Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_year ? _journal_page_first ? loop_ _publ_author_name S.D.Bull M.G.Davidson A.L.Johnson D.E.E.Robinson M.F.Mahon _publ_contact_author_name 'Prof. Matthew G. Davidson' _publ_contact_author_address ; Department of Chemistry University of Bath Claverton Down Bath BA2 7AY UNITED KINGDOM ; _publ_contact_author_email M.G.Davidson@bath.ac.uk _publ_section_title ; Synthesis, Structure and Catalytic Activity of an Air-Stable Titanium Triflate Supported by an Amine Tris(phenolate) Ligand. ; #===End data_3 _database_code_CSD 209584 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H37 N O4 Ti' _chemical_formula_weight 523.51 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' O O 0.0106 0.0060 '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' 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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 13.07600(10) _cell_length_b 14.2000(2) _cell_length_c 16.4720(3) _cell_angle_alpha 82.1700(10) _cell_angle_beta 88.7580(10) _cell_angle_gamma 62.7850(10) _cell_volume 2691.70(7) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 10600 _cell_measurement_theta_min 3.59 _cell_measurement_theta_max 25.03 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.292 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1112 _exptl_absorpt_coefficient_mu 0.353 _exptl_absorpt_correction_type Semi-empirical _exptl_absorpt_correction_T_min 0.9169 _exptl_absorpt_correction_T_max 0.9424 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 52968 _diffrn_reflns_av_R_equivalents 0.0556 _diffrn_reflns_av_sigmaI/netI 0.0545 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.64 _diffrn_reflns_theta_max 27.51 _reflns_number_total 12285 _reflns_number_gt 8795 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect, Nonius program suite version 1.9 (1997)' _computing_cell_refinement 'Collect, Nonius program suite version 1.9 (1997)' _computing_data_reduction 'Denzo and Scalepack (otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _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^)+(0.0514P)^2^+1.7810P] 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 SHELXL _refine_ls_extinction_coef 0.0106(12) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 12285 _refine_ls_number_parameters 666 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0803 _refine_ls_R_factor_gt 0.0500 _refine_ls_wR_factor_ref 0.1306 _refine_ls_wR_factor_gt 0.1181 _refine_ls_goodness_of_fit_ref 1.024 _refine_ls_restrained_S_all 1.024 _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 0.89583(3) 0.18049(3) 0.26153(2) 0.03332(12) Uani 1 1 d . . . Ti2 Ti 0.43563(4) 0.16410(3) 0.76376(2) 0.03459(12) Uani 1 1 d . . . O1 O 0.96452(14) 0.23435(13) 0.18065(10) 0.0397(4) Uani 1 1 d . . . O2 O 0.74965(13) 0.27292(12) 0.28850(10) 0.0381(4) Uani 1 1 d . . . O3 O 0.99376(13) 0.06683(12) 0.33701(10) 0.0369(4) Uani 1 1 d . . . O4 O 0.85778(15) 0.10652(14) 0.20061(10) 0.0447(4) Uani 1 1 d . . . O5 O 0.48385(13) 0.26160(12) 0.78579(10) 0.0387(4) Uani 1 1 d . . . O6 O 0.32176(15) 0.21048(14) 0.68087(10) 0.0432(4) Uani 1 1 d . . . O7 O 0.44485(13) 0.05429(12) 0.84238(10) 0.0381(4) Uani 1 1 d . . . O8 O 0.55394(15) 0.08643(13) 0.70657(10) 0.0452(4) Uani 1 1 d . . . N1 N 0.94631(15) 0.27587(14) 0.34070(11) 0.0303(4) Uani 1 1 d . . . N2 N 0.28169(15) 0.26353(14) 0.83718(11) 0.0318(4) Uani 1 1 d . . . C1 C 1.06372(19) 0.26183(18) 0.32202(14) 0.0343(5) Uani 1 1 d . . . H1A H 1.1179 0.1844 0.3298 0.041 Uiso 1 1 calc R . . H1B H 1.0878 0.2951 0.3618 0.041 Uiso 1 1 calc R . . C2 C 0.86423(19) 0.39191(17) 0.32434(14) 0.0332(5) Uani 1 1 d . . . H2A H 0.8640 0.4170 0.2652 0.040 Uiso 1 1 calc R . . H2B H 0.8926 0.4311 0.3552 0.040 Uiso 1 1 calc R . . C3 C 0.94381(19) 0.23564(17) 0.42886(13) 0.0328(5) Uani 1 1 d . . . H3A H 0.8686 0.2363 0.4389 0.039 Uiso 1 1 calc R . . H3B H 0.9509 0.2846 0.4632 0.039 Uiso 1 1 calc R . . C5 C 0.24837(19) 0.37980(17) 0.81748(14) 0.0345(5) Uani 1 1 d . . . H5A H 0.1772 0.4205 0.8458 0.041 Uiso 1 1 calc R . . H5B H 0.2304 0.4017 0.7577 0.041 Uiso 1 1 calc R . . C6 C 0.18121(19) 0.24669(18) 0.81800(14) 0.0356(5) Uani 1 1 d . . . H6A H 0.1200 0.2809 0.8563 0.043 Uiso 1 1 calc R . . H6B H 0.2047 0.1690 0.8270 0.043 Uiso 1 1 calc R . . C7 C 0.3154(2) 0.22969(17) 0.92659(13) 0.0339(5) Uani 1 1 d . . . H7A H 0.2550 0.2807 0.9582 0.041 Uiso 1 1 calc R . . H7B H 0.3879 0.2331 0.9371 0.041 Uiso 1 1 calc R . . C11 C 1.02419(19) 0.29192(18) 0.16951(14) 0.0368(5) Uani 1 1 d . . . C12 C 1.0351(2) 0.3336(2) 0.08964(15) 0.0412(6) Uani 1 1 d . . . C13 C 1.0994(2) 0.3899(2) 0.07942(16) 0.0445(6) Uani 1 1 d . . . H13 H 1.1066 0.4192 0.0255 0.053 Uiso 1 1 calc R . . C14 C 1.1532(2) 0.4049(2) 0.14452(16) 0.0436(6) Uani 1 1 d . . . C15 C 1.1369(2) 0.36531(18) 0.22283(15) 0.0395(5) Uani 1 1 d . . . H15 H 1.1706 0.3768 0.2686 0.047 Uiso 1 1 calc R . . C16 C 1.07312(19) 0.30939(18) 0.23659(14) 0.0348(5) Uani 1 1 d . . . C17 C 0.9838(2) 0.3119(2) 0.01825(15) 0.0511(7) Uani 1 1 d . . . H17A H 0.9877 0.3558 -0.0319 0.077 Uiso 1 1 calc R . . H17B H 0.9033 0.3296 0.0280 0.077 Uiso 1 1 calc R . . H17C H 1.0270 0.2361 0.0120 0.077 Uiso 1 1 calc R . . C18 C 1.2291(3) 0.4595(2) 0.13109(19) 0.0589(8) Uani 1 1 d . . . H18A H 1.1921 0.5285 0.1517 0.088 Uiso 1 1 calc R . . H18B H 1.2408 0.4711 0.0723 0.088 Uiso 1 1 calc R . . H18C H 1.3037 0.4143 0.1605 0.088 Uiso 1 1 calc R . . C21 C 0.68931(19) 0.36157(18) 0.32463(14) 