# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Edit Y. Tshuva' _publ_contact_author_email TSHUVA@CHEM.CH.HUJI.AC.IL _publ_section_title ; Markedly Different Cytotoxicity of the Two Enantiomers of C2-Symmetrical Ti(IV) Phenolato Complexes; Mechanistic Implications ; loop_ _publ_author_name 'Edit Tshuva' 'Cesar M. Manna' # Attachment 'Tshuva_CIFs.cif' data_RacL5Ti(OiPr)2 _database_code_depnum_ccdc_archive 'CCDC 738409' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '3(C28 H42 N2 O4 Ti),0.5(C4 H10 O)' _chemical_formula_sum 'C86 H131 N6 O12.50 Ti3' _chemical_formula_weight 1592.67 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_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 16.003(2) _cell_length_b 16.419(2) _cell_length_c 18.826(3) _cell_angle_alpha 71.809(2) _cell_angle_beta 75.644(2) _cell_angle_gamma 76.478(2) _cell_volume 4486.4(10) _cell_formula_units_Z 2 _cell_measurement_temperature 173(1) _cell_measurement_reflns_used 3639 _cell_measurement_theta_min 2.32 _cell_measurement_theta_max 27.43 _exptl_crystal_description plate _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.179 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1710 _exptl_absorpt_coefficient_mu 0.320 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(1) _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 35322 _diffrn_reflns_av_R_equivalents 0.0720 _diffrn_reflns_av_sigmaI/netI 0.1448 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.29 _diffrn_reflns_theta_max 27.00 _reflns_number_total 19083 _reflns_number_gt 10133 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.1245P)^2^+3.7688P] 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 19083 _refine_ls_number_parameters 1001 _refine_ls_number_restraints 16 _refine_ls_R_factor_all 0.1989 _refine_ls_R_factor_gt 0.1157 _refine_ls_wR_factor_ref 0.2979 _refine_ls_wR_factor_gt 0.2546 _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_restrained_S_all 1.055 _refine_ls_shift/su_max 0.003 _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 C1 C 0.9749(4) 0.6870(4) 0.3481(3) 0.0376(15) Uani 1 1 d . . . C2 C 1.0149(4) 0.6086(5) 0.3931(3) 0.0474(18) Uani 1 1 d . . . H2 H 1.0557 0.6103 0.4214 0.057 Uiso 1 1 calc R . . C3 C 0.9959(5) 0.5293(5) 0.3968(4) 0.0550(19) Uani 1 1 d . . . H3 H 1.0242 0.4778 0.4276 0.066 Uiso 1 1 calc R . . C4 C 0.9379(5) 0.5226(5) 0.3575(4) 0.0554(19) Uani 1 1 d . . . C5 C 0.8973(4) 0.5993(4) 0.3133(4) 0.0485(17) Uani 1 1 d . . . H5 H 0.8562 0.5959 0.2860 0.058 Uiso 1 1 calc R . . C6 C 0.9140(4) 0.6803(4) 0.3070(3) 0.0422(16) Uani 1 1 d . . . C7 C 0.8747(4) 0.7596(4) 0.2524(4) 0.0440(16) Uani 1 1 d . . . H7A H 0.9172 0.7722 0.2038 0.053 Uiso 1 1 calc R . . H7B H 0.8218 0.7479 0.2415 0.053 Uiso 1 1 calc R . . C8 C 0.7866(4) 0.8254(4) 0.3556(4) 0.0457(17) Uani 1 1 d . . . H8 H 0.8110 0.7720 0.3926 0.055 Uiso 1 1 calc R . . C9 C 0.6979(5) 0.8136(5) 0.3489(5) 0.069(2) Uani 1 1 d . . . H9A H 0.6743 0.8636 0.3096 0.083 Uiso 1 1 calc R . . H9B H 0.7047 0.7602 0.3326 0.083 Uiso 1 1 calc R . . C10 C 0.6341(6) 0.8065(6) 0.4239(7) 0.118(4) Uani 1 1 d . . . H10A H 0.6557 0.7545 0.4627 0.141 Uiso 1 1 calc R . . H10B H 0.5765 0.8001 0.4178 0.141 Uiso 1 1 calc R . . C11 C 0.6243(6) 0.8874(6) 0.4502(6) 0.105(4) Uani 1 1 d . . . H11A H 0.5826 0.8824 0.4993 0.127 Uiso 1 1 calc R . . H11B H 0.6004 0.9391 0.4123 0.127 Uiso 1 1 calc R . . C12 C 0.7141(6) 0.8986(6) 0.4597(5) 0.082(3) Uani 1 1 d . . . H12A H 0.7073 0.9529 0.4746 0.098 Uiso 1 1 calc R . . H12B H 0.7356 0.8493 0.5006 0.098 Uiso 1 1 calc R . . C13 C 0.7804(4) 0.9023(4) 0.3853(4) 0.0491(18) Uani 1 1 d . . . H13 H 0.7602 0.9561 0.3465 0.059 Uiso 1 1 calc R . . C14 C 0.8777(5) 0.9861(4) 0.4084(4) 0.0521(18) Uani 1 1 d . . . H14A H 0.9386 0.9827 0.4136 0.063 Uiso 1 1 calc R . . H14B H 0.8389 0.9903 0.4575 0.063 Uiso 1 1 calc R . . C15 C 0.8534(4) 1.0665(4) 0.3470(4) 0.0448(16) Uani 1 1 d . . . C16 C 0.8113(5) 1.1421(5) 0.3676(5) 0.0574(19) Uani 1 1 d . . . H16 H 0.7952 1.1392 0.4203 0.069 Uiso 1 1 calc R . . C17 C 0.7912(5) 1.2215(5) 0.3160(6) 0.065(2) Uani 1 1 d . . . C18 C 0.8130(5) 1.2203(5) 0.2404(5) 0.062(2) Uani 1 1 d . . . H18 H 0.7990 1.2728 0.2027 0.075 Uiso 1 1 calc R . . C19 C 0.8538(4) 1.1472(4) 0.2175(4) 0.0502(17) Uani 1 1 d . . . H19 H 0.8678 1.1501 0.1647 0.060 Uiso 1 1 calc R . . C20 C 0.8750(4) 1.0688(4) 0.2705(4) 0.0439(16) Uani 1 1 d . . . C21 C 0.9186(6) 0.4354(5) 0.3602(5) 0.086(3) Uani 1 1 d . . . H21A H 0.9712 0.4020 0.3365 0.129 Uiso 1 1 calc R . . H21B H 0.8712 0.4447 0.3326 0.129 Uiso 1 1 calc R . . H21C H 0.9009 0.4031 0.4134 0.129 Uiso 1 1 calc R . . C22 C 0.7448(7) 1.3041(5) 0.3406(7) 0.106(4) Uani 1 1 d . . . H22A H 0.7869 1.3432 0.3300 0.159 Uiso 1 1 calc R . . H22B H 0.7203 1.2884 0.3952 0.159 Uiso 1 1 calc R . . H22C H 0.6975 1.3336 0.3121 0.159 Uiso 1 1 calc R . . C23 C 1.0394(4) 0.9267(4) 0.1211(3) 0.0494(17) Uani 1 1 d D . . H23 H 0.9835 0.9673 0.1117 0.059 Uiso 1 1 calc R . . C24 C 1.0678(5) 0.8728(4) 0.0632(3) 0.065(2) Uani 1 1 d D . . H24A H 1.1249 0.8364 0.0695 0.098 Uiso 1 1 calc R . . H24B H 1.0722 0.9119 0.0115 0.098 Uiso 1 1 calc R . . H24C H 1.0245 0.8357 0.0716 0.098 Uiso 1 1 calc R . . C25 C 1.1095(5) 0.9796(5) 0.1145(4) 0.069(2) Uani 1 1 d D . . H25A H 1.0906 1.0121 0.1531 0.104 Uiso 1 1 calc R . . H25B H 1.1180 1.0204 0.0637 0.104 Uiso 1 1 calc R . . H25C H 1.1647 0.9402 0.1226 0.104 Uiso 1 1 calc R . . C26 C 1.1380(6) 0.8879(6) 0.3304(6) 0.093(3) Uani 1 1 d D . . H26 H 1.1697 0.8750 0.2813 0.112 Uiso 1 1 calc R . . C27 C 1.1616(9) 0.8071(8) 0.3940(7) 0.160(6) Uani 1 1 d D . . H27A H 1.1411 0.8207 0.4432 0.241 Uiso 1 1 calc R . . H27B H 1.2252 0.7885 0.3858 0.241 Uiso 1 1 calc R . . H27C H 1.1335 0.7601 0.3938 0.241 Uiso 1 1 calc R . . C28 C 1.1698(9) 0.9673(8) 0.3342(10) 0.195(8) Uani 1 1 d D . . H28A H 1.1486 1.0187 0.2957 0.293 Uiso 1 1 calc R . . H28B H 1.2340 0.9570 0.3243 0.293 Uiso 1 1 calc R . . H28C H 1.1473 0.9767 0.3849 0.293 Uiso 1 1 calc R . . C31 C 0.2626(4) 0.1172(4) 0.9065(3) 0.0348(14) Uani 1 1 d . . . C32 C 0.2047(4) 0.0720(4) 0.8958(3) 0.0348(14) Uani 1 1 d . . . H32 H 0.1438 0.0855 0.9147 0.042 Uiso 1 1 calc R . . C33 C 0.2353(4) 0.0078(4) 0.8580(3) 0.0391(15) Uani 1 1 d . . . H33 H 0.1948 -0.0232 0.8530 0.047 Uiso 1 1 calc R . . C34 