ? Ti1 C27 2.207(2) . ? Ti1 N3 2.2167(18) . ? Ti1 N2 2.2234(18) . ? O1 C8 1.374(3) . ? O1 C9 1.430(3) . ? N1 C1 1.441(3) . ? C1 C2 1.510(4) . ? C1 C4 1.529(5) . ? C1 C3 1.539(4) . ? N2 C5 1.287(3) . ? N2 C13 1.445(3) . ? O2 C10 1.385(3) . ? O2 C9 1.410(3) . ? N3 C25 1.290(3) . ? N3 C44 1.446(3) . ? O3 C30 1.362(3) . ? O3 C29 1.428(4) . ? O4 C28 1.389(3) . ? O4 C29 1.423(3) . ? C5 C12 1.444(3) . ? C6 C7 1.388(3) . ? C6 C12 1.395(3) . ? C7 C8 1.360(3) . ? C8 C10 1.386(3) . ? C10 C11 1.371(3) . ? C11 C12 1.414(3) . ? C13 C24 1.397(3) . ? C13 C14 1.400(3) . ? C14 C18 1.389(3) . ? C14 C15 1.516(3) . ? C15 C17 1.523(3) . ? C15 C16 1.530(3) . ? C18 C19 1.375(4) . ? C19 C20 1.366(4) . ? C20 C24 1.391(3) . ? C21 C24 1.519(4) . ? C21 C23 1.520(5) . ? C21 C22 1.531(5) . ? C25 C26 1.441(3) . ? C26 C32 1.400(3) . ? C26 C27 1.425(3) . ? C27 C28 1.362(3) . ? C28 C30 1.392(3) . ? C30 C31 1.367(4) . ? C31 C32 1.388(4) . ? C33 C42 1.529(3) . ? C34 C38 1.394(3) . ? C34 C44 1.399(3) . ? C34 C35 1.501(4) . ? C35 C37 1.520(4) . ? C35 C36 1.524(4) . ? C38 C39 1.368(4) . ? C39 C40 1.372(4) . ? C40 C41 1.397(3) . ? C41 C44 1.392(3) . ? C41 C42 1.505(3) . ? C42 C43 1.523(3) . ? 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 C11 102.58(8) . . ? N1 Ti1 C27 101.52(8) . . ? C11 Ti1 C27 155.90(8) . . ? N1 Ti1 N3 114.98(8) . . ? C11 Ti1 N3 93.17(7) . . ? C27 Ti1 N3 76.28(7) . . ? N1 Ti1 N2 117.76(9) . . ? C11 Ti1 N2 76.22(7) . . ? C27 Ti1 N2 92.81(7) . . ? N3 Ti1 N2 127.26(6) . . ? C8 O1 C9 104.98(17) . . ? C1 N1 Ti1 176.53(17) . . ? N1 C1 C2 109.9(2) . . ? N1 C1 C4 108.8(3) . . ? C2 C1 C4 112.8(3) . . ? N1 C1 C3 106.9(2) . . ? C2 C1 C3 110.1(3) . . ? C4 C1 C3 108.0(3) . . ? C5 N2 C13 117.49(17) . . ? C5 N2 Ti1 113.75(13) . . ? C13 N2 Ti1 128.45(13) . . ? C10 O2 C9 105.97(17) . . ? C25 N3 C44 117.20(18) . . ? C25 N3 Ti1 114.38(14) . . ? C44 N3 Ti1 128.22(12) . . ? C30 O3 C29 105.9(2) . . ? C28 O4 C29 105.9(2) . . ? N2 C5 C12 121.49(19) . . ? C7 C6 C12 120.6(2) . . ? C8 C7 C6 115.81(19) . . ? C7 C8 O1 127.1(2) . . ? C7 C8 C10 122.6(2) . . ? O1 C8 C10 110.2(2) . . ? O2 C9 O1 107.87(18) . . ? C11 C10 O2 126.85(18) . . ? C11 C10 C8 124.8(2) . . ? O2 C10 C8 108.27(17) . . ? C10 C11 C12 111.60(17) . . ? C10 C11 Ti1 135.18(15) . . ? C12 C11 Ti1 113.06(13) . . ? C6 C12 C11 124.51(19) . . ? C6 C12 C5 120.02(19) . . ? C11 C12 C5 115.45(17) . . ? C24 C13 C14 121.8(2) . . ? C24 C13 N2 119.96(19) . . ? C14 C13 N2 118.22(18) . . ? C18 C14 C13 117.4(2) . . ? C18 C14 C15 121.3(2) . . ? C13 C14 C15 121.23(19) . . ? C14 C15 C17 113.3(2) . . ? C14 C15 C16 110.78(19) . . ? C17 C15 C16 110.4(2) . . ? C19 C18 C14 121.4(2) . . ? C20 C19 C18 120.2(2) . . ? C19 C20 C24 121.1(2) . . ? C24 C21 C23 110.7(3) . . ? C24 C21 C22 111.2(3) . . ? C23 C21 C22 111.1(3) . . ? C20 C24 C13 118.0(2) . . ? C20 C24 C21 119.9(2) . . ? C13 C24 C21 122.1(2) . . ? N3 C25 C26 121.0(2) . . ? C32 C26 C27 124.6(2) . . ? C32 C26 C25 119.5(2) . . ? C27 C26 C25 115.85(18) . . ? C28 C27 C26 111.6(2) . . ? C28 C27 Ti1 135.83(18) . . ? C26 C27 Ti1 112.44(14) . . ? C27 C28 O4 126.6(2) . . ? C27 C28 C30 124.9(3) . . ? O4 C28 C30 108.4(2) . . ? O4 C29 O3 108.0(2) . . ? O3 C30 C31 127.0(2) . . ? O3 C30 C28 110.4(3) . . ? C31 C30 C28 122.6(2) . . ? C30 C31 C32 116.0(2) . . ? C31 C32 C26 120.2(3) . . ? C38 C34 C44 117.2(2) . . ? C38 C34 C35 121.8(2) . . ? C44 C34 C35 121.0(2) . . ? C34 C35 C37 111.0(3) . . ? C34 C35 C36 113.9(2) . . ? C37 C35 C36 110.1(3) . . ? C39 C38 C34 121.3(2) . . ? C38 C39 C40 120.5(2) . . ? C39 C40 C41 121.1(3) . . ? C44 C41 C40 117.3(2) . . ? C44 C41 C42 121.92(19) . . ? C40 C41 C42 120.8(2) . . ? C41 C42 C43 112.6(2) . . ? C41 C42 C33 111.4(2) . . ? C43 C42 C33 110.5(2) . . ? C41 C44 C34 122.5(2) . . ? C41 C44 N3 119.14(19) . . ? C34 C44 N3 118.3(2) . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 28.49 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.365 _refine_diff_density_min -0.423 _refine_diff_density_rms 0.055