0.0353(5) Uani 1 1 d . . . C22 C 0.5725(2) 0.39413(19) 0.33839(15) 0.0411(6) Uani 1 1 d . . . C23 C 0.5119(2) 0.4865(2) 0.37380(16) 0.0448(6) Uani 1 1 d . . . H23 H 0.4326 0.5091 0.3831 0.054 Uiso 1 1 calc R . . C24 C 0.5621(2) 0.54744(19) 0.39626(15) 0.0422(6) Uani 1 1 d . . . C25 C 0.6788(2) 0.51224(18) 0.38277(14) 0.0376(5) Uani 1 1 d . . . H25 H 0.7156 0.5517 0.3985 0.045 Uiso 1 1 calc R . . C26 C 0.74267(19) 0.42048(17) 0.34667(13) 0.0340(5) Uani 1 1 d . . . C27 C 0.5146(2) 0.3315(2) 0.31321(19) 0.0540(7) Uani 1 1 d . . . H27A H 0.4309 0.3745 0.3134 0.081 Uiso 1 1 calc R . . H27B H 0.5386 0.2654 0.3519 0.081 Uiso 1 1 calc R . . H27C H 0.5366 0.3137 0.2579 0.081 Uiso 1 1 calc R . . C28 C 0.4915(2) 0.6498(2) 0.43115(18) 0.0547(7) Uani 1 1 d . . . H28A H 0.4650 0.7104 0.3869 0.082 Uiso 1 1 calc R . . H28B H 0.5387 0.6586 0.4719 0.082 Uiso 1 1 calc R . . H28C H 0.4248 0.6468 0.4573 0.082 Uiso 1 1 calc R . . C31 C 1.05719(19) 0.04405(18) 0.40732(14) 0.0345(5) Uani 1 1 d . . . C32 C 1.14418(19) -0.06083(18) 0.43131(15) 0.0377(5) Uani 1 1 d . . . C33 C 1.2101(2) -0.08109(19) 0.50277(16) 0.0421(6) Uani 1 1 d . . . H33 H 1.2688 -0.1518 0.5196 0.051 Uiso 1 1 calc R . . C34 C 1.1937(2) -0.00244(19) 0.55051(15) 0.0399(6) Uani 1 1 d . . . C35 C 1.10692(19) 0.10008(18) 0.52514(14) 0.0369(5) Uani 1 1 d . . . H35 H 1.0939 0.1552 0.5569 0.044 Uiso 1 1 calc R . . C36 C 1.03874(18) 0.12401(17) 0.45459(14) 0.0330(5) Uani 1 1 d . . . C37 C 1.1646(2) -0.1466(2) 0.37940(18) 0.0490(6) Uani 1 1 d . . . H37A H 1.1955 -0.1317 0.3272 0.073 Uiso 1 1 calc R . . H37B H 1.0917 -0.1477 0.3688 0.073 Uiso 1 1 calc R . . H37C H 1.2198 -0.2162 0.4084 0.073 Uiso 1 1 calc R . . C38 C 1.2693(2) -0.0261(2) 0.62638(16) 0.0502(7) Uani 1 1 d . . . H38A H 1.2632 -0.0817 0.6655 0.075 Uiso 1 1 calc R . . H38B H 1.2443 0.0391 0.6517 0.075 Uiso 1 1 calc R . . H38C H 1.3494 -0.0511 0.6111 0.075 Uiso 1 1 calc R . . C41 C 0.8660(3) 0.0315(3) 0.1494(2) 0.0625(8) Uani 1 1 d . . . H41 H 0.7913 0.0283 0.1483 0.075 Uiso 1 1 calc R . . C42 C 0.8882(3) 0.0683(4) 0.0646(2) 0.0911(13) Uani 1 1 d . . . H42A H 0.8250 0.1389 0.0446 0.137 Uiso 1 1 calc R . . H42B H 0.8935 0.0172 0.0283 0.137 Uiso 1 1 calc R . . H42C H 0.9607 0.0728 0.0653 0.137 Uiso 1 1 calc R . . C43 C 0.9609(3) -0.0783(3) 0.1850(3) 0.0813(11) Uani 1 1 d . . . H43A H 1.0327 -0.0739 0.1924 0.122 Uiso 1 1 calc R . . H43B H 0.9722 -0.1297 0.1474 0.122 Uiso 1 1 calc R . . H43C H 0.9386 -0.1017 0.2382 0.122 Uiso 1 1 calc R . . C51 C 0.4523(2) 0.35173(18) 0.82101(14) 0.0361(5) Uani 1 1 d . . . C52 C 0.5350(2) 0.38452(19) 0.83574(15) 0.0414(6) Uani 1 1 d . . . C53 C 0.4997(2) 0.4775(2) 0.87161(16) 0.0465(6) Uani 1 1 d . . . H53 H 0.5551 0.5008 0.8817 0.056 Uiso 1 1 calc R . . C54 C 0.3873(2) 0.53730(19) 0.89324(15) 0.0425(6) Uani 1 1 d . . . C55 C 0.3074(2) 0.50150(18) 0.87718(14) 0.0387(5) Uani 1 1 d . . . H55 H 0.2298 0.5409 0.8913 0.046 Uiso 1 1 calc R . . C56 C 0.3384(2) 0.40995(17) 0.84122(13) 0.0344(5) Uani 1 1 d . . . C57 C 0.6566(2) 0.3242(2) 0.8109(2) 0.0548(7) Uani 1 1 d . . . H57A H 0.6906 0.3733 0.7998 0.082 Uiso 1 1 calc R . . H57B H 0.6571 0.2930 0.7613 0.082 Uiso 1 1 calc R . . H57C H 0.7017 0.2671 0.8553 0.082 Uiso 1 1 calc R . . C58 C 0.3522(3) 0.6389(2) 0.92926(18) 0.0547(7) Uani 1 1 d . . . H58A H 0.4194 0.6363 0.9566 0.082 Uiso 1 1 calc R . . H58B H 0.2932 0.6465 0.9692 0.082 Uiso 1 1 calc R . . H58C H 0.3210 0.7001 0.8854 0.082 Uiso 1 1 calc R . . C61 C 0.2071(2) 0.26997(19) 0.66651(15) 0.0406(6) Uani 1 1 d . . . C62 C 0.1638(3) 0.3101(2) 0.58542(16) 0.0478(6) Uani 1 1 d . . . C63 C 0.0449(3) 0.3703(2) 0.57228(17) 0.0557(8) Uani 1 1 d . . . H63 H 0.0148 0.3999 0.5176 0.067 Uiso 1 1 calc R . . C64 C -0.0319(2) 0.3893(2) 0.63510(19) 0.0533(7) Uani 1 1 d . . . C65 C 0.0148(2) 0.35026(19) 0.71488(17) 0.0447(6) Uani 1 1 d . . . H65 H -0.0353 0.3641 0.7592 0.054 Uiso 1 1 calc R . . C66 C 0.1330(2) 0.29138(18) 0.73141(15) 0.0381(5) Uani 1 1 d . . . C67 C 0.2444(3) 0.2826(3) 0.51611(17) 0.0642(8) Uani 1 1 d . . . H67A H 0.2042 0.3288 0.4653 0.096 Uiso 1 1 calc R . . H67B H 0.2707 0.2076 0.5094 0.096 Uiso 1 1 calc R . . H67C H 0.3109 0.2936 0.5285 0.096 Uiso 1 1 calc R . . C68 C -0.1608(3) 0.4461(3) 0.6181(2) 0.0756(10) Uani 1 1 d . . . H68A H -0.1778 0.4688 0.5590 0.113 Uiso 1 1 calc R . . H68B H -0.1951 0.5090 0.6468 0.113 Uiso 1 1 calc R . . H68C H -0.1931 0.3974 0.6376 0.113 Uiso 1 1 calc R . . C71 C 0.39913(19) 0.03470(18) 0.91365(14) 0.0354(5) Uani 1 1 d . . . C72 C 0.4183(2) -0.07013(18) 0.94254(15) 0.0392(5) Uani 1 1 d . . . C73 C 0.3683(2) -0.0863(2) 1.01535(16) 0.0431(6) Uani 1 1 d . . . H73 H 0.3809 -0.1568 1.0358 0.052 Uiso 1 1 calc R . . C74 C 0.3010(2) -0.0040(2) 1.05915(15) 0.0416(6) Uani 1 1 d . . . C75 C 0.2840(2) 0.09813(19) 1.02885(14) 0.0385(5) Uani 1 1 d . . . H75 H 0.2383 0.1557 1.0580 0.046 Uiso 1 1 calc R . . C76 C 0.33229(19) 0.11847(18) 0.95687(14) 0.0350(5) Uani 1 1 d . . . C77 C 0.4895(2) -0.15962(19) 0.89499(17) 0.0479(6) Uani 1 1 d . . . H77A H 0.4993 -0.2277 0.9256 0.072 Uiso 1 1 calc R . . H77B H 0.5651 -0.1621 0.8867 0.072 Uiso 1 1 calc R . . H77C H 0.4505 -0.1475 0.8416 0.072 Uiso 1 1 calc R . . C78 C 0.2444(2) -0.0234(2) 1.13613(16) 0.0519(7) Uani 1 1 d . . . H78A H 0.2021 -0.0626 1.1253 0.078 Uiso 1 1 calc R . . H78B H 0.1909 0.0453 1.1530 0.078 Uiso 1 1 calc R . . H78C H 0.3035 -0.0655 1.1800 0.078 Uiso 1 1 calc R . . C81 C 0.6183(2) 0.0042(2) 0.65874(18) 0.0533(7) Uani 1 1 d . . . H81 H 