C 0.3226(4) -0.0126(4) 0.8274(3) 0.0419(15) Uani 1 1 d . . . C35 C 0.3799(4) 0.0316(4) 0.8386(3) 0.0389(15) Uani 1 1 d . . . H35 H 0.4406 0.0186 0.8184 0.047 Uiso 1 1 calc R . . C36 C 0.3512(4) 0.0950(4) 0.8788(3) 0.0350(14) Uani 1 1 d . . . C37 C 0.4190(4) 0.1336(4) 0.8945(3) 0.0395(15) Uani 1 1 d . . . H37A H 0.4333 0.0999 0.9449 0.047 Uiso 1 1 calc R . . H37B H 0.4730 0.1280 0.8558 0.047 Uiso 1 1 calc R . . C38 C 0.3767(4) 0.2851(4) 0.8181(3) 0.0375(15) Uani 1 1 d . . . H38 H 0.3379 0.2607 0.7987 0.045 Uiso 1 1 calc R . . C39 C 0.4627(5) 0.2926(5) 0.7595(3) 0.0553(19) Uani 1 1 d . . . H39A H 0.5052 0.3088 0.7808 0.066 Uiso 1 1 calc R . . H39B H 0.4880 0.2355 0.7490 0.066 Uiso 1 1 calc R . . C40 C 0.4473(6) 0.3609(5) 0.6852(3) 0.066(2) Uani 1 1 d . . . H40A H 0.5042 0.3676 0.6501 0.079 Uiso 1 1 calc R . . H40B H 0.4110 0.3409 0.6606 0.079 Uiso 1 1 calc R . . C41 C 0.4025(6) 0.4469(5) 0.6991(4) 0.064(2) Uani 1 1 d . . . H41A H 0.3921 0.4892 0.6502 0.077 Uiso 1 1 calc R . . H41B H 0.4410 0.4691 0.7200 0.077 Uiso 1 1 calc R . . C42 C 0.3155(5) 0.4397(4) 0.7546(3) 0.0494(18) Uani 1 1 d . . . H42A H 0.2750 0.4225 0.7319 0.059 Uiso 1 1 calc R . . H42B H 0.2888 0.4969 0.7642 0.059 Uiso 1 1 calc R . . C43 C 0.3291(4) 0.3723(4) 0.8297(3) 0.0391(15) Uani 1 1 d . . . H43 H 0.3670 0.3938 0.8524 0.047 Uiso 1 1 calc R . . C44 C 0.1998(4) 0.4356(4) 0.9119(3) 0.0406(15) Uani 1 1 d . . . H44A H 0.1469 0.4202 0.9500 0.049 Uiso 1 1 calc R . . H44B H 0.1804 0.4812 0.8677 0.049 Uiso 1 1 calc R . . C45 C 0.2539(4) 0.4714(4) 0.9464(3) 0.0383(15) Uani 1 1 d . . . C46 C 0.2412(4) 0.5603(4) 0.9378(3) 0.0434(16) Uani 1 1 d . . . H46 H 0.1988 0.5973 0.9092 0.052 Uiso 1 1 calc R . . C47 C 0.2871(5) 0.5974(5) 0.9691(4) 0.0517(19) Uani 1 1 d . . . C48 C 0.3498(5) 0.5422(5) 1.0100(4) 0.054(2) Uani 1 1 d . . . H48 H 0.3828 0.5661 1.0315 0.065 Uiso 1 1 calc R . . C49 C 0.3648(4) 0.4535(5) 1.0199(3) 0.0456(17) Uani 1 1 d . . . H49 H 0.4084 0.4173 1.0474 0.055 Uiso 1 1 calc R . . C50 C 0.3163(4) 0.4165(4) 0.9896(3) 0.0383(15) Uani 1 1 d . . . C51 C 0.3565(5) -0.0827(5) 0.7857(4) 0.061(2) Uani 1 1 d . . . H51A H 0.3986 -0.0617 0.7395 0.091 Uiso 1 1 calc R . . H51B H 0.3074 -0.0967 0.7718 0.091 Uiso 1 1 calc R . . H51C H 0.3853 -0.1349 0.8188 0.091 Uiso 1 1 calc R . . C52 C 0.2698(6) 0.6946(5) 0.9601(4) 0.072(2) Uani 1 1 d . . . H52A H 0.2617 0.7052 1.0100 0.108 Uiso 1 1 calc R . . H52B H 0.2168 0.7213 0.9386 0.108 Uiso 1 1 calc R . . H52C H 0.3197 0.7201 0.9260 0.108 Uiso 1 1 calc R . . C53 C 0.3443(5) 0.1234(4) 1.1280(4) 0.071(2) Uani 1 1 d D . . H53 H 0.2877 0.1437 1.1596 0.085 Uiso 1 1 calc R . . C54 C 0.3570(6) 0.0242(4) 1.1509(5) 0.080(3) Uani 1 1 d D . . H54A H 0.3037 0.0058 1.1491 0.120 Uiso 1 1 calc R . . H54B H 0.3691 0.0015 1.2027 0.120 Uiso 1 1 calc R . . H54C H 0.4064 0.0016 1.1155 0.120 Uiso 1 1 calc R . . C55 C 0.4140(5) 0.1622(5) 1.1424(4) 0.068(2) Uani 1 1 d D . . H55A H 0.4706 0.1452 1.1114 0.102 Uiso 1 1 calc R . . H55B H 0.4180 0.1406 1.1964 0.102 Uiso 1 1 calc R . . H55C H 0.3983 0.2257 1.1287 0.102 Uiso 1 1 calc R . . C56 C 0.0907(4) 0.2401(4) 1.0757(3) 0.0523(18) Uani 1 1 d D . . H56 H 0.0888 0.1960 1.0498 0.063 Uiso 1 1 calc R . . C57 C 0.0853(5) 0.1970(5) 1.1611(3) 0.068(2) Uani 1 1 d D . . H57A H 0.1341 0.1483 1.1691 0.102 Uiso 1 1 calc R . . H57B H 0.0298 0.1753 1.1825 0.102 Uiso 1 1 calc R . . H57C H 0.0887 0.2396 1.1864 0.102 Uiso 1 1 calc R . . C58 C 0.0129(5) 0.3142(5) 1.0631(5) 0.082(3) Uani 1 1 d D . . H58A H 0.0148 0.3578 1.0880 0.123 Uiso 1 1 calc R . . H58B H -0.0418 0.2910 1.0848 0.123 Uiso 1 1 calc R . . H58C H 0.0159 0.3413 1.0084 0.123 Uiso 1 1 calc R . . C61 C 0.1884(4) 0.3358(4) 0.3843(3) 0.0368(14) Uani 1 1 d . . . C62 C 0.1260(4) 0.3151(4) 0.4514(3) 0.0411(16) Uani 1 1 d . . . H62 H 0.1215 0.3415 0.4908 0.049 Uiso 1 1 calc R . . C63 C 0.0713(4) 0.2578(5) 0.4613(3) 0.0472(18) Uani 1 1 d . . . H63 H 0.0300 0.2447 0.5075 0.057 Uiso 1 1 calc R . . C64 C 0.0756(5) 0.2188(5) 0.4048(4) 0.0541(19) Uani 1 1 d . . . C65 C 0.1382(5) 0.2388(4) 0.3378(4) 0.0498(17) Uani 1 1 d . . . H65 H 0.1423 0.2119 0.2988 0.060 Uiso 1 1 calc R . . C66 C 0.1945(4) 0.2968(4) 0.3265(3) 0.0379(15) Uani 1 1 d . . . C67 C 0.2589(4) 0.3173(4) 0.2528(3) 0.0405(15) Uani 1 1 d . . . H67A H 0.3176 0.2840 0.2604 0.049 Uiso 1 1 calc R . . H67B H 0.2414 0.2992 0.2140 0.049 Uiso 1 1 calc R . . C68 C 0.1785(4) 0.4680(4) 0.2124(3) 0.0350(14) Uani 1 1 d . . . H68 H 0.1344 0.4525 0.2603 0.042 Uiso 1 1 calc R . . C69 C 0.1439(4) 0.4579(4) 0.1484(3) 0.0414(15) Uani 1 1 d . . . H69A H 0.1346 0.3972 0.1600 0.050 Uiso 1 1 calc R . . H69B H 0.1877 0.4699 0.1006 0.050 Uiso 1 1 calc R . . C70 C 0.0583(4) 0.5196(4) 0.1373(4) 0.0487(17) Uani 1 1 d . . . H70A H 0.0130 0.5044 0.1835 0.058 Uiso 1 1 calc R . . H70B H 0.0383 0.5131 0.0939 0.058 Uiso 1 1 calc R . . C71 C 0.0692(5) 0.6134(5) 0.1221(4) 0.0501(18) Uani 1 1 d . . . H71A H 0.0121 0.6521 0.1175 0.060 Uiso 1 1 calc R . . H71B H 0.1104 0.6304 0.0733 0.060 Uiso 1 1 calc R . . C72 C 0.1042(4) 0.6245(4) 0.1866(3) 0.0374(14) Uani 1 1 d . . . H72A H 0.1147 0.6849 0.1740 0.045 Uiso 1 1 calc R . . H72B H 0.0597 0.6143 0.2341 0.045 Uiso 1 1 calc R . . C73 C 0.1893(4) 0.5611(4) 0.1997(3) 0.0352(14) Uani 1 1 d . . . H73 H 0.2355 0.5765 0.1534 0.042 Uiso 1 1 calc R . . C74 C 0.2458(4) 0.6498(4) 0.2580(3) 0.0363(14) Uani 1 1 d . . . H74A H 0.2659 0.6478 0.3042 0.044 Uiso 1 1 calc R . . H74B H 0.1940 0.6965 0.2521 0.044 Uiso 1 1 calc R . . C75 C 0.3175(4) 0.6704(4) 0.1895(3) 0.0373(15) Uani 1 1 d . . . C76 C 0.3144(4) 0.7533(4) 0.1422(3) 0.0439(16) Uani 1 1 d . . . H76 H 0.2666 0.7967 0.1542 0.053 Uiso 1 1 calc R . . C77 C 0.3774(4) 0.7772(5) 0.0776(3) 0.0453(17) Uani 1 1 d . . . C78 C 0.4478(4) 0.7117(5) 0.0623(3) 0.0479(18) Uani 1 1 d . . . H78 H 0.4929 0.7254 0.0191 0.057 Uiso 1 1 calc R . . C79 C 0.4523(4) 0.6282(4) 0.1088(3) 0.0403(15) Uani 1 1 d . . . H79 H 0.5009 0.5855 0.0969 0.048 Uiso 1 1 calc R . . C80 C 0.3883(4) 0.6039(4) 0.1729(3) 0.0363(14) Uani 1 1 d . . . C81 C 0.0134(6) 0.1580(6) 0.4133(5) 0.089(3) Uani 1 1 d . . . H81A H 0.0347 0.1268 0.3738 0.134 Uiso 1 1 calc R . . H81B H -0.0450 0.1918 0.4079 0.134 Uiso 1 1 calc R . . H81C H 0.0103 0.1161 0.4636 0.134 Uiso 1 1 calc R . . C82 C 0.3691(5) 0.8687(5) 0.0245(4) 