0.6979 -0.0032 0.6547 0.064 Uiso 1 1 calc R . . C82 C 0.6254(3) -0.1003(2) 0.6994(2) 0.0701(9) Uani 1 1 d . . . H82A H 0.6653 -0.1196 0.7534 0.105 Uiso 1 1 calc R . . H82B H 0.6681 -0.1563 0.6654 0.105 Uiso 1 1 calc R . . H82C H 0.5476 -0.0930 0.7060 0.105 Uiso 1 1 calc R . . C83 C 0.5623(3) 0.0367(3) 0.5748(2) 0.0701(9) Uani 1 1 d . . . H83A H 0.4838 0.0448 0.5780 0.105 Uiso 1 1 calc R . . H83B H 0.6067 -0.0182 0.5403 0.105 Uiso 1 1 calc R . . H83C H 0.5596 0.1050 0.5509 0.105 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 0.0335(2) 0.0283(2) 0.0376(2) -0.00434(17) -0.00099(16) -0.01371(18) Ti2 0.0367(2) 0.0297(2) 0.0374(2) -0.00296(17) 0.00245(17) -0.01579(18) O1 0.0437(9) 0.0425(10) 0.0374(9) -0.0071(7) 0.0015(7) -0.0233(8) O2 0.0335(8) 0.0330(9) 0.0458(9) -0.0051(7) -0.0012(7) -0.0136(7) O3 0.0398(9) 0.0268(8) 0.0424(9) -0.0043(7) -0.0010(7) -0.0137(7) O4 0.0480(10) 0.0411(10) 0.0492(10) -0.0123(8) -0.0024(8) -0.0223(8) O5 0.0388(9) 0.0318(9) 0.0472(10) -0.0039(7) 0.0028(7) -0.0181(7) O6 0.0459(10) 0.0475(10) 0.0392(9) -0.0066(8) -0.0004(7) -0.0237(8) O7 0.0393(9) 0.0289(8) 0.0431(9) -0.0027(7) 0.0033(7) -0.0140(7) O8 0.0464(10) 0.0398(10) 0.0494(10) -0.0105(8) 0.0116(8) -0.0190(8) N1 0.0298(9) 0.0244(9) 0.0333(10) 0.0003(7) -0.0017(7) -0.0104(8) N2 0.0336(10) 0.0263(9) 0.0339(10) 0.0023(7) -0.0028(7) -0.0138(8) C1 0.0329(11) 0.0297(12) 0.0391(12) -0.0006(9) -0.0024(9) -0.0143(10) C2 0.0364(12) 0.0231(11) 0.0367(12) -0.0005(9) -0.0024(9) -0.0116(9) C3 0.0367(12) 0.0254(11) 0.0332(11) -0.0005(9) -0.0013(9) -0.0124(10) C5 0.0378(12) 0.0242(11) 0.0386(12) 0.0009(9) -0.0037(9) -0.0129(10) C6 0.0347(12) 0.0304(12) 0.0411(13) -0.0012(10) -0.0023(9) -0.0154(10) C7 0.0369(12) 0.0279(11) 0.0336(12) 0.0004(9) -0.0002(9) -0.0133(10) C11 0.0325(12) 0.0349(13) 0.0405(13) -0.0037(10) 0.0050(9) -0.0140(10) C12 0.0370(12) 0.0420(14) 0.0375(13) -0.0059(10) 0.0042(10) -0.0121(11) C13 0.0416(13) 0.0407(14) 0.0436(14) -0.0009(11) 0.0113(11) -0.0141(11) C14 0.0386(13) 0.0371(13) 0.0528(15) -0.0013(11) 0.0059(11) -0.0170(11) C15 0.0364(12) 0.0340(13) 0.0458(14) -0.0019(10) -0.0008(10) -0.0152(11) C16 0.0318(11) 0.0293(12) 0.0396(12) -0.0020(9) 0.0022(9) -0.0115(10) C17 0.0511(15) 0.0606(18) 0.0391(14) -0.0072(12) 0.0076(11) -0.0238(14) C18 0.0589(17) 0.0616(19) 0.0649(18) 0.0025(15) 0.0062(14) -0.0382(16) C21 0.0335(12) 0.0273(12) 0.0377(12) 0.0001(9) -0.0022(9) -0.0088(10) C22 0.0341(12) 0.0360(13) 0.0467(14) 0.0047(11) -0.0016(10) -0.0131(11) C23 0.0340(12) 0.0388(14) 0.0507(15) 0.0024(11) 0.0047(11) -0.0098(11) C24 0.0427(13) 0.0330(13) 0.0386(13) 0.0009(10) 0.0036(10) -0.0086(11) C25 0.0420(13) 0.0286(12) 0.0358(12) 0.0020(9) -0.0011(10) -0.0125(10) C26 0.0353(12) 0.0269(11) 0.0320(11) 0.0034(9) -0.0021(9) -0.0095(10) C27 0.0349(13) 0.0480(16) 0.078(2) -0.0050(14) -0.0008(13) -0.0193(12) C28 0.0532(16) 0.0405(15) 0.0585(17) -0.0071(13) 0.0122(13) -0.0116(13) C31 0.0329(11) 0.0294(12) 0.0409(13) 0.0010(9) 0.0008(9) -0.0155(10) C32 0.0309(11) 0.0275(12) 0.0530(14) -0.0020(10) 0.0053(10) -0.0129(10) C33 0.0316(12) 0.0283(12) 0.0594(16) 0.0062(11) -0.0003(11) -0.0109(10) C34 0.0350(12) 0.0362(13) 0.0472(14) 0.0078(11) -0.0044(10) -0.0187(11) C35 0.0385(12) 0.0312(12) 0.0407(13) 0.0036(10) -0.0009(10) -0.0180(10) C36 0.0319(11) 0.0246(11) 0.0391(12) 0.0019(9) 0.0003(9) -0.0118(9) C37 0.0433(14) 0.0310(13) 0.0652(17) -0.0068(12) 0.0038(12) -0.0107(11) C38 0.0457(14) 0.0440(15) 0.0548(16) 0.0107(12) -0.0119(12) -0.0195(12) C41 0.0528(17) 0.069(2) 0.081(2) -0.0393(17) 0.0076(15) -0.0337(16) C42 0.084(3) 0.126(4) 0.075(2) -0.054(2) 0.012(2) -0.048(3) C43 0.067(2) 0.0507(19) 0.140(3) -0.036(2) 0.013(2) -0.0330(17) C51 0.0444(13) 0.0285(12) 0.0357(12) 0.0018(9) -0.0026(10) -0.0186(10) C52 0.0446(14) 0.0348(13) 0.0457(14) 0.0047(11) -0.0052(11) -0.0215(11) C53 0.0545(16) 0.0410(14) 0.0516(15) 0.0037(12) -0.0122(12) -0.0306(13) C54 0.0565(16) 0.0340(13) 0.0397(13) 0.0000(10) -0.0087(11) -0.0239(12) C55 0.0456(13) 0.0310(12) 0.0365(12) -0.0001(10) -0.0047(10) -0.0160(11) C56 0.0415(13) 0.0279(11) 0.0326(11) 0.0042(9) -0.0050(9) -0.0171(10) C57 0.0454(15) 0.0464(16) 0.079(2) -0.0046(14) 0.0025(14) -0.0277(13) C58 0.0684(18) 0.0442(16) 0.0586(17) -0.0093(13) -0.0095(14) -0.0310(14) C61 0.0527(15) 0.0348(13) 0.0405(13) -0.0032(10) -0.0070(11) -0.0256(12) C62 0.0679(18) 0.0411(14) 0.0422(14) -0.0020(11) -0.0121(12) -0.0322(14) C63 0.082(2) 0.0390(15) 0.0473(16) 0.0037(12) -0.0287(15) -0.0304(15) C64 0.0577(17) 0.0318(14) 0.0643(18) -0.0018(12) -0.0257(14) -0.0155(12) C65 0.0447(14) 0.0302(13) 0.0568(16) -0.0048(11) -0.0079(12) -0.0149(11) C66 0.0407(13) 0.0268(12) 0.0467(14) -0.0001(10) -0.0088(10) -0.0162(10) C67 0.094(2) 0.074(2) 0.0377(15) -0.0034(14) -0.0081(15) -0.0510(19) C68 0.065(2) 0.0487(18) 0.096(3) -0.0038(17) -0.0402(18) -0.0116(16) C71 0.0328(11) 0.0316(12) 0.0386(12) 0.0032(10) -0.0030(9) -0.0141(10) C72 0.0352(12) 0.0301(12) 0.0491(14) 0.0031(10) -0.0067(10) -0.0142(10) C73 0.0393(13) 0.0351(13) 0.0538(15) 0.0094(11) -0.0060(11) -0.0198(11) C74 0.0367(13) 0.0401(14) 0.0437(14) 0.0096(11) -0.0056(10) -0.0178(11) C75 0.0342(12) 0.0363(13) 0.0388(13) 0.0031(10) -0.0044(10) -0.0127(10) C76 0.0344(12) 0.0277(12) 0.0394(12) 0.0033(9) -0.0045(9) -0.0131(10) C77 0.0489(15) 0.0310(13) 0.0622(17) -0.0011(12) -0.0013(12) -0.0183(12) C78 0.0487(15) 0.0496(16) 0.0506(16) 0.0119(12) 0.0018(12) -0.0219(13) C81 0.0420(14) 0.0559(17) 0.0655(18) -0.0214(14) 0.0172(13) -0.0226(13) C82 