0.065(2) Uani 1 1 d . . . H82A H 0.3137 0.9034 0.0425 0.098 Uiso 1 1 calc R . . H82B H 0.3701 0.8660 -0.0270 0.098 Uiso 1 1 calc R . . H82C H 0.4180 0.8956 0.0237 0.098 Uiso 1 1 calc R . . C83 C 0.5015(5) 0.3314(4) 0.2883(4) 0.061(2) Uani 1 1 d D . . H83 H 0.5282 0.3726 0.3017 0.073 Uiso 1 1 calc R . . C84 C 0.5344(7) 0.3368(7) 0.2034(4) 0.123(5) Uani 1 1 d D . . H84A H 0.5135 0.2925 0.1908 0.184 Uiso 1 1 calc R . . H84B H 0.5986 0.3267 0.1925 0.184 Uiso 1 1 calc R . . H84C H 0.5123 0.3946 0.1729 0.184 Uiso 1 1 calc R . . C85 C 0.5259(6) 0.2394(5) 0.3390(5) 0.088(3) Uani 1 1 d D . . H85A H 0.5027 0.2384 0.3925 0.132 Uiso 1 1 calc R . . H85B H 0.5898 0.2227 0.3312 0.132 Uiso 1 1 calc R . . H85C H 0.5009 0.1983 0.3257 0.132 Uiso 1 1 calc R . . C86 C 0.3332(5) 0.4698(6) 0.4515(4) 0.091(3) Uani 1 1 d D . . H86 H 0.2964 0.4230 0.4716 0.109 Uiso 1 1 calc R . . C87 C 0.4239(6) 0.4348(7) 0.4728(5) 0.114(4) Uani 1 1 d D . . H87A H 0.4549 0.3897 0.4472 0.172 Uiso 1 1 calc R . . H87B H 0.4173 0.4099 0.5281 0.172 Uiso 1 1 calc R . . H87C H 0.4575 0.4824 0.4569 0.172 Uiso 1 1 calc R . . C88 C 0.2871(11) 0.5488(9) 0.4811(7) 0.244(11) Uani 1 1 d D . . H88A H 0.3248 0.5932 0.4629 0.365 Uiso 1 1 calc R . . H88B H 0.2748 0.5311 0.5369 0.365 Uiso 1 1 calc R . . H88C H 0.2319 0.5728 0.4625 0.365 Uiso 1 1 calc R . . C91 C 0.4155(9) 1.0109(9) 0.3696(8) 0.056(4) Uani 0.50 1 d PD . . H91A H 0.4655 1.0316 0.3303 0.068 Uiso 0.50 1 calc PR . . H91B H 0.4272 1.0077 0.4197 0.068 Uiso 0.50 1 calc PR . . C92 C 0.3331(9) 1.0782(9) 0.3557(7) 0.070(5) Uani 0.50 1 d PD . . H92A H 0.3200 1.0815 0.3066 0.104 Uiso 0.50 1 calc PR . . H92B H 0.3427 1.1352 0.3552 0.104 Uiso 0.50 1 calc PR . . H92C H 0.2838 1.0610 0.3965 0.104 Uiso 0.50 1 calc PR . . C93 C 0.3779(13) 0.8803(9) 0.4350(9) 0.088(6) Uiso 0.50 1 d PD . . H93A H 0.3149 0.9041 0.4475 0.105 Uiso 0.50 1 calc PR . . H93B H 0.4062 0.8837 0.4749 0.105 Uiso 0.50 1 calc PR . . C94 C 0.3872(12) 0.7845(9) 0.4377(10) 0.085(5) Uiso 0.50 1 d PD . . H94A H 0.3332 0.7743 0.4288 0.128 Uiso 0.50 1 calc PR . . H94B H 0.3979 0.7479 0.4879 0.128 Uiso 0.50 1 calc PR . . H94C H 0.4364 0.7699 0.3983 0.128 Uiso 0.50 1 calc PR . . N1 N 0.8504(3) 0.8371(3) 0.2833(3) 0.0401(13) Uani 1 1 d . . . H1 H 0.8229 0.8817 0.2479 0.048 Uiso 1 1 calc R . . N2 N 0.8705(3) 0.9063(3) 0.3920(3) 0.0441(13) Uani 1 1 d . . . H2A H 0.8844 0.8605 0.4334 0.053 Uiso 1 1 calc R . . N3 N 0.3904(3) 0.2265(3) 0.8939(2) 0.0344(12) Uani 1 1 d . . . H3A H 0.4366 0.2429 0.9047 0.041 Uiso 1 1 calc R . . N4 N 0.2484(3) 0.3581(3) 0.8869(2) 0.0339(11) Uani 1 1 d . . . H4 H 0.2115 0.3425 0.8640 0.041 Uiso 1 1 calc R . . N5 N 0.2630(3) 0.4116(3) 0.2253(2) 0.0361(12) Uani 1 1 d . . . H5A H 0.3003 0.4198 0.1780 0.043 Uiso 1 1 calc R . . N6 N 0.2204(3) 0.5646(3) 0.2671(2) 0.0344(12) Uani 1 1 d . . . H6 H 0.1730 0.5587 0.3075 0.041 Uiso 1 1 calc R . . O1 O 0.9957(3) 0.7631(3) 0.3439(2) 0.0407(10) Uani 1 1 d . . . O2 O 0.9147(3) 0.9977(3) 0.2469(2) 0.0437(11) Uani 1 1 d . . . O3 O 1.0256(3) 0.8707(3) 0.1961(2) 0.0455(11) Uani 1 1 d . . . O4 O 1.0516(3) 0.9110(3) 0.3262(3) 0.0506(12) Uani 1 1 d . . . O5 O 0.2297(3) 0.1793(3) 0.9424(2) 0.0375(10) Uani 1 1 d . . . O6 O 0.3311(3) 0.3292(3) 1.0029(2) 0.0398(10) Uani 1 1 d . . . O7 O 0.3333(3) 0.1547(3) 1.0523(2) 0.0568(13) Uani 1 1 d . . . O8 O 0.1700(3) 0.2730(3) 1.0450(2) 0.0453(11) Uani 1 1 d . . . O9 O 0.2371(3) 0.3952(3) 0.3765(2) 0.0386(10) Uani 1 1 d . . . O10 O 0.3929(3) 0.5225(3) 0.2149(2) 0.0394(10) Uani 1 1 d . . . O11 O 0.4110(3) 0.3557(3) 0.3024(3) 0.0524(12) Uani 1 1 d . . . O12 O 0.3456(3) 0.4975(3) 0.3720(2) 0.0530(12) Uani 1 1 d . . . O13 O 0.4123(9) 0.9304(10) 0.3684(7) 0.112(5) Uani 0.50 1 d PD . . Ti1 Ti 0.97129(7) 0.88282(7) 0.28970(6) 0.0369(3) Uani 1 1 d . . . Ti2 Ti 0.27608(7) 0.24418(7) 0.98902(5) 0.0354(3) Uani 1 1 d . . . Ti3 Ti 0.32735(7) 0.45148(8) 0.30229(6) 0.0377(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 C1 0.032(3) 0.044(4) 0.022(3) 0.002(3) -0.004(2) 0.002(3) C2 0.046(4) 0.064(5) 0.017(3) -0.006(3) -0.003(3) 0.010(3) C3 0.060(5) 0.042(4) 0.040(4) 0.009(3) 0.000(3) -0.004(4) C4 0.043(4) 0.042(4) 0.063(4) 0.006(4) -0.004(4) -0.005(3) C5 0.032(4) 0.044(4) 0.058(4) 0.002(3) -0.004(3) -0.010(3) C6 0.034(4) 0.036(4) 0.040(3) 0.008(3) -0.001(3) -0.006(3) C7 0.041(4) 0.037(4) 0.053(4) -0.009(3) -0.014(3) -0.004(3) C8 0.037(4) 0.032(4) 0.048(4) 0.006(3) 0.003(3) -0.003(3) C9 0.037(4) 0.053(5) 0.109(7) -0.018(5) 0.000(4) -0.011(4) C10 0.067(6) 0.081(7) 0.180(11) -0.043(7) 0.051(7) -0.034(6) C11 0.047(5) 0.080(7) 0.154(10) -0.031(7) 0.047(6) -0.012(5) C12 0.076(6) 0.065(6) 0.071(5) -0.011(4) 0.031(5) -0.005(5) C13 0.027(4) 0.046(4) 0.055(4) -0.007(3) 0.009(3) 0.003(3) C14 0.052(4) 0.056(5) 0.044(4) -0.014(3) -0.012(3) 0.002(4) C15 0.030(4) 0.041(4) 0.064(4) -0.018(3) -0.010(3) -0.001(3) C16 0.044(4) 0.055(5) 0.078(5) -0.019(4) -0.018(4) -0.009(4) C17 0.051(5) 0.038(4) 0.112(7) -0.017(5) -0.029(5) -0.008(4) C18 0.059(5) 0.033(4) 0.091(6) 0.010(4) -0.031(5) -0.021(4) C19 0.050(4) 0.034(4) 0.065(4) -0.002(3) -0.017(4) -0.012(3) C20 0.032(4) 0.046(4) 0.051(4) 0.000(3) -0.012(3) -0.014(3) C21 0.070(6) 0.047(5) 0.120(8) 0.009(5) -0.017(5) -0.017(4) C22 0.106(8) 0.046(5) 0.178(11) -0.048(6) -0.037(8) -0.002(5) C23 0.052(4) 0.048(4) 0.035(3) 0.002(3) -0.005(3) -0.005(3) C24 0.087(6) 0.067(5) 0.029(3) -0.008(3) -0.005(4) -0.005(5) C25 0.090(6) 0.047(5) 0.055(4) 0.004(4) 0.007(4) -0.025(4) C26 0.062(6) 0.118(9) 0.101(7) -0.017(7) -0.031(5) -0.020(6) C27 0.116(11) 0.202(16) 0.152(12) -0.015(11) -0.060(10) -0.012(10) C28 0.134(12) 0.187(16) 0.29(2) -0.001(14) -0.118(13) -0.076(11) C31 0.037(4) 0.042(4) 0.023(3) -0.002(3) -0.009(2) -0.007(3) C32 0.033(3) 0.033(3) 0.031(3) 0.002(3) -0.012(3) -0.001(3) C33 0.044(4) 0.032(4) 0.040(3) 0.000(3) -0.015(3) -0.008(3) C34 0.055(4) 0.034(4) 0.040(3) -0.007(3) -0.018(3) -0.010(3) C35 0.042(4) 0.035(4) 0.041(3) -0.013(3) -0.012(3) 0.001(3) C36 0.043(4) 0.039(4) 0.025(3) 0.001(3) -0.015(3) -0.014(3) C37 0.041(4) 0.046(4) 0.039(3) -0.026(3) -0.006(3) -0.003(3) C38 0.042(4) 0.050(4) 0.029(3) -0.015(3) -0.010(3) -0.015(3) C39 0.062(5) 0.070(5) 0.039(4) -0.024(4) 0.003(3) -0.023(4) C40 0.097(6) 0.081(6) 0.029(3) -0.021(4) 0.010(4) -0.046(5) C41 0.099(6) 0.065(5) 0.033(3) -0.002(3) -0.007(4) -0.043(5) C42 0.071(5) 0.045(4) 0.035(3) 0.003(3) -0.024(3) -0.019(4) C43 0.049(4) 0.051(4) 0.026(3) -0.008(3) -0.012(3) -0.022(3) C44 0.045(4) 0.035(4) 0.044(3) -0.003(3) -0.021(3) -0.008(3) C45 0.039(4) 0.049(4) 0.032(3) -0.018(3) -0.003(3) -0.011(3) C46 0.051(4) 0.041(4) 0.038(3) -0.016(3) 0.000(3) -0.009(3) C47 0.065(5) 0.061(5) 0.041(4) -0.034(4) 0.009(3) -0.025(4) C48 0.049(4) 0.089(6) 0.042(4) -0.043(4) 0.009(3) -0.031(4) C49 0.040(4) 0.072(5) 0.038(3) -0.033(3) -0.004(3) -0.013(4) C50 0.035(4) 0.053(4) 0.030(3) -0.020(3) 0.003(3) -0.010(3) C51 0.059(5) 0.058(5) 0.075(5) -0.033(4) -0.017(4) -0.005(4) C52 0.110(7) 0.064(5) 0.054(4) -0.034(4) 0.007(4) -0.039(5) C53 0.086(6) 0.068(6) 0.056(5) 0.011(4) -0.036(4) -0.023(5) C54 0.098(7) 0.064(6) 0.073(5) -0.003(4) -0.045(5) 0.003(5) C55 0.079(6) 0.072(6) 0.060(5) -0.017(4) -0.041(4) 0.003(5) C56 0.058(5) 0.064(5) 0.042(4) -0.025(3) 0.000(3) -0.021(4) C57 0.058(5) 0.086(6) 0.048(4) 0.013(4) -0.013(4) -0.028(5) C58 0.050(5) 0.091(7) 0.083(6) 0.019(5) -0.031(4) -0.010(5) C61 0.033(3) 0.037(4) 0.030(3) 0.006(3) -0.010(3) -0.002(3) C62 0.035(4) 0.053(4) 0.027(3) 0.000(3) -0.010(3) -0.001(3) C63 0.035(4) 0.065(5) 0.028(3) 0.005(3) -0.010(3) -0.002(3) C64 0.047(4) 0.058(5) 0.046(4) 0.017(3) -0.021(3) -0.016(4) C65 0.055(4) 0.051(4) 0.040(4) -0.002(3) -0.018(3) -0.007(4) C66 0.041(4) 0.039(4) 0.030(3) -0.006(3) -0.012(3) -0.001(3) C67 0.040(4) 0.040(4) 0.036(3) -0.010(3) -0.005(3) 0.000(3) C68 0.036(3) 0.043(4) 0.022(3) -0.005(3) -0.008(2) -0.001(3) C69 0.050(4) 0.043(4) 0.034(3) -0.014(3) -0.008(3) -0.008(3) C70 0.049(4) 0.060(5) 0.041(4) -0.011(3) -0.018(3) -0.011(4) C71 0.044(4) 0.059(5) 0.042(4) -0.004(3) -0.014(3) -0.005(3) C72 0.035(3) 0.043(4) 0.028(3) -0.006(3) -0.009(3) 0.002(3) C73 0.030(3) 0.048(4) 0.022(3) -0.001(3) -0.008(2) -0.003(3) C74 0.037(4) 0.047(4) 0.027(3) -0.014(3) -0.003(3) -0.010(3) C75 0.042(4) 0.048(4) 0.026(3) -0.012(3) -0.005(3) -0.014(3) C76 0.046(4) 0.056(4) 0.034(3) -0.011(3) -0.012(3) -0.013(3) C77 0.042(4) 0.061(5) 0.031(3) 0.000(3) -0.013(3) -0.016(4) C78 0.041(4) 0.082(5) 0.024(3) -0.003(3) -0.008(3) -0.029(4) C79 0.032(3) 0.065(5) 0.029(3) -0.019(3) -0.006(3) -0.010(3) C80 0.040(4) 0.050(4) 0.026(3) -0.018(3) -0.005(3) -0.012(3) C81 0.090(7) 0.109(8) 0.076(6) -0.001(5) -0.019(5) -0.061(6) C82 0.075(6) 0.064(5) 0.050(4) 0.002(4) -0.007(4) -0.026(4) C83 0.049(5) 0.053(5) 0.084(5) -0.019(4) -0.013(4) -0.012(4) C84 0.114(9) 0.102(8) 0.079(7) 0.000(6) 0.036(6) 0.029(7) C85 0.064(6) 0.074(6) 0.108(7) -0.010(5) -0.031(5) 0.015(5) C86 0.106(8) 0.145(9) 0.036(4) -0.013(5) -0.016(5) -0.062(7) C87 0.134(10) 0.142(10) 0.058(5) 0.001(6) -0.053(6) -0.006(8) C88 0.238(19) 0.36(3) 0.095(9) -0.132(14) -0.051(11) 0.137(18) C91 0.060(10) 0.058(10) 0.054(9) -0.018(8) -0.029(8) 0.007(8) C92 0.095(13) 0.098(13) 0.022(6) -0.012(7) -0.008(7) -0.040(11) N1 0.038(3) 0.033(3) 0.037(3) 0.006(2) -0.013(2) 0.003(2) N2 0.041(3) 0.042(3) 0.035(3) -0.001(2) -0.002(2) 0.003(3) N3 0.031(3) 0.048(3) 0.030(2) -0.012(2) -0.013(2) -0.008(2) N4 0.037(3) 0.040(3) 0.031(2) -0.009(2) -0.016(2) -0.009(2) N5 0.033(3) 0.043(3) 0.025(2) -0.009(2) -0.003(2) 0.003(2) N6 0.026(3) 0.053(3) 0.023(2) -0.013(2) 0.0038(19) -0.009(2) O1 0.043(3) 0.041(3) 0.033(2) -0.0066(19) -0.0113(19) 0.002(2) O2 0.046(3) 0.037(3) 0.042(2) -0.006(2) -0.007(2) -0.003(2) O3 0.045(3) 0.045(3) 0.036(2) 0.000(2) -0.005(2) -0.003(2) O4 0.034(3) 0.059(3) 0.063(3) -0.025(2) -0.012(2) -0.001(2) O5 0.031(2) 0.046(3) 0.037(2) -0.014(2) -0.0035(18) -0.0088(19) O6 0.035(2) 0.053(3) 0.035(2) -0.013(2) -0.0162(18) -0.002(2) O7 0.077(4) 0.060(3) 0.031(2) -0.008(2) -0.025(2) 0.002(3) O8 0.047(3) 0.051(3) 0.041(2) -0.021(2) 0.004(2) -0.018(2) O9 0.040(2) 0.045(3) 0.029(2) -0.0129(19) -0.0012(18) -0.006(2) O10 0.030(2) 0.049(3) 0.036(2) -0.010(2) -0.0055(18) -0.001(2) O11 0.036(3) 0.052(3) 0.060(3) -0.009(2) -0.005(2) -0.002(2) O12 0.060(3) 0.069(3) 0.029(2) 0.000(2) -0.016(2) -0.018(3) O13 0.096(10) 0.177(16) 0.094(10) -0.059(10) -0.049(8) -0.022(10) Ti1 0.0326(6) 0.0413(7) 0.0311(6) -0.0040(5) -0.0061(5) -0.0032(5) Ti2 0.0396(7) 0.0421(7) 0.0232(5) -0.0068(5) -0.0095(5) -0.0039(5) Ti3 0.0328(6) 0.0467(7) 0.0300(5) -0.0071(5) -0.0075(5) -0.0026(5) _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 C1 O1 1.340(7) . ? C1 C2 1.409(8) . ? C1 C6 1.427(9) . ? C2 C3 1.382(10) . ? C2 H2 0.9500 . ? C3 C4 1.364(10) . ? C3 H3 0.9500 . ? C4 C5 1.390(9) . ? C4 C21 1.517(10) . ? C5 C6 1.381(9) . ? C5 H5 0.9500 . ? C6 C7 1.500(8) . ? C7 N1 1.493(8) . ? C7 H7A 0.9900 . ? C7 H7B 0.9900 . ? C8 N1 1.474(7) . ? C8 C13 1.507(9) . ? C8 C9 1.516(10) . ? C8 H8 1.0000 . ? C9 C10 1.513(11) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 C11 1.517(13) . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 C12 1.551(13) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 C13 1.527(9) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 N2 1.496(8) . ? C13 H13 1.0000 . ? C14 N2 1.472(8) . ? C14 C15 1.504(9) . ? C14 H14A 0.9900 . ? C14 H14B 0.9900 . ? C15 C20 1.386(9) . ? C15 C16 1.388(9) . ? C16 C17 1.384(10) . ? C16 H16 0.9500 . ? C17 C18 1.383(11) . ? C17 C22 1.535(11) . ? C18 C19 1.368(10) . ? C18 H18 0.9500 . ? C19 C20 1.389(9) . ? C19 H19 0.9500 . ? C20 O2 1.341(8) . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? C23 O3 1.421(7) . ? C23 C24 1.531(4) . ? C23 C25 1.532(5) . ? C23 H23 1.0000 . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C25 H25A 0.9800 . ? C25 H25B 0.9800 . ? C25 H25C 0.9800 . ? C26 O4 1.360(9) . ? C26 C27 1.528(5) . ? C26 C28 1.532(5) . ? C26 H26 1.0000 . ? C27 H27A 0.9800 . ? C27 H27B 0.9800 . ? C27 H27C 0.9800 . ? C28 H28A 0.9800 . ? C28 H28B 0.9800 . ? C28 H28C 0.9800 . ? C31 O5 1.332(7) . ? C31 C36 1.388(8) . ? C31 C32 1.401(8) . ? C32 C33 1.382(8) . ? C32 H32 0.9500 . ? C33 C34 1.378(9) . ? C33 H33 0.9500 . ? C34 C35 1.383(8) . ? C34 C51 1.516(9) . ? C35 C36 1.401(8) . ? C35 H35 0.9500 . ? C36 C37 1.505(8) . ? C37 N3 1.484(7) . ? C37 H37A 0.9900 . ? C37 H37B 0.9900 . ? C38 N3 1.485(7) . ? C38 C43 1.510(9) . ? C38 C39 1.539(8) . ? C38 H38 1.0000 . ? C39 C40 1.528(9) . ? C39 H39A 0.9900 . ? C39 H39B 0.9900 . ? C40 C41 1.498(10) . ? C40 H40A 0.9900 . ? C40 H40B 0.9900 . ? C41 C42 1.523(10) . ? C41 H41A 0.9900 . ? C41 H41B 0.9900 . ? C42 C43 1.528(8) . ? C42 H42A 0.9900 . ? C42 H42B 0.9900 . ? C43 N4 1.475(7) . ? C43 H43 1.0000 . ? C44 N4 1.475(7) . ? C44 C45 1.506(8) . ? C44 H44A 0.9900 . ? C44 H44B 0.9900 . ? C45 C46 1.389(8) . ? C45 C50 1.412(8) . ? C46 C47 1.380(9) . ? C46 H46 0.9500 . ? C47 C48 1.393(10) . ? C47 C52 1.518(10) . ? C48 C49 1.379(10) . ? C48 H48 0.9500 . ? C49 C50 1.396(8) . ? C49 H49 0.9500 . ? C50 O6 1.350(7) . ? C51 H51A 0.9800 . ? C51 H51B 0.9800 . ? C51 H51C 0.9800 . ? C52 H52A 0.9800 . ? C52 H52B 0.9800 . ? C52 H52C 0.9800 . ? C53 O7 1.397(7) . ? C53 C55 1.522(5) . ? C53 C54 1.526(5) . ? C53 H53 1.0000 . ? C54 H54A 0.9800 . ? C54 H54B 0.9800 . ? C54 H54C 0.9800 . ? C55 H55A 0.9800 . ? C55 H55B 0.9800 . ? C55 H55C 0.9800 . ? C56 O8 1.413(7) . ? C56 C57 1.531(4) . ? C56 C58 1.532(5) . ? C56 H56 1.0000 . ? C57 H57A 0.9800 . ? C57 H57B 0.9800 . ? C57 H57C 0.9800 . ? C58 H58A 0.9800 . ? C58 H58B 0.9800 . ? C58 H58C 0.9800 . ? C61 O9 1.337(7) . ? C61 C66 1.399(8) . ? C61 C62 1.405(8) . ? C62 C63 1.371(9) . ? C62 H62 0.9500 . ? C63 C64 1.385(10) . ? C63 H63 0.9500 . ? C64 C65 1.404(9) . ? C64 C81 1.516(10) . ? C65 C66 1.394(9) . ? C65 H65 0.9500 . ? C66 C67 1.502(8) . ? C67 N5 1.483(7) . ? C67 H67A 0.9900 . ? C67 H67B 0.9900 . ? C68 N5 1.477(7) . ? C68 C69 1.512(8) . ? C68 C73 1.517(8) . ? C68 H68 1.0000 . ? C69 C70 1.519(9) . ? C69 H69A 0.9900 . ? C69 H69B 0.9900 . ? C70 C71 1.521(9) . ? C70 H70A 0.9900 . ? C70 H70B 0.9900 . ? C71 C72 1.531(8) . ? C71 H71A 0.9900 . ? C71 H71B 0.9900 . ? C72 C73 1.530(8) . ? C72 H72A 0.9900 . ? C72 H72B 0.9900 . ? C73 N6 1.496(7) . ? C73 H73 1.0000 . ? C74 N6 1.493(7) . ? C74 C75 1.506(8) . ? C74 H74A 0.9900 . ? C74 H74B 0.9900 . ? C75 C76 1.373(8) . ? C75 C80 1.425(8) . ? C76 C77 1.388(8) . ? C76 H76 0.9500 . ? C77 C78 1.406(9) . ? C77 C82 1.519(9) . ? C78 C79 1.374(9) . ? C78 H78 0.9500 . ? C79 C80 1.394(8) . ? C79 H79 0.9500 . ? C80 O10 1.319(7) . ? C81 H81A 0.9800 . ? C81 H81B 0.9800 . ? C81 H81C 0.9800 . ? C82 H82A 0.9800 . ? C82 H82B 0.9800 . ? C82 H82C 0.9800 . ? C83 O11 1.390(8) . ? C83 C84 1.534(5) . ? C83 C85 1.536(5) . ? C83 H83 1.0000 . ? C84 H84A 0.9800 . ? C84 H84B 0.9800 . ? C84 H84C 0.9800 . ? C85 H85A 0.9800 . ? C85 H85B 0.9800 . ? C85 H85C 0.9800 . ? C86 O12 1.398(8) . ? C86 C88 1.531(5) . ? C86 C87 1.534(5) . ? C86 H86 1.0000 . ? C87 H87A 0.9800 . ? C87 H87B 0.9800 . ? C87 H87C 0.9800 . ? C88 H88A 0.9800 . ? C88 H88B 0.9800 . ? C88 H88C 0.9800 . ? C91 O13 1.341(5) . ? C91 C92 1.529(5) . ? C91 H91A 0.9900 . ? C91 H91B 0.9900 . ? C92 H92A 0.9800 . ? C92 H92B 0.9800 . ? C92 H92C 0.9800 . ? C93 O13 1.332(5) . ? C93 C94 1.531(5) . ? C93 H93A 0.9900 . ? C93 H93B 0.9900 . ? C94 H94A 0.9800 . ? C94 H94B 0.9800 . ? C94 H94C 0.9800 . ? N1 Ti1 2.274(5) . ? N1 H1 0.9300 . ? N2 Ti1 2.256(5) . ? N2 H2A 0.9300 . ? N3 Ti2 2.256(5) . ? N3 H3A 0.9300 . ? N4 Ti2 2.276(4) . ? N4 H4 0.9300 . ? N5 Ti3 2.289(5) . ? N5 H5A 0.9300 . ? N6 Ti3 2.264(5) . ? N6 H6 0.9300 . ? O1 Ti1 1.909(4) . ? O2 Ti1 1.908(4) . ? O3 Ti1 1.810(4) . ? O4 Ti1 1.805(4) . ? O5 Ti2 1.932(4) . ? O6 Ti2 1.926(4) . ? O7 Ti2 1.799(4) . ? O8 Ti2 1.806(4) . ? O9 Ti3 1.927(4) . ? O10 Ti3 1.920(4) . ? O11 Ti3 1.812(5) . ? O12 Ti3 1.814(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 O1 C1 C2 120.4(6) . . ? O1 C1 C6 122.8(5) . . ? C2 C1 C6 116.7(6) . . ? C3 C2 C1 121.3(7) . . ? C3 C2 H2 119.3 . . ? C1 C2 H2 119.3 . . ? C4 C3 C2 122.1(7) . . ? C4 C3 H3 119.0 . . ? C2 C3 H3 119.0 . . ? C3 C4 C5 117.4(7) . . ? C3 C4 C21 122.1(7) . . ? C5 C4 C21 120.5(7) . . ? C6 C5 C4 123.1(7) . . ? C6 C5 H5 118.4 . . ? C4 C5 H5 118.4 . . ? C5 C6 C1 119.3(6) . . ? C5 C6 C7 120.3(6) . . ? C1 C6 C7 120.2(6) . . ? N1 C7 C6 111.8(5) . . ? N1 C7 H7A 109.3 . . ? C6 C7 H7A 109.3 . . ? N1 C7 H7B 109.3 . . ? C6 C7 H7B 109.3 . . ? H7A C7 H7B 107.9 . . ? N1 C8 C13 107.0(5) . . ? N1 C8 C9 113.8(6) . . ? C13 C8 C9 112.3(6) . . ? N1 C8 H8 107.8 . . ? C13 C8 H8 107.8 . . ? C9 C8 H8 107.8 . . ? C10 C9 C8 111.3(8) . . ? C10 C9 H9A 109.4 . . ? C8 C9 H9A 109.4 . . ? C10 C9 H9B 109.4 . . ? C8 C9 H9B 109.4 . . ? H9A C9 H9B 108.0 . . ? C9 C10 C11 109.8(7) . . ? C9 C10 H10A 109.7 . . ? C11 C10 H10A 109.7 . . ? C9 C10 H10B 109.7 . . ? C11 C10 H10B 109.7 . . ? H10A C10 H10B 108.2 . . ? C10 C11 C12 110.4(7) . . ? C10 C11 H11A 109.6 . . ? C12 C11 H11A 109.6 . . ? C10 C11 H11B 109.6 . . ? C12 C11 H11B 109.6 . . ? H11A C11 H11B 108.1 . . ? C13 C12 C11 110.3(8) . . ? C13 C12 H12A 109.6 . . ? C11 C12 H12A 109.6 . . ? C13 C12 H12B 109.6 . . ? C11 C12 H12B 109.6 . . ? H12A C12 H12B 108.1 . . ? N2 C13 C8 107.9(5) . . ? N2 C13 C12 113.3(6) . . ? C8 C13 C12 111.9(6) . . ? N2 C13 H13 107.9 . . ? C8 C13 H13 107.9 . . ? C12 C13 H13 107.9 . . ? N2 C14 C15 112.1(5) . . ? N2 C14 H14A 109.2 . . ? C15 C14 H14A 109.2 . . ? N2 C14 H14B 109.2 . . ? C15 C14 H14B 109.2 . . ? H14A C14 H14B 107.9 . . ? C20 C15 C16 119.0(7) . . ? C20 C15 C14 122.4(6) . . ? C16 C15 C14 118.6(6) . . ? C17 C16 C15 123.9(8) . . ? C17 C16 H16 118.0 . . ? C15 C16 H16 118.0 . . ? C18 C17 C16 115.0(7) . . ? C18 C17 C22 122.3(8) . . ? C16 C17 C22 122.7(9) . . ? C19 C18 C17 123.1(7) . . ? C19 C18 H18 118.4 . . ? C17 C18 H18 118.4 . . ? C18 C19 C20 120.7(7) . . ? C18 C19 H19 119.7 . . ? C20 C19 H19 119.7 . . ? O2 C20 C15 121.9(6) . . ? O2 C20 C19 119.8(6) . . ? C15 C20 C19 118.3(7) . . ? C4 C21 H21A 109.5 . . ? C4 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C4 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C17 C22 H22A 109.5 . . ? C17 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C17 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? O3 C23 C24 109.8(5) . . ? O3 C23 C25 108.4(5) . . ? C24 C23 C25 111.0(6) . . ? O3 C23 H23 109.2 . . ? C24 C23 H23 109.2 . . ? C25 C23 H23 109.2 . . ? C23 C24 H24A 109.5 . . ? C23 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C23 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C23 C25 H25A 109.5 . . ? C23 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? C23 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? O4 C26 C27 115.7(8) . . ? O4 C26 C28 108.2(8) . . ? C27 C26 C28 112.1(10) . . ? O4 C26 H26 106.8 . . ? C27 C26 H26 106.8 . . ? C28 C26 H26 106.8 . . ? C26 C27 H27A 109.5 . . ? C26 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C26 