0.0580(18) 0.0440(17) 0.104(3) -0.0197(17) 0.0245(18) -0.0185(15) C83 0.068(2) 0.086(2) 0.064(2) -0.0340(18) 0.0191(16) -0.0369(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 O4 1.7733(16) . ? Ti1 O2 1.8441(16) . ? Ti1 O3 1.8500(16) . ? Ti1 O1 1.8617(16) . ? Ti1 N1 2.3037(18) . ? Ti2 O8 1.7767(17) . ? Ti2 O5 1.8414(16) . ? Ti2 O7 1.8461(16) . ? Ti2 O6 1.8605(17) . ? Ti2 N2 2.2952(19) . ? O1 C11 1.359(3) . ? O2 C21 1.355(3) . ? O3 C31 1.352(3) . ? O4 C41 1.412(3) . ? O5 C51 1.362(3) . ? O6 C61 1.349(3) . ? O7 C71 1.358(3) . ? O8 C81 1.420(3) . ? N1 C1 1.486(3) . ? N1 C2 1.488(3) . ? N1 C3 1.492(3) . ? N2 C6 1.486(3) . ? N2 C5 1.491(3) . ? N2 C7 1.495(3) . ? C1 C16 1.504(3) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 C26 1.501(3) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C3 C36 1.508(3) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C5 C56 1.499(3) . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C6 C66 1.504(3) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C7 C76 1.504(3) . ? C7 H7A 0.9900 . ? C7 H7B 0.9900 . ? C11 C16 1.394(3) . ? C11 C12 1.400(3) . ? C12 C13 1.394(4) . ? C12 C17 1.500(4) . ? C13 C14 1.386(4) . ? C13 H13 0.9500 . ? C14 C15 1.387(3) . ? C14 C18 1.512(3) . ? C15 C16 1.388(3) . ? C15 H15 0.9500 . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? C21 C26 1.395(3) . ? C21 C22 1.402(3) . ? C22 C23 1.388(4) . ? C22 C27 1.506(4) . ? C23 C24 1.391(4) . ? C23 H23 0.9500 . ? C24 C25 1.395(3) . ? C24 C28 1.507(4) . ? C25 C26 1.394(3) . ? C25 H25 0.9500 . ? 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 C36 1.391(3) . ? C31 C32 1.406(3) . ? C32 C33 1.391(3) . ? C32 C37 1.504(3) . ? C33 C34 1.387(4) . ? C33 H33 0.9500 . ? C34 C35 1.387(3) . ? C34 C38 1.513(3) . ? C35 C36 1.386(3) . ? C35 H35 0.9500 . ? C37 H37A 0.9800 . ? C37 H37B 0.9800 . ? C37 H37C 0.9800 . ? C38 H38A 0.9800 . ? C38 H38B 0.9800 . ? C38 H38C 0.9800 . ? C41 C42 1.493(5) . ? C41 C43 1.525(5) . ? C41 H41 1.0000 . ? C42 H42A 0.9800 . ? C42 H42B 0.9800 . ? C42 H42C 0.9800 . ? C43 H43A 0.9800 . ? C43 H43B 0.9800 . ? C43 H43C 0.9800 . ? C51 C56 1.393(3) . ? C51 C52 1.395(3) . ? C52 C53 1.396(4) . ? C52 C57 1.501(4) . ? C53 C54 1.389(4) . ? C53 H53 0.9500 . ? C54 C55 1.398(3) . ? C54 C58 1.503(4) . ? C55 C56 1.387(3) . ? C55 H55 0.9500 . ? 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 C66 1.396(4) . ? C61 C62 1.400(3) . ? C62 C63 1.393(4) . ? C62 C67 1.503(4) . ? C63 C64 1.391(4) . ? C63 H63 0.9500 . ? C64 C65 1.390(4) . ? C64 C68 1.512(4) . ? C65 C66 1.391(3) . ? C65 H65 0.9500 . ? C67 H67A 0.9800 . ? C67 H67B 0.9800 . ? C67 H67C 0.9800 . ? C68 H68A 0.9800 . ? C68 H68B 0.9800 . ? C68 H68C 0.9800 . ? C71 C76 1.392(3) . ? C71 C72 1.406(3) . ? C72 C73 1.395(3) . ? C72 C77 1.501(4) . ? C73 C74 1.386(4) . ? C73 H73 0.9500 . ? C74 C75 1.384(3) . ? C74 C78 1.510(3) . ? C75 C76 1.389(3) . ? C75 H75 0.9500 . ? C77 H77A 0.9800 . ? C77 H77B 0.9800 . ? C77 H77C 0.9800 . ? C78 H78A 0.9800 . ? C78 H78B 0.9800 . ? C78 H78C 0.9800 . ? C81 C83 1.490(4) . ? C81 C82 1.505(4) . ? C81 H81 1.0000 . ? C82 H82A 0.9800 . ? C82 H82B 0.9800 . ? C82 H82C 0.9800 . ? C83 H83A 0.9800 . ? C83 H83B 0.9800 . ? C83 H83C 0.9800 . ? 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 O4 Ti1 O2 98.09(8) . . ? O4 Ti1 O3 97.64(8) . . ? O2 Ti1 O3 120.84(7) . . ? O4 Ti1 O1 97.62(8) . . ? O2 Ti1 O1 117.07(7) . . ? O3 Ti1 O1 116.67(7) . . ? O4 Ti1 N1 179.68(8) . . ? O2 Ti1 N1 82.23(7) . . ? O3 Ti1 N1 82.13(6) . . ? O1 Ti1 N1 82.30(7) . . ? O8 Ti2 O5 98.17(8) . . ? O8 Ti2 O7 97.56(8) . . ? O5 Ti2 O7 121.98(7) . . ? O8 Ti2 O6 97.32(8) . . ? O5 Ti2 O6 116.54(8) . . ? O7 Ti2 O6 116.18(7) . . ? O8 Ti2 N2 179.37(8) . . ? O5 Ti2 N2 82.44(7) . . ? O7 Ti2 N2 82.21(7) . . ? O6 Ti2 N2 82.26(7) . . ? C11 O1 Ti1 141.70(15) . . ? C21 O2 Ti1 143.19(15) . . ? C31 O3 Ti1 141.87(14) . . ? C41 O4 Ti1 161.56(18) . . ? C51 O5 Ti2 143.20(15) . . ? C61 O6 Ti2 141.30(16) . . ? C71 O7 Ti2 142.17(15) . . ? C81 O8 Ti2 156.08(17) . . ? C1 N1 C2 108.52(16) . . ? C1 N1 C3 109.73(16) . . ? C2 N1 C3 109.16(17) . . ? C1 N1 Ti1 110.16(13) . . ? C2 N1 Ti1 110.73(13) . . ? C3 N1 Ti1 108.53(13) . . ? C6 N2 C5 108.75(16) . . ? C6 N2 C7 110.04(17) . . ? C5 N2 C7 108.28(17) . . ? C6 N2 Ti2 110.16(14) . . ? C5 N2 Ti2 111.01(13) . . ? C7 N2 Ti2 108.57(13) . . ? N1 C1 C16 114.10(18) . . ? N1 C1 H1A 108.7 . . ? C16 C1 H1A 108.7 . . ? N1 C1 H1B 108.7 . . ? C16 C1 H1B 108.7 . . ? H1A C1 H1B 107.6 . . ? N1 C2 C26 115.10(17) . . ? N1 C2 H2A 108.5 . . ? C26 C2 H2A 108.5 . . ? N1 C2 H2B 108.5 . . ? C26 C2 H2B 108.5 . . ? H2A C2 H2B 107.5 . . ? N1 C3 C36 112.82(18) . . ? N1 C3 H3A 109.0 . . ? C36 C3 H3A 109.0 . . ? N1 C3 H3B 109.0 . . ? C36 C3 H3B 109.0 . . ? H3A C3 H3B 107.8 . . ? N2 C5 C56 114.51(18) . . ? N2 C5 H5A 108.6 . . ? C56 C5 H5A 108.6 . . ? N2 C5 H5B 108.6 . . ? C56 C5 H5B 108.6 . . ? H5A C5 H5B 107.6 . . ? N2 C6 C66 113.17(18) . . ? N2 C6 H6A 108.9 . . ? C66 C6 H6A 108.9 . . ? N2 C6 H6B 108.9 . . ? C66 C6 H6B 108.9 . . ? H6A C6 H6B 107.8 . . ? N2 C7 C76 113.20(19) . . ? N2 C7 H7A 108.9 . . ? C76 C7 H7A 108.9 . . ? N2 C7 H7B 108.9 . . ? C76 C7 H7B 108.9 . . ? H7A C7 H7B 107.8 . . ? O1 C11 C16 120.4(2) . . ? O1 C11 C12 118.9(2) . . ? C16 C11 C12 120.7(2) . . ? C13 C12 C11 117.9(2) . . ? C13 C12 C17 122.3(2) . . ? C11 C12 C17 119.7(2) . . ? C14 C13 C12 122.8(2) . . ? C14 C13 H13 118.6 . . ? C12 C13 H13 118.6 . . ? C13 C14 C15 117.3(2) . . ? C13 C14 C18 121.6(2) . . ? C15 C14 C18 121.0(2) . . ? C14 C15 C16 122.2(2) . . ? C14 C15 H15 118.9 . . ? C16 C15 H15 118.9 . . ? C15 C16 C11 118.9(2) . . ? C15 C16 C1 120.6(2) . . ? C11 C16 C1 120.4(2) . . ? C12 C17 H17A 109.5 . . ? C12 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C12 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C14 C18 H18A 109.5 . . ? C14 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C14 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? O2 C21 C26 120.2(2) . . ? O2 C21 C22 119.2(2) . . ? C26 C21 C22 120.5(2) . . ? C23 C22 C21 118.2(2) . . ? C23 C22 C27 121.4(2) . . ? C21 C22 C27 120.4(2) . . ? C22 C23 C24 122.9(2) . . ? C22 C23 H23 118.6 . . ? C24 C23 H23 118.6 . . ? C23 C24 C25 117.6(2) . . ? C23 C24 C28 120.9(2) . . ? C25 C24 C28 121.5(2) . . ? C26 C25 C24 121.4(2) . . ? C26 C25 H25 119.3 . . ? C24 C25 H25 119.3 . . ? C25 C26 C21 119.4(2) . . ? C25 C26 C2 119.9(2) . . ? C21 C26 C2 120.4(2) . . ? C22 C27 H27A 109.5 . . ? C22 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C22 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C24 C28 H28A 109.5 . . ? C24 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C24 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? O3 C31 C36 120.45(19) . . ? O3 C31 C32 119.4(2) . . ? C36 C31 C32 120.1(2) . . ? C33 C32 C31 118.0(2) . . ? C33 C32 C37 122.1(2) . . ? C31 C32 C37 119.9(2) . . ? C34 C33 C32 122.8(2) . . ? C34 C33 H33 118.6 . . ? C32 C33 H33 118.6 . . ? C33 C34 C35 117.7(2) . . ? C33 C34 C38 121.6(2) . . ? C35 C34 C38 120.8(2) . . ? C36 C35 C34 121.6(2) . . ? C36 C35 H35 119.2 . . ? C34 C35 H35 119.2 . . ? C35 C36 C31 119.8(2) . . ? C35 C36 C3 120.7(2) . . ? C31 C36 C3 119.5(2) . . ? C32 C37 H37A 109.5 . . ? C32 C37 H37B 109.5 . . ? H37A C37 H37B 109.5 . . ? C32 C37 H37C 109.5 . . ? H37A C37 H37C 109.5 . . ? H37B C37 H37C 109.5 . . ? C34 C38 H38A 109.5 . . ? C34 C38 H38B 109.5 . . ? H38A C38 H38B 109.5 . . ? C34 C38 H38C 109.5 . . ? H38A C38 H38C 109.5 . . ? H38B C38 H38C 109.5 . . ? O4 C41 C42 108.6(3) . . ? O4 C41 C43 108.7(3) . . ? C42 C41 C43 112.7(3) . . ? O4 C41 H41 108.9 . . ? C42 C41 H41 108.9 . . ? C43 C41 H41 108.9 . . ? C41 C42 H42A 109.5 . . ? C41 C42 H42B 109.5 . . ? H42A C42 H42B 109.5 . . ? C41 C42 H42C 109.5 . . ? H42A C42 H42C 109.5 . . ? H42B C42 H42C 109.5 . . ? C41 C43 H43A 109.5 . . ? C41 C43 H43B 109.5 . . ? H43A C43 H43B 109.5 . . ? C41 C43 H43C 109.5 . . ? H43A C43 H43C 109.5 . . ? H43B C43 H43C 109.5 . . ? O5 C51 C56 119.7(2) . . ? O5 C51 C52 119.2(2) . . ? C56 C51 C52 121.1(2) . . ? C51 C52 C53 117.8(2) . . ? C51 C52 C57 121.1(2) . . ? C53 C52 C57 121.1(2) . . ? C54 C53 C52 122.9(2) . . ? C54 C53 H53 118.6 . . ? C52 C53 H53 118.6 . . ? C53 C54 C55 117.3(2) . . ? C53 C54 C58 121.1(2) . . ? C55 C54 C58 121.5(2) . . ? C56 C55 C54 121.7(2) . . ? C56 C55 H55 119.1 . . ? C54 C55 H55 119.1 . . ? C55 C56 C51 119.1(2) . . ? C55 C56 C5 120.2(2) . . ? C51 C56 C5 120.4(2) . . ? C52 C57 H57A 109.5 . . ? C52 C57 H57B 109.5 . . ? H57A C57 H57B 109.5 . . ? C52 C57 H57C 109.5 . . ? H57A C57 H57C 109.5 . . ? H57B C57 H57C 109.5 . . ? C54 C58 H58A 109.5 . . ? C54 C58 H58B 109.5 . . ? H58A C58 H58B 109.5 . . ? C54 C58 H58C 109.5 . . ? H58A C58 H58C 109.5 . . ? H58B C58 H58C 109.5 . . ? O6 C61 C66 120.6(2) . . ? O6 C61 C62 118.9(2) . . ? C66 C61 C62 120.6(2) . . ? C63 C62 C61 117.7(3) . . ? C63 C62 C67 122.4(2) . . ? C61 C62 C67 119.8(3) . . ? C64 C63 C62 123.3(2) . . ? C64 C63 H63 118.3 . . ? C62 C63 H63 118.3 . . ? C65 C64 C63 117.1(3) . . ? C65 C64 C68 120.8(3) . . ? C63 C64 C68 122.0(3) . . ? C64 C65 C66 121.7(3) . . ? C64 C65 H65 119.1 . . ? C66 C65 H65 119.1 . . ? C65 C66 C61 119.5(2) . . ? C65 C66 C6 120.7(2) . . ? C61 C66 C6 119.7(2) . . ? C62 C67 H67A 109.5 . . ? C62 C67 H67B 109.5 . . ? H67A C67 H67B 109.5 . . ? C62 C67 H67C 109.5 . . ? H67A C67 H67C 109.5 . . ? H67B C67 H67C 109.5 . . ? C64 C68 H68A 109.5 . . ? C64 C68 H68B 109.5 . . ? H68A C68 H68B 109.5 . . ? C64 C68 H68C 109.5 . . ? H68A C68 H68C 109.5 . . ? H68B C68 H68C 109.5 . . ? O7 C71 C76 120.0(2) . . ? O7 C71 C72 119.6(2) . . ? C76 C71 C72 120.4(2) . . ? C73 C72 C71 117.6(2) . . ? C73 C72 C77 122.4(2) . . ? C71 C72 C77 120.0(2) . . ? C74 C73 C72 122.9(2) . . ? C74 C73 H73 118.5 . . ? C72 C73 H73 118.5 . . ? C75 C74 C73 117.8(2) . . ? C75 C74 C78 120.5(2) . . ? C73 C74 C78 121.7(2) . . ? C74 C75 C76 121.5(2) . . ? C74 C75 H75 119.2 . . ? C76 C75 H75 119.2 . . ? C75 C76 C71 119.6(2) . . ? C75 C76 C7 120.5(2) . . ? C71 C76 C7 119.9(2) . . ? C72 C77 H77A 109.5 . . ? C72 C77 H77B 109.5 . . ? H77A C77 H77B 109.5 . . ? C72 C77 H77C 109.5 . . ? H77A C77 H77C 109.5 . . ? H77B C77 H77C 109.5 . . ? C74 C78 H78A 109.5 . . ? C74 C78 H78B 109.5 . . ? H78A C78 H78B 109.5 . . ? C74 C78 H78C 109.5 . . ? H78A C78 H78C 109.5 . . ? H78B C78 H78C 109.5 . . ? O8 C81 C83 108.2(2) . . ? O8 C81 C82 109.9(2) . . ? C83 C81 C82 112.4(3) . . ? O8 C81 H81 108.8 . . ? C83 C81 H81 108.8 . . ? C82 C81 H81 108.8 . . ? C81 C82 H82A 109.5 . . ? C81 C82 H82B 109.5 . . ? H82A C82 H82B 109.5 . . ? C81 C82 H82C 109.5 . . ? H82A C82 H82C 109.5 . . ? H82B C82 H82C 109.5 . . ? C81 C83 H83A 109.5 . . ? C81 C83 H83B 109.5 . . ? H83A C83 H83B 109.5 . . ? C81 C83 H83C 109.5 . . ? H83A C83 H83C 109.5 . . ? H83B C83 H83C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.337 _refine_diff_density_min -0.602 _refine_diff_density_rms 0.080 data_2a _database_code_CSD 209585 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C29.75 H32 F3 N O6 S Ti' _chemical_formula_weight 