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C26 C28 H28A 109.5 . . ? C26 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C26 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? O5 C31 C36 123.7(5) . . ? O5 C31 C32 118.3(5) . . ? C36 C31 C32 117.9(6) . . ? C33 C32 C31 120.7(6) . . ? C33 C32 H32 119.7 . . ? C31 C32 H32 119.7 . . ? C34 C33 C32 122.0(6) . . ? C34 C33 H33 119.0 . . ? C32 C33 H33 119.0 . . ? C33 C34 C35 117.3(6) . . ? C33 C34 C51 122.3(6) . . ? C35 C34 C51 120.4(6) . . ? C34 C35 C36 121.9(6) . . ? C34 C35 H35 119.0 . . ? C36 C35 H35 119.0 . . ? C31 C36 C35 120.0(6) . . ? C31 C36 C37 121.6(5) . . ? C35 C36 C37 118.3(6) . . ? N3 C37 C36 113.4(5) . . ? N3 C37 H37A 108.9 . . ? C36 C37 H37A 108.9 . . ? N3 C37 H37B 108.9 . . ? C36 C37 H37B 108.9 . . ? H37A C37 H37B 107.7 . . ? N3 C38 C43 107.5(4) . . ? N3 C38 C39 112.7(5) . . ? C43 C38 C39 112.1(5) . . ? N3 C38 H38 108.1 . . ? C43 C38 H38 108.1 . . ? C39 C38 H38 108.1 . . ? C40 C39 C38 111.1(6) . . ? C40 C39 H39A 109.4 . . ? C38 C39 H39A 109.4 . . ? C40 C39 H39B 109.4 . . ? C38 C39 H39B 109.4 . . ? H39A C39 H39B 108.0 . . ? C41 C40 C39 111.3(5) . . ? C41 C40 H40A 109.4 . . ? C39 C40 H40A 109.4 . . ? C41 C40 H40B 109.4 . . ? C39 C40 H40B 109.4 . . ? H40A C40 H40B 108.0 . . ? C40 C41 C42 111.5(6) . . ? C40 C41 H41A 109.3 . . ? C42 C41 H41A 109.3 . . ? C40 C41 H41B 109.3 . . ? C42 C41 H41B 109.3 . . ? H41A C41 H41B 108.0 . . ? C41 C42 C43 110.5(6) . . ? C41 C42 H42A 109.5 . . ? C43 C42 H42A 109.5 . . ? C41 C42 H42B 109.5 . . ? C43 C42 H42B 109.5 . . ? H42A C42 H42B 108.1 . . ? N4 C43 C38 108.0(5) . . ? N4 C43 C42 115.0(5) . . ? C38 C43 C42 112.1(5) . . ? N4 C43 H43 107.1 . . ? C38 C43 H43 107.1 . . ? C42 C43 H43 107.1 . . ? N4 C44 C45 112.5(5) . . ? N4 C44 H44A 109.1 . . ? C45 C44 H44A 109.1 . . ? N4 C44 H44B 109.1 . . ? C45 C44 H44B 109.1 . . ? H44A C44 H44B 107.8 . . ? C46 C45 C50 118.3(6) . . ? C46 C45 C44 119.9(6) . . ? C50 C45 C44 121.8(6) . . ? C47 C46 C45 123.0(7) . . ? C47 C46 H46 118.5 . . ? C45 C46 H46 118.5 . . ? C46 C47 C48 117.7(6) . . ? C46 C47 C52 121.5(7) . . ? C48 C47 C52 120.9(7) . . ? C49 C48 C47 121.4(6) . . ? C49 C48 H48 119.3 . . ? C47 C48 H48 119.3 . . ? C48 C49 C50 120.4(7) . . ? C48 C49 H49 119.8 . . ? C50 C49 H49 119.8 . . ? O6 C50 C49 118.4(6) . . ? O6 C50 C45 122.4(5) . . ? C49 C50 C45 119.2(6) . . ? C34 C51 H51A 109.5 . . ? C34 C51 H51B 109.5 . . ? H51A C51 H51B 109.5 . . ? C34 C51 H51C 109.5 . . ? H51A C51 H51C 109.5 . . ? H51B C51 H51C 109.5 . . ? C47 C52 H52A 109.5 . . ? C47 C52 H52B 109.5 . . ? H52A C52 H52B 109.5 . . ? C47 C52 H52C 109.5 . . ? H52A C52 H52C 109.5 . . ? H52B C52 H52C 109.5 . . ? O7 C53 C55 111.9(6) . . ? O7 C53 C54 108.9(6) . . ? C55 C53 C54 115.7(6) . . ? O7 C53 H53 106.6 . . ? C55 C53 H53 106.6 . . ? C54 C53 H53 106.6 . . ? C53 C54 H54A 109.5 . . ? C53 C54 H54B 109.5 . . ? H54A C54 H54B 109.5 . . ? C53 C54 H54C 109.5 . . ? H54A C54 H54C 109.5 . . ? H54B C54 H54C 109.5 . . ? C53 C55 H55A 109.5 . . ? C53 C55 H55B 109.5 . . ? H55A C55 H55B 109.5 . . ? C53 C55 H55C 109.5 . . ? H55A C55 H55C 109.5 . . ? H55B C55 H55C 109.5 . . ? O8 C56 C57 109.6(5) . . ? O8 C56 C58 110.0(5) . . ? C57 C56 C58 109.5(6) . . ? O8 C56 H56 109.3 . . ? C57 C56 H56 109.3 . . ? C58 C56 H56 109.3 . . ? C56 C57 H57A 109.5 . . ? C56 C57 H57B 109.5 . . ? H57A C57 H57B 109.5 . . ? C56 C57 H57C 109.5 . . ? H57A C57 H57C 109.5 . . ? H57B C57 H57C 109.5 . . ? C56 C58 H58A 109.5 . . ? C56 C58 H58B 109.5 . . ? H58A C58 H58B 109.5 . . ? C56 C58 H58C 109.5 . . ? H58A C58 H58C 109.5 . . ? H58B C58 H58C 109.5 . . ? O9 C61 C66 122.3(5) . . ? O9 C61 C62 118.7(6) . . ? C66 C61 C62 118.9(6) . . ? C63 C62 C61 121.5(6) . . ? C63 C62 H62 119.2 . . ? C61 C62 H62 119.2 . . ? C62 C63 C64 120.7(6) . . ? C62 C63 H63 119.7 . . ? C64 C63 H63 119.7 . . ? C63 C64 C65 118.0(7) . . ? C63 C64 C81 121.6(7) . . ? C65 C64 C81 120.4(7) . . ? C66 C65 C64 122.3(6) . . ? C66 C65 H65 118.9 . . ? C64 C65 H65 118.9 . . ? C65 C66 C61 118.6(6) . . ? C65 C66 C67 120.0(6) . . ? C61 C66 C67 121.5(6) . . ? N5 C67 C66 111.3(5) . . ? N5 C67 H67A 109.4 . . ? C66 C67 H67A 109.4 . . ? N5 C67 H67B 109.4 . . ? C66 C67 H67B 109.4 . . ? H67A C67 H67B 108.0 . . ? N5 C68 C69 114.3(5) . . ? N5 C68 C73 107.6(5) . . ? C69 C68 C73 111.6(5) . . ? N5 C68 H68 107.7 . . ? C69 C68 H68 107.7 . . ? C73 C68 H68 107.7 . . ? C68 C69 C70 111.2(5) . . ? C68 C69 H69A 109.4 . . ? C70 C69 H69A 109.4 . . ? C68 C69 H69B 109.4 . . ? C70 C69 H69B 109.4 . . ? H69A C69 H69B 108.0 . . ? C69 C70 C71 110.9(6) . . ? C69 C70 H70A 109.5 . . ? C71 C70 H70A 109.5 . . ? C69 C70 H70B 109.5 . . ? C71 C70 H70B 109.5 . . ? H70A C70 H70B 108.0 . . ? C70 C71 C72 110.6(5) . . ? C70 C71 H71A 109.5 . . ? C72 C71 H71A 109.5 . . ? C70 C71 H71B 109.5 . . ? C72 C71 H71B 109.5 . . ? H71A C71 H71B 108.1 . . ? C73 C72 C71 111.5(5) . . ? C73 C72 H72A 109.3 . . ? C71 C72 H72A 109.3 . . ? C73 C72 H72B 109.3 . . ? C71 C72 H72B 109.3 . . ? H72A C72 H72B 108.0 . . ? N6 C73 C68 107.4(4) . . ? N6 C73 C72 112.6(5) . . ? C68 C73 C72 111.3(5) . . ? N6 C73 H73 108.5 . . ? C68 C73 H73 108.5 . . ? C72 C73 H73 108.5 . . ? N6 C74 C75 111.1(4) . . ? N6 C74 H74A 109.4 . . ? C75 C74 H74A 109.4 . . ? N6 C74 H74B 109.4 . . ? C75 C74 H74B 109.4 . . ? H74A C74 H74B 108.0 . . ? C76 C75 C80 119.6(6) . . ? C76 C75 C74 120.0(6) . . ? C80 C75 C74 120.4(5) . . ? C75 C76 C77 123.5(7) . . ? C75 C76 H76 118.3 . . ? C77 C76 H76 118.3 . . ? C76 C77 C78 116.7(6) . . ? C76 C77 C82 121.8(7) . . ? C78 C77 C82 121.5(6) . . ? C79 C78 C77 120.9(6) . . ? C79 C78 H78 119.5 . . ? C77 C78 H78 119.5 . . ? C78 C79 C80 122.4(6) . . ? C78 C79 H79 118.8 . . ? C80 C79 H79 118.8 . . ? O10 C80 C79 120.9(6) . . ? O10 C80 C75 122.1(5) . . ? C79 C80 C75 117.0(6) . . ? C64 C81 H81A 109.5 . . ? C64 C81 H81B 109.5 . . ? H81A C81 H81B 109.5 . . ? C64 C81 H81C 109.5 . . ? H81A C81 H81C 109.5 . . ? H81B C81 H81C 109.5 . . ? C77 C82 H82A 109.5 . . ? C77 C82 H82B 109.5 . . ? H82A C82 H82B 109.5 . . ? C77 C82 H82C 109.5 . . ? H82A C82 H82C 109.5 . . ? H82B C82 H82C 109.5 . . ? O11 C83 C84 109.7(6) . . ? O11 C83 C85 108.8(6) . . ? C84 C83 C85 112.0(7) . . ? O11 C83 H83 108.8 . . ? C84 C83 H83 108.8 . . ? C85 C83 H83 108.8 . . ? C83 C84 H84A 109.5 . . ? C83 C84 H84B 109.5 . . ? H84A C84 H84B 109.5 . . ? C83 C84 H84C 109.5 . . ? H84A C84 H84C 109.5 . . ? H84B C84 H84C 109.5 . . ? C83 C85 H85A 109.5 . . ? C83 C85 H85B 109.5 . . ? H85A C85 H85B 109.5 . . ? C83 C85 H85C 109.5 . . ? H85A C85 H85C 109.5 . . ? H85B C85 H85C 109.5 . . ? O12 C86 C88 107.2(7) . . ? O12 C86 C87 107.4(6) . . ? C88 C86 C87 111.6(9) . . ? O12 C86 H86 110.2 . . ? C88 C86 H86 110.2 . . ? C87 C86 H86 110.2 . . ? C86 C87 H87A 109.5 . . ? C86 C87 H87B 109.5 . . ? H87A C87 H87B 109.5 . . ? C86 C87 H87C 109.5 . . ? H87A C87 H87C 109.5 . . ? H87B C87 H87C 109.5 . . ? C86 C88 H88A 109.5 . . ? C86 C88 H88B 109.5 . . ? H88A C88 H88B 109.5 . . ? C86 C88 H88C 109.5 . . ? H88A C88 H88C 109.5 . . ? H88B C88 H88C 109.5 . . ? O13 C91 C92 115.5(13) . . ? O13 C91 H91A 108.4 . . ? C92 C91 H91A 108.4 . . ? O13 C91 H91B 108.4 . . ? C92 C91 H91B 108.4 . . ? H91A C91 H91B 107.5 . . ? C91 C92 H92A 109.5 . . ? C91 C92 H92B 109.5 . . ? H92A C92 H92B 109.5 . . ? C91 C92 H92C 109.5 . . ? H92A C92 H92C 109.5 . . ? H92B C92 H92C 109.5 . . ? O13 C93 C94 115.0(15) . . ? O13 C93 H93A 108.5 . . ? C94 C93 H93A 108.5 . . ? O13 C93 H93B 108.5 . . ? C94 C93 H93B 108.5 . . ? H93A C93 H93B 107.5 . . ? C93 C94 H94A 109.5 . . ? C93 C94 H94B 109.5 . . ? H94A C94 H94B 109.5 . . ? C93 C94 H94C 109.5 . . ? H94A C94 H94C 109.5 . . ? H94B C94 H94C 109.5 . . ? C8 N1 C7 113.7(5) . . ? C8 N1 Ti1 112.6(4) . . ? C7 N1 Ti1 111.3(4) . . ? C8 N1 H1 106.2 . . ? C7 N1 H1 106.2 . . ? Ti1 N1 H1 106.2 . . ? C14 N2 C13 114.3(5) . . ? C14 N2 Ti1 110.9(4) . . ? C13 N2 Ti1 111.9(4) . . ? C14 N2 H2A 106.3 . . ? C13 N2 H2A 106.3 . . ? Ti1 N2 H2A 106.3 . . ? C37 N3 C38 113.6(4) . . ? C37 N3 Ti2 111.5(3) . . ? C38 N3 Ti2 113.6(4) . . ? C37 N3 H3A 105.7 . . ? C38 N3 H3A 105.7 . . ? Ti2 N3 H3A 105.7 . . ? C43 N4 C44 114.7(5) . . ? C43 N4 Ti2 111.1(3) . . ? C44 N4 Ti2 110.5(3) . . ? C43 N4 H4 106.7 . . ? C44 N4 H4 106.7 . . ? Ti2 N4 H4 106.7 . . ? C68 N5 C67 114.2(5) . . ? C68 N5 Ti3 112.6(3) . . ? C67 N5 Ti3 110.7(3) . . ? C68 N5 H5A 106.3 . . ? C67 N5 H5A 106.3 . . ? Ti3 N5 H5A 106.3 . . ? C74 N6 C73 113.5(4) . . ? C74 N6 Ti3 111.8(3) . . ? C73 N6 Ti3 112.4(3) . . ? C74 N6 H6 106.2 . . ? C73 N6 H6 106.2 . . ? Ti3 N6 H6 106.2 . . ? C1 O1 Ti1 138.7(4) . . ? C20 O2 Ti1 137.5(4) . . ? C23 O3 Ti1 136.2(4) . . ? C26 O4 Ti1 140.1(5) . . ? C31 O5 Ti2 135.8(4) . . ? C50 O6 Ti2 136.4(4) . . ? C53 O7 Ti2 141.7(5) . . ? C56 O8 Ti2 138.6(4) . . ? C61 O9 Ti3 138.8(4) . . ? C80 O10 Ti3 140.1(4) . . ? C83 O11 Ti3 140.8(4) . . ? C86 O12 Ti3 132.2(5) . . ? C93 O13 C91 114.6(13) . . ? O4 Ti1 O3 105.3(2) . . ? O4 Ti1 O2 98.3(2) . . ? O3 Ti1 O2 91.37(18) . . ? O4 Ti1 O1 92.3(2) . . ? O3 Ti1 O1 96.96(18) . . ? O2 Ti1 O1 164.28(19) . . ? O4 Ti1 N2 89.0(2) . . ? O3 Ti1 N2 164.2(2) . . ? O2 Ti1 N2 79.68(18) . . ? O1 Ti1 N2 89.02(18) . . ? O4 Ti1 N1 161.87(19) . . ? O3 Ti1 N1 92.02(19) . . ? O2 Ti1 N1 86.40(18) . . ? O1 Ti1 N1 80.03(18) . . ? N2 Ti1 N1 74.56(19) . . ? O7 Ti2 O8 105.7(2) . . ? O7 Ti2 O6 93.6(2) . . ? O8 Ti2 O6 96.58(18) . . ? O7 Ti2 O5 99.0(2) . . ? O8 Ti2 O5 92.16(18) . . ? O6 Ti2 O5 162.13(17) . . ? O7 Ti2 N3 88.23(19) . . ? O8 Ti2 N3 165.16(18) . . ? O6 Ti2 N3 87.37(17) . . ? O5 Ti2 N3 80.45(17) . . ? O7 Ti2 N4 161.4(2) . . ? O8 Ti2 N4 92.17(19) . . ? O6 Ti2 N4 79.17(17) . . ? O5 Ti2 N4 84.96(17) . . ? N3 Ti2 N4 74.47(17) . . ? O11 Ti3 O12 105.4(2) . . ? O11 Ti3 O10 93.17(19) . . ? O12 Ti3 O10 96.50(19) . . ? O11 Ti3 O9 97.55(19) . . ? O12 Ti3 O9 90.40(18) . . ? O10 Ti3 O9 165.25(18) . . ? O11 Ti3 N6 161.91(19) . . ? O12 Ti3 N6 91.94(19) . . ? O10 Ti3 N6 79.63(17) . . ? O9 Ti3 N6 87.14(17) . . ? O11 Ti3 N5 89.27(19) . . ? O12 Ti3 N5 163.2(2) . . ? O10 Ti3 N5 90.62(17) . . ? O9 Ti3 N5 79.46(17) . . ? N6 Ti3 N5 74.36(17) . . ? _diffrn_measured_fraction_theta_max 0.974 _diffrn_reflns_theta_full 27.00 _diffrn_measured_fraction_theta_full 0.974 _refine_diff_density_max 1.031 _refine_diff_density_min -0.708 _refine_diff_density_rms 0.089 #===END data_sslambdaL5Ti(OiPr)2 _database_code_depnum_ccdc_archive 'CCDC 738410' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C28 H42 N2 O4 Ti' _chemical_formula_sum 'C28 H42 N2 O4 Ti' _chemical_formula_weight 518.54 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 Tetragonal _symmetry_space_group_name_H-M P4(3)2(1)2 _symmetry_space_group_name_Hall 'P 4nw 2abw' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-y+1/2, x+1/2, z+3/4' 'y+1/2, -x+1/2, z+1/4' '-x+1/2, y+1/2, -z+3/4' 'x+1/2, -y+1/2, -z+1/4' 'y, x, -z' '-y, -x, -z+1/2' _cell_length_a 10.0092(4) _cell_length_b 10.0092(4) _cell_length_c 28.225(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2827.7(3) _cell_formula_units_Z 4 _cell_measurement_temperature 173(1) _cell_measurement_reflns_used 9814 _cell_measurement_theta_min 2.16 _cell_measurement_theta_max 27.93 _exptl_crystal_description shapeless _exptl_crystal_colour colorless _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.36 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.218 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1112 _exptl_absorpt_coefficient_mu 0.336 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(1) _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 30643 _diffrn_reflns_av_R_equivalents 0.0310 _diffrn_reflns_av_sigmaI/netI 0.0174 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -35 _diffrn_reflns_limit_l_max 35 _diffrn_reflns_theta_min 2.16 _diffrn_reflns_theta_max 26.99 _reflns_number_total 3089 _reflns_number_gt 2791 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.1709P)^2^+1.3157P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _chemical_absolute_configuration ad _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.05(7) _refine_ls_number_reflns 3089 _refine_ls_number_parameters 165 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0940 _refine_ls_R_factor_gt 0.0879 _refine_ls_wR_factor_ref 0.2614 _refine_ls_wR_factor_gt 0.2533 _refine_ls_goodness_of_fit_ref 1.082 _refine_ls_restrained_S_all 1.093 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.001 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 C1 C 0.4597(5) 0.1488(4) 0.06771(15) 0.0669(12) Uani 1 1 d . . . C2 C 0.5600(7) 0.0530(5) 0.0758(2) 0.0855(19) Uani 1 1 d . . . H2 H 0.6282 0.0402 0.0528 0.103 Uiso 1 1 calc R . . C3 C 0.5606(9) -0.0224(5) 