636.52 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' F F 0.0171 0.0103 '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' S S 0.1246 0.1234 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.1340(2) _cell_length_b 16.8420(3) _cell_length_c 18.2010(4) _cell_angle_alpha 101.6130(10) _cell_angle_beta 93.7620(10) _cell_angle_gamma 95.2590(10) _cell_volume 3018.81(10) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 12285 _cell_measurement_theta_min 3.64 _cell_measurement_theta_max 27.51 _exptl_crystal_description Block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.401 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1322 _exptl_absorpt_coefficient_mu 0.414 _exptl_absorpt_correction_type Semi-empirical _exptl_absorpt_correction_T_min 0.9145 _exptl_absorpt_correction_T_max 0.9405 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type "'Nonius Kappa CCD" _diffrn_measurement_method \f-rotation _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 41484 _diffrn_reflns_av_R_equivalents 0.0420 _diffrn_reflns_av_sigmaI/netI 0.0414 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.59 _diffrn_reflns_theta_max 25.03 _reflns_number_total 10600 _reflns_number_gt 8214 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect, Nonius program suite version 1.9 (1997)' _computing_cell_refinement 'Collect, Nonius program suite version 1.9 (1997)' _computing_data_reduction 'Denzo and Scalepack (otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _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^)+(0.0473P)^2^+2.2691P] 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 SHELXL _refine_ls_extinction_coef 0.0023(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 10600 _refine_ls_number_parameters 786 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0630 _refine_ls_R_factor_gt 0.0436 _refine_ls_wR_factor_ref 0.1159 _refine_ls_wR_factor_gt 0.1056 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 1.026 _refine_ls_shift/su_max 0.009 _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 0.36640(4) 0.71229(3) 0.84169(2) 0.03032(13) Uani 1 1 d . . . Ti2 Ti 0.82938(5) 0.80421(3) 0.35752(3) 0.03775(14) Uani 1 1 d . . . F1 F 0.73672(18) 0.82927(12) 0.89215(12) 0.0704(5) Uani 1 1 d . . . F2 F 0.79943(16) 0.71079(11) 0.89078(11) 0.0634(5) Uani 1 1 d . . . F3 F 0.86441(16) 0.80910(11) 0.98467(11) 0.0627(5) Uani 1 1 d . . . F4 F 1.0078(3) 0.93938(15) 0.65258(13) 0.1100(9) Uani 1 1 d . . . F5 F 0.8037(3) 0.90718(15) 0.61289(15) 0.1020(8) Uani 1 1 d . . . F6 F 0.9310(3) 0.97715(13) 0.55549(14) 0.0955(8) Uani 1 1 d . . . N1 N 0.20489(19) 0.71092(12) 0.75313(11) 0.0313(5) Uani 1 1 d . . . N2 N 0.76514(19) 0.79033(13) 0.23662(12) 0.0342(5) Uani 1 1 d . . . O1 O 0.28147(17) 0.61702(11) 0.85080(11) 0.0417(4) Uani 1 1 d . . . O2 O 0.30088(17) 0.80288(11) 0.88869(10) 0.0393(4) Uani 1 1 d . . . O3 O 0.47307(16) 0.71181(11) 0.76579(9) 0.0374(4) Uani 1 1 d . . . O4A O 0.51812(16) 0.71657(11) 0.91904(10) 0.0387(4) Uani 1 1 d . . . O4B O 0.5902(2) 0.82816(13) 1.02530(12) 0.0591(6) Uani 1 1 d . . . O4C O 0.6544(2) 0.69207(13) 1.02358(12) 0.0598(6) Uani 1 1 d . . . O5 O 0.99438(17) 0.80467(12) 0.32659(10) 0.0443(5) Uani 1 1 d . . . O6 O 0.72487(17) 0.70880(11) 0.34723(10) 0.0409(4) Uani 1 1 d . . . O7 O 0.76236(19) 0.90071(12) 0.36738(11) 0.0464(5) Uani 1 1 d . . . O8A O 0.8697(2) 0.81151(14) 0.46881(11) 0.0560(5) Uani 1 1 d . . . O8B O 1.0988(2) 0.84038(16) 0.51555(14) 0.0725(7) Uani 1 1 d . . . O8C O 0.9418(3) 0.76420(14) 0.57922(14) 0.0716(7) Uani 1 1 d . . . S1 S 0.61761(6) 0.75198(4) 0.98317(4) 0.04059(18) Uani 1 1 d . . . S2 S 0.96657(7) 0.82315(5) 0.53430(4) 0.04752(19) Uani 1 1 d . . . C1 C 0.1748(3) 0.62586(16) 0.70633(15) 0.0416(6) Uani 1 1 d . . . H1A H 0.2579 0.6071 0.6866 0.050 Uiso 1 1 calc R . . H1B H 0.1118 0.6270 0.6627 0.050 Uiso 1 1 calc R . . C2 C 0.0802(2) 0.73706(16) 0.78611(15) 0.0390(6) Uani 1 1 d . . . H2A H 0.0530 0.7013 0.8207 0.047 Uiso 1 1 calc R . . H2B H 0.0083 0.7299 0.7451 0.047 Uiso 1 1 calc R . . C3 C 0.2461(2) 0.76698(16) 0.70243(15) 0.0377(6) Uani 1 1 d . . . H3A H 0.2708 0.8224 0.7334 0.045 Uiso 1 1 calc R . . H3B H 0.1689 0.7696 0.6671 0.045 Uiso 1 1 calc R . . C4 C 0.7627(3) 0.77591(18) 0.93488(17) 0.0461(7) Uani 1 1 d . . . C5 C 0.8448(2) 0.73052(16) 0.19080(15) 0.0366(6) Uani 1 1 d . . . H5A H 0.8069 0.7182 0.1377 0.044 Uiso 1 1 calc R . . H5B H 0.8370 0.6791 0.2094 0.044 Uiso 1 1 calc R . . C6 C 0.6200(2) 0.75904(16) 0.22089(15) 0.0370(6) Uani 1 1 d . . . H6A H 0.5681 0.7955 0.2546 0.044 Uiso 1 1 calc R . . H6B H 0.5909 0.7611 0.1684 0.044 Uiso 1 1 calc R . . C7 C 0.7837(3) 0.87061(16) 0.21221(15) 0.0395(6) Uani 1 1 d . . . H7A H 0.8776 0.8941 0.2247 0.047 Uiso 1 1 calc R . . H7B H 0.7649 0.8610 0.1569 0.047 Uiso 1 1 calc R . . C8 C 0.9247(4) 0.9171(2) 0.59141(19) 0.0647(9) Uani 1 1 d . . . C11 C 0.1736(2) 0.56188(16) 0.82063(16) 0.0405(6) Uani 1 1 d . . . C12 C 0.1247(3) 0.50640(17) 0.86203(18) 0.0469(7) Uani 1 1 d . . . C13 C 0.0125(3) 0.45394(17) 0.8294(2) 0.0528(8) Uani 1 1 d . . . H13 H -0.0234 0.4155 0.8564 0.063 Uiso 1 1 calc R . . C14 C -0.0493(3) 0.45500(17) 0.7596(2) 0.0536(8) Uani 1 1 d . . . C15 C 0.0039(3) 0.51153(17) 0.71952(19) 0.0494(7) Uani 1 1 d . . . H15 H -0.0366 0.5131 0.6713 0.059 Uiso 1 1 calc R . . C16 C 0.1156(3) 0.56542(16) 0.74987(17) 0.0421(7) Uani 1 1 d . . . C17 C 0.1918(4) 0.5031(2) 0.9370(2) 0.0656(9) Uani 1 1 d . . . H17A H 0.2012 0.5575 0.9697 0.098 Uiso 1 1 calc R . . H17B H 0.2799 0.4846 0.9302 0.098 Uiso 1 1 calc R . . H17C H 0.1381 0.4650 0.9601 0.098 Uiso 1 1 calc R . . C18 C -0.1692(3) 0.3952(2) 0.7249(2) 0.0716(11) Uani 1 1 d . . . H18A H -0.2013 0.3655 0.7625 0.107 Uiso 1 1 calc R . . H18B H -0.1436 0.3564 0.6818 0.107 Uiso 1 1 calc R . . H18C H -0.2399 0.4250 0.7079 0.107 Uiso 1 1 calc R . . C21 C 0.2041(3) 0.85355(16) 0.88185(15) 0.0373(6) Uani 1 1 d . . . C22 C 0.2170(3) 0.93096(16) 0.92728(17) 0.0442(7) Uani 1 1 d . . . C23 C 0.1187(3) 0.98076(17) 0.91570(19) 0.0509(8) Uani 1 1 d . . . H23 H 0.1245 1.0338 0.9466 0.061 Uiso 1 1 calc R . . C24 C 0.0135(3) 0.95668(17) 0.86145(18) 0.0471(7) Uani 1 1 d . . . C25 C 0.0019(3) 0.87743(17) 0.81781(17) 0.0434(7) Uani 1 1 d . . . H25 H -0.0706 0.8595 0.7806 0.052 Uiso 1 1 calc R . . C26 C 0.0961(2) 0.82449(16) 0.82850(15) 0.0377(6) Uani 1 1 d . . . C27 C 0.3332(3) 0.95960(19) 0.9850(2) 0.0631(9) Uani 1 1 d . . . H27A H 0.4149 0.9431 0.9633 0.095 Uiso 1 1 calc R . . H27B H 0.3199 0.9353 1.0289 0.095 Uiso 1 1 calc R . . H27C H 0.3406 1.0191 1.0005 0.095 Uiso 1 1 calc R . . C28 C -0.0896(3) 1.01380(19) 0.8501(2) 0.0645(10) Uani 1 1 d . . . H28A H -0.0513 1.0703 0.8696 0.097 Uiso 1 1 calc R . . H28B H -0.1670 1.0019 0.8772 0.097 Uiso 1 1 calc R . . H28C H -0.1170 1.0062 0.7963 0.097 Uiso 1 1 calc R . . C31 C 0.4733(2) 0.71879(16) 0.69199(14) 0.0357(6) Uani 1 1 d . . . C32 C 0.5864(2) 0.70456(17) 0.65382(15) 0.0398(6) Uani 1 1 d . . . C33 C 0.5826(3) 0.71378(18) 0.57956(15) 0.0457(7) Uani 1 1 d . . . H33 H 0.6596 0.7055 0.5531 0.055 Uiso 1 1 calc R . . C34 C 0.4709(3) 0.73459(19) 0.54254(15) 0.0481(7) Uani 1 1 d . . . C35 C 0.3609(3) 0.74871(18) 0.58265(15) 0.0460(7) Uani 1 1 d . . . H35 H 0.2836 0.7631 0.5583 0.055 Uiso 1 1 calc R . . C36 C 0.3608(3) 0.74241(16) 0.65749(14) 0.0379(6) Uani 1 1 d . . . C37 C 0.7085(3) 0.6819(2) 0.69325(18) 0.0569(8) Uani 1 1 d . . . H37A H 0.7823 0.6826 0.6611 0.085 Uiso 1 1 calc R . . H37B H 0.6900 0.6272 0.7034 0.085 Uiso 1 1 calc R . . H37C H 0.7324 0.7213 0.7408 0.085 Uiso 1 1 calc R . . C38 C 0.4700(4) 0.7445(3) 0.46166(17) 0.0707(11) Uani 1 1 d . . . H38A H 0.3922 0.7714 0.4492 0.106 Uiso 1 1 calc R . . H38B H 0.4661 0.6908 0.4281 0.106 Uiso 1 1 calc R . . H38C H 0.5513 0.7779 0.4553 0.106 Uiso 1 1 calc R . . C51 C 1.0607(2) 0.79714(16) 0.26259(15) 0.0384(6) Uani 1 1 d . . . C52 C 1.1957(3) 0.82620(17) 0.26828(17) 0.0433(7) Uani 1 1 d . . . C53 C 1.2577(3) 0.81433(18) 0.20117(19) 0.0487(7) Uani 1 1 d . . . H53 H 1.3494 0.8331 0.2031 0.058 Uiso 1 1 calc R . . C54 C 1.1926(3) 0.77676(18) 0.13214(18) 0.0478(7) Uani 1 1 d . . . C55 C 1.0564(3) 0.75168(17) 0.12888(16) 0.0423(6) Uani 1 1 d . . . H55 H 1.0088 0.7277 0.0817 0.051 Uiso 1 1 calc R . . C56 C 0.9900(2) 0.76147(16) 0.19403(15) 0.0377(6) Uani 1 1 d . . . C57 C 1.2672(3) 0.8675(2) 0.34266(19) 0.0598(9) Uani 1 1 d . . . H57A H 1.2359 0.8401 0.3820 0.090 Uiso 1 1 calc R . . H57B H 1.2495 0.9247 0.3544 0.090 Uiso 1 1 calc R . . H57C H 1.3630 0.8646 0.3404 0.090 Uiso 1 1 calc R . . C58 C 1.2638(3) 0.7630(2) 0.0612(2) 0.0704(10) Uani 1 1 d . . . H58A H 1.2844 0.7063 0.0492 0.106 Uiso 1 1 calc R . . H58B H 1.3465 0.7998 0.0687 0.106 Uiso 1 1 calc R . . H58C H 1.2067 0.7739 0.0196 0.106 Uiso 1 1 calc R . . C61 C 0.6406(2) 0.65209(16) 0.29686(15) 0.0379(6) Uani 1 1 d . . . C62 C 0.6091(3) 0.57484(17) 0.31151(16) 0.0430(7) Uani 1 1 d . . . C63 C 0.5245(3) 0.51966(17) 0.25775(18) 0.0486(7) Uani 1 1 d . . . H63 H 0.5015 0.4667 0.2666 0.058 Uiso 1 1 calc R . . C64 C 0.4723(3) 0.53847(18) 0.19179(18) 0.0499(7) Uani 1 1 d . . . C65 C 0.5065(3) 0.61628(17) 0.17950(16) 0.0446(7) Uani 1 1 d . . . H65 H 0.4722 0.6303 0.1345 0.054 Uiso 1 1 calc R . . C66 C 0.5897(2) 0.67393(16) 0.23170(15) 0.0380(6) Uani 1 1 d . . . C67 C 0.6651(3) 0.55321(19) 0.38255(18) 0.0556(8) Uani 1 1 d . . . H67A H 0.6224 0.5000 0.3870 0.083 Uiso 1 1 calc R . . H67B H 0.6483 0.5947 0.4260 0.083 Uiso 1 1 calc R . . H67C H 0.7612 0.5508 0.3809 0.083 Uiso 1 1 calc R . . C68 C 0.3791(4) 0.4772(2) 0.1349(2) 0.0700(10) Uani 1 1 d . . . H68A H 0.3558 0.4289 0.1557 0.105 Uiso 1 1 calc R . . H68B H 0.4230 0.4612 0.0886 0.105 Uiso 1 1 calc R . . H68C H 0.2981 0.5017 0.1236 0.105 Uiso 1 1 calc R . . C71 C 0.6931(3) 0.94673(17) 0.32751(17) 0.0443(7) Uani 1 1 d . . . C72 C 0.6214(3) 1.00633(17) 0.36529(19) 0.0511(8) Uani 1 1 d . . . C73 C 0.5449(3) 1.04663(17) 0.3216(2) 0.0554(9) Uani 1 1 d . . . H73 H 0.4941 1.0871 0.3461 0.067 Uiso 1 1 calc R . . C74 C 0.5396(3) 1.03023(17) 0.2434(2) 0.0532(8) Uani 1 1 d . . . C75 C 0.6165(3) 0.97228(16) 0.20781(18) 0.0462(7) Uani 1 1 d . . . H75 H 0.6152 0.9609 0.1545 0.055 Uiso 1 1 calc R . . C76 C 0.6949(2) 0.93088(16) 0.24899(16) 0.0403(6) Uani 1 1 d . . . C77 C 0.6314(4) 1.0249(2) 0.4500(2) 0.0701(10) Uani 1 1 d . . . H77A H 0.7226 1.0473 0.4695 0.105 Uiso 1 1 calc R . . H77B H 0.6082 0.9747 0.4679 0.105 Uiso 1 1 calc R . . H77C H 0.5699 1.0648 0.4679 0.105 Uiso 1 1 calc R . . C78 C 0.4534(3) 1.0742(2) 0.1976(2) 0.0712(11) Uani 1 1 d . . . H78A H 0.3902 1.0344 0.1627 0.107 Uiso 1 1 calc R . . H78B H 0.5095 1.1052 0.1690 0.107 Uiso 1 1 calc R . . H78C H 0.4045 1.1116 0.2314 0.107 Uiso 1 1 calc R . . C91 C 0.1625(9) 0.5168(8) 0.4706(6) 0.108(5) Uani 0.50 1 d PG A -1 C92 C 0.0909(12) 0.5837(6) 0.4878(6) 0.110(6) Uani 0.50 1 d PG A -1 H92 H 0.1310 0.6366 0.4868 0.132 Uiso 0.50 1 calc PR A -1 C93 C -0.0394(12) 0.5731(7) 0.5065(6) 0.131(8) Uani 0.50 1 d PG A -1 H93 H -0.0884 0.6188 0.5182 