0.1165(2) 0.109(3) Uani 1 1 d . . . H3 H 0.6293 -0.0866 0.1211 0.130 Uiso 1 1 calc R . . C4 C 0.4642(10) -0.0071(6) 0.1508(2) 0.105(3) Uani 1 1 d . . . C5 C 0.3617(10) 0.0849(5) 0.14285(18) 0.100(2) Uani 1 1 d . . . H5 H 0.2927 0.0946 0.1657 0.120 Uiso 1 1 calc R . . C6 C 0.3594(7) 0.1629(4) 0.10186(17) 0.0777(15) Uani 1 1 d . . . C7 C 0.4655(15) -0.0909(8) 0.1960(2) 0.158(5) Uani 1 1 d . . . H7A H 0.5264 -0.1667 0.1920 0.237 Uiso 1 1 calc R . . H7B H 0.3752 -0.1241 0.2025 0.237 Uiso 1 1 calc R . . H7C H 0.4957 -0.0357 0.2226 0.237 Uiso 1 1 calc R . . C8 C 0.2445(7) 0.2620(4) 0.09572(18) 0.0828(16) Uani 1 1 d . . . H8A H 0.1681 0.2335 0.1156 0.099 Uiso 1 1 calc R . . H8B H 0.2736 0.3513 0.1068 0.099 Uiso 1 1 calc R . . C9 C 0.1492(4) 0.1417(4) 0.0270(2) 0.0755(13) Uani 1 1 d . . . H9 H 0.2151 0.0706 0.0356 0.091 Uiso 1 1 calc R . . C10 C 0.0160(6) 0.1019(6) 0.0468(3) 0.117(3) Uani 1 1 d . . . H10A H -0.0506 0.1716 0.0389 0.141 Uiso 1 1 calc R . . H10B H 0.0223 0.0963 0.0817 0.141 Uiso 1 1 calc R . . C11 C -0.0315(7) -0.0317(7) 0.0274(4) 0.154(5) Uani 1 1 d . . . H11A H -0.1229 -0.0501 0.0391 0.185 Uiso 1 1 calc R . . H11B H 0.0279 -0.1037 0.0391 0.185 Uiso 1 1 calc R . . C12 C 0.4231(10) 0.6087(6) 0.0529(4) 0.145(4) Uani 1 1 d D . . H12 H 0.3679 0.6061 0.0825 0.174 Uiso 1 1 calc R . . C13 C 0.5480(13) 0.6341(10) 0.0825(6) 0.236(10) Uani 1 1 d D . . H13A H 0.5228 0.6763 0.1125 0.354 Uiso 1 1 calc R . . H13B H 0.6085 0.6934 0.0650 0.354 Uiso 1 1 calc R . . H13C H 0.5931 0.5491 0.0889 0.354 Uiso 1 1 calc R . . C14 C 0.3476(12) 0.7297(6) 0.0364(5) 0.182(6) Uani 1 1 d D . . H14A H 0.2598 0.7025 0.0246 0.273 Uiso 1 1 calc R . . H14B H 0.3977 0.7738 0.0110 0.273 Uiso 1 1 calc R . . H14C H 0.3362 0.7918 0.0630 0.273 Uiso 1 1 calc R . . N1 N 0.2006(4) 0.2716(3) 0.04546(16) 0.0682(11) Uani 1 1 d . . . H1N H 0.142(6) 0.340(6) 0.0476(18) 0.082 Uiso 1 1 d . . . O1 O 0.4624(3) 0.2187(4) 0.02852(11) 0.0681(9) Uani 1 1 d . . . O2 O 0.3925(5) 0.4887(4) 0.04439(13) 0.0874(13) Uani 1 1 d . . . Ti1 Ti 0.36169(7) 0.36169(7) 0.0000 0.0596(4) Uani 1 2 d S . . 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 C1 0.091(3) 0.047(2) 0.063(2) -0.0153(18) -0.025(2) 0.009(2) C2 0.107(4) 0.066(3) 0.084(3) -0.021(2) -0.056(3) 0.010(3) C3 0.152(7) 0.049(3) 0.125(5) -0.015(3) -0.088(5) 0.005(3) C4 0.180(8) 0.053(3) 0.080(3) 0.010(3) -0.045(4) -0.026(4) C5 0.189(7) 0.045(2) 0.065(3) -0.001(2) -0.006(4) -0.019(4) C6 0.134(5) 0.0364(18) 0.063(2) -0.0028(16) -0.005(3) -0.001(2) C7 0.296(15) 0.077(4) 0.101(5) 0.029(4) -0.078(7) -0.029(7) C8 0.130(5) 0.040(2) 0.078(3) -0.001(2) 0.031(3) 0.007(2) C9 0.056(2) 0.0359(18) 0.134(4) 0.006(2) 0.011(3) 0.0010(17) C10 0.074(4) 0.057(3) 0.221(9) 0.031(4) 0.047(5) -0.002(2) C11 0.057(3) 0.062(4) 0.344(17) 0.055(8) 0.001(7) -0.015(2) C12 0.173(9) 0.063(4) 0.199(10) -0.017(5) -0.069(8) 0.007(4) C13 0.257(16) 0.102(7) 0.349(19) -0.059(9) -0.210(16) 0.059(9) C14 0.202(12) 0.073(4) 0.270(13) 0.041(6) -0.130(11) -0.042(6) N1 0.067(2) 0.0353(15) 0.102(3) 0.0079(17) 0.021(2) 0.0051(14) O1 0.0623(18) 0.074(2) 0.0681(17) 0.0009(15) -0.0130(14) 0.0087(15) O2 0.120(3) 0.0604(19) 0.082(2) 0.0101(17) -0.027(2) -0.028(2) Ti1 0.0566(4) 0.0566(4) 0.0655(6) 0.0096(4) -0.0096(4) -0.0134(5) _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 C1 O1 1.309(6) . ? C1 C6 1.399(8) . ? C1 C2 1.407(7) . ? C2 C3 1.375(8) . ? C2 H2 0.9500 . ? C3 C4 1.375(12) . ? C3 H3 0.9500 . ? C4 C5 1.396(12) . ? C4 C7 1.528(8) . ? C5 C6 1.396(7) . ? C5 H5 0.9500 . ? C6 C8 1.529(9) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 N1 1.488(7) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 N1 1.493(6) . ? C9 C10 1.498(7) . ? C9 C9 1.530(12) 7 ? C9 H9 1.0000 . ? C10 C11 1.521(11) . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 C11 1.55(2) 7 ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 O2 1.262(7) . ? C12 C14 1.501(5) . ? C12 C13 1.525(5) . ? C12 H12 1.0000 . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? N1 Ti1 2.249(4) . ? N1 H1N 0.90(6) . ? O1 Ti1 1.927(3) . ? O2 Ti1 1.811(4) . ? Ti1 O2 1.811(4) 7 ? Ti1 O1 1.927(3) 7 ? Ti1 N1 2.249(4) 7 ? 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 O1 C1 C6 122.9(4) . . ? O1 C1 C2 119.1(5) . . ? C6 C1 C2 117.9(5) . . ? C3 C2 C1 120.9(7) . . ? C3 C2 H2 119.6 . . ? C1 C2 H2 119.6 . . ? C4 C3 C2 121.6(6) . . ? C4 C3 H3 119.2 . . ? C2 C3 H3 119.2 . . ? C3 C4 C5 118.5(5) . . ? C3 C4 C7 121.4(9) . . ? C5 C4 C7 120.1(9) . . ? C6 C5 C4 120.9(7) . . ? C6 C5 H5 119.5 . . ? C4 C5 H5 119.5 . . ? C5 C6 C1 120.2(6) . . ? C5 C6 C8 118.0(6) . . ? C1 C6 C8 121.8(4) . . ? C4 C7 H7A 109.5 . . ? C4 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C4 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? N1 C8 C6 111.9(4) . . ? N1 C8 H8A 109.2 . . ? C6 C8 H8A 109.2 . . ? N1 C8 H8B 109.2 . . ? C6 C8 H8B 109.2 . . ? H8A C8 H8B 107.9 . . ? N1 C9 C10 114.1(5) . . ? N1 C9 C9 108.8(3) . 7 ? C10 C9 C9 109.9(5) . 7 ? N1 C9 H9 108.0 . . ? C10 C9 H9 108.0 . . ? C9 C9 H9 108.0 7 . ? C9 C10 C11 112.3(6) . . ? C9 C10 H10A 109.2 . . ? C11 C10 H10A 109.2 . . ? C9 C10 H10B 109.2 . . ? C11 C10 H10B 109.2 . . ? H10A C10 H10B 107.9 . . ? C10 C11 C11 111.0(6) . 7 ? C10 C11 H11A 109.4 . . ? C11 C11 H11A 109.4 7 . ? C10 C11 H11B 109.4 . . ? C11 C11 H11B 109.4 7 . ? H11A C11 H11B 108.0 . . ? O2 C12 C14 125.9(6) . . ? O2 C12 C13 117.5(6) . . ? C14 C12 C13 116.5(6) . . ? O2 C12 H12 90.1 . . ? C14 C12 H12 90.1 . . ? C13 C12 H12 90.1 . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C8 N1 C9 112.2(4) . . ? C8 N1 Ti1 111.0(4) . . ? C9 N1 Ti1 113.4(3) . . ? C8 N1 H1N 100(3) . . ? C9 N1 H1N 117(4) . . ? Ti1 N1 H1N 102(4) . . ? C1 O1 Ti1 137.7(3) . . ? C12 O2 Ti1 147.2(6) . . ? O2 Ti1 O2 103.9(3) . 7 ? O2 Ti1 O1 92.76(17) . 7 ? O2 Ti1 O1 98.24(16) 7 7 ? O2 Ti1 O1 98.24(16) . . ? O2 Ti1 O1 92.76(17) 7 . ? O1 Ti1 O1 162.1(2) 7 . ? O2 Ti1 N1 165.0(2) . 7 ? O2 Ti1 N1 90.50(18) 7 7 ? O1 Ti1 N1 80.74(15) 7 7 ? O1 Ti1 N1 85.15(15) . 7 ? O2 Ti1 N1 90.50(18) . . ? O2 Ti1 N1 165.0(2) 7 . ? O1 Ti1 N1 85.15(15) 7 . ? O1 Ti1 N1 80.74(15) . . ? N1 Ti1 N1 75.6(2) 7 . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.99 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.902 _refine_diff_density_min -0.298 _refine_diff_density_rms 0.092