0.157 Uiso 0.50 1 calc PR A -1 C94 C -0.0981(8) 0.4956(7) 0.5080(6) 0.127(7) Uani 0.50 1 d PG A -1 H94 H -0.1872 0.4883 0.5208 0.152 Uiso 0.50 1 calc PR A -1 C95 C -0.0265(8) 0.4287(6) 0.4908(6) 0.085(4) Uani 0.50 1 d PG A -1 H95 H -0.0666 0.3757 0.4918 0.102 Uiso 0.50 1 calc PR A -1 C96 C 0.1039(8) 0.4393(7) 0.4721(6) 0.082(3) Uani 0.50 1 d PG A -1 H96 H 0.1528 0.3935 0.4604 0.099 Uiso 0.50 1 calc PR A -1 C97 C 0.2974(14) 0.5304(7) 0.4527(6) 0.129(4) Uani 0.50 1 d P A -1 H97A H 0.3095 0.5810 0.4341 0.193 Uiso 0.50 1 calc PR A -1 H97B H 0.3170 0.4847 0.4138 0.193 Uiso 0.50 1 calc PR A -1 H97C H 0.3578 0.5347 0.4980 0.193 Uiso 0.50 1 calc PR A -1 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 0.0274(2) 0.0312(3) 0.0297(2) 0.00172(19) 0.00134(18) -0.00055(17) Ti2 0.0335(3) 0.0452(3) 0.0309(3) 0.0008(2) 0.00372(19) 0.0006(2) F1 0.0575(11) 0.0780(14) 0.0864(14) 0.0421(12) 0.0145(10) 0.0029(9) F2 0.0449(10) 0.0611(11) 0.0750(13) -0.0102(10) 0.0145(9) 0.0058(8) F3 0.0353(9) 0.0650(12) 0.0758(13) -0.0035(10) -0.0083(8) -0.0087(8) F4 0.156(2) 0.0924(18) 0.0581(14) -0.0102(13) -0.0206(15) -0.0339(16) F5 0.1069(19) 0.0833(16) 0.1105(19) -0.0056(14) 0.0560(16) 0.0062(13) F6 0.149(2) 0.0487(12) 0.0916(17) 0.0182(12) 0.0230(15) 0.0080(13) N1 0.0278(10) 0.0303(11) 0.0328(11) 0.0010(9) 0.0022(8) -0.0005(8) N2 0.0281(11) 0.0379(12) 0.0352(12) 0.0038(10) 0.0048(9) 0.0034(9) O1 0.0374(10) 0.0375(10) 0.0485(11) 0.0113(9) -0.0031(8) -0.0051(8) O2 0.0389(10) 0.0367(10) 0.0373(10) -0.0031(8) -0.0020(8) 0.0056(8) O3 0.0287(9) 0.0494(11) 0.0324(10) 0.0053(8) 0.0021(7) 0.0029(8) O4A 0.0314(9) 0.0470(11) 0.0341(10) 0.0040(8) -0.0029(7) -0.0007(8) O4B 0.0515(12) 0.0571(13) 0.0564(13) -0.0163(11) 0.0100(10) -0.0006(10) O4C 0.0674(14) 0.0646(14) 0.0467(12) 0.0229(11) -0.0176(10) -0.0063(11) O5 0.0323(10) 0.0617(13) 0.0359(10) 0.0055(9) 0.0023(8) 0.0006(8) O6 0.0421(10) 0.0452(11) 0.0327(10) 0.0037(8) 0.0047(8) -0.0008(8) O7 0.0494(11) 0.0443(11) 0.0412(11) -0.0011(9) 0.0058(9) 0.0038(9) O8A 0.0509(12) 0.0763(15) 0.0351(11) 0.0016(10) -0.0018(9) 0.0031(10) O8B 0.0435(13) 0.0968(19) 0.0767(17) 0.0223(14) 0.0002(11) -0.0011(12) O8C 0.0981(18) 0.0542(14) 0.0660(15) 0.0278(12) 0.0030(13) -0.0038(12) S1 0.0356(4) 0.0462(4) 0.0346(4) 0.0001(3) -0.0019(3) -0.0019(3) S2 0.0507(4) 0.0491(4) 0.0404(4) 0.0090(3) -0.0019(3) -0.0023(3) C1 0.0363(14) 0.0400(16) 0.0409(15) -0.0066(12) -0.0024(12) 0.0014(11) C2 0.0277(13) 0.0442(16) 0.0416(15) 0.0022(13) 0.0031(11) 0.0012(11) C3 0.0345(14) 0.0401(15) 0.0375(15) 0.0070(12) 0.0021(11) 0.0020(11) C4 0.0353(15) 0.0447(17) 0.0531(18) 0.0004(14) 0.0009(13) 0.0008(12) C5 0.0350(14) 0.0421(15) 0.0314(14) 0.0027(12) 0.0051(11) 0.0062(11) C6 0.0279(13) 0.0431(15) 0.0377(15) 0.0041(12) 0.0029(11) 0.0007(11) C7 0.0367(14) 0.0400(15) 0.0408(15) 0.0074(12) 0.0035(12) 0.0011(11) C8 0.091(3) 0.052(2) 0.046(2) 0.0071(16) 0.0071(19) -0.0090(18) C11 0.0317(14) 0.0323(14) 0.0536(18) 0.0034(13) 0.0001(12) -0.0015(11) C12 0.0408(16) 0.0336(15) 0.067(2) 0.0105(14) 0.0112(14) 0.0033(12) C13 0.0418(16) 0.0345(16) 0.085(2) 0.0167(16) 0.0154(16) 0.0020(12) C14 0.0324(15) 0.0316(16) 0.093(3) 0.0045(16) 0.0064(16) -0.0001(12) C15 0.0343(15) 0.0392(16) 0.068(2) -0.0023(15) -0.0018(14) 0.0003(12) C16 0.0342(14) 0.0313(14) 0.0550(18) -0.0044(13) 0.0061(13) 0.0015(11) C17 0.072(2) 0.054(2) 0.075(2) 0.0305(18) 0.0022(19) -0.0062(16) C18 0.0409(17) 0.0443(19) 0.123(3) 0.012(2) -0.0045(19) -0.0085(14) C21 0.0365(14) 0.0343(14) 0.0405(15) 0.0049(12) 0.0075(12) 0.0040(11) C22 0.0403(15) 0.0356(15) 0.0519(17) -0.0012(13) 0.0098(13) -0.0019(12) C23 0.0479(17) 0.0300(15) 0.071(2) -0.0010(14) 0.0206(16) 0.0000(12) C24 0.0385(15) 0.0361(16) 0.071(2) 0.0142(15) 0.0197(15) 0.0063(12) C25 0.0328(14) 0.0429(16) 0.0563(18) 0.0117(14) 0.0114(12) 0.0045(11) C26 0.0336(14) 0.0375(15) 0.0419(15) 0.0065(12) 0.0090(12) 0.0030(11) C27 0.061(2) 0.0437(18) 0.069(2) -0.0182(16) -0.0026(17) -0.0002(15) C28 0.0463(18) 0.0423(18) 0.109(3) 0.0177(18) 0.0221(18) 0.0106(14) C31 0.0345(14) 0.0398(15) 0.0302(14) 0.0017(11) 0.0027(11) 0.0022(11) C32 0.0323(14) 0.0458(16) 0.0387(15) 0.0037(12) 0.0045(11) 0.0019(11) C33 0.0422(16) 0.0572(19) 0.0379(16) 0.0054(14) 0.0125(12) 0.0105(13) C34 0.0554(18) 0.0587(19) 0.0322(15) 0.0074(14) 0.0101(13) 0.0169(14) C35 0.0448(16) 0.0563(18) 0.0361(15) 0.0048(14) 0.0016(12) 0.0129(13) C36 0.0380(14) 0.0404(15) 0.0334(14) 0.0031(12) 0.0054(11) 0.0036(11) C37 0.0345(15) 0.091(3) 0.0488(18) 0.0182(17) 0.0088(13) 0.0120(15) C38 0.081(2) 0.102(3) 0.0397(18) 0.0209(19) 0.0185(17) 0.044(2) C51 0.0311(14) 0.0437(16) 0.0420(16) 0.0117(13) 0.0054(12) 0.0054(11) C52 0.0321(14) 0.0433(16) 0.0579(18) 0.0171(14) 0.0028(13) 0.0078(11) C53 0.0318(14) 0.0515(18) 0.071(2) 0.0281(16) 0.0111(14) 0.0114(12) C54 0.0456(17) 0.0490(17) 0.062(2) 0.0292(16) 0.0232(15) 0.0195(13) C55 0.0436(16) 0.0442(16) 0.0450(16) 0.0160(13) 0.0117(13) 0.0149(12) C56 0.0342(14) 0.0407(15) 0.0416(16) 0.0124(12) 0.0088(12) 0.0093(11) C57 0.0384(16) 0.066(2) 0.073(2) 0.0180(18) -0.0062(15) -0.0036(14) C58 0.061(2) 0.086(3) 0.077(2) 0.032(2) 0.0363(19) 0.0215(18) C61 0.0337(14) 0.0411(15) 0.0362(15) 0.0004(12) 0.0092(11) 0.0014(11) C62 0.0446(16) 0.0426(16) 0.0421(16) 0.0049(13) 0.0133(13) 0.0085(12) C63 0.0474(17) 0.0348(16) 0.062(2) 0.0041(14) 0.0127(15) 0.0039(12) C64 0.0424(16) 0.0425(17) 0.0575(19) -0.0037(14) 0.0022(14) -0.0007(13) C65 0.0393(15) 0.0459(17) 0.0447(17) 0.0021(13) 0.0008(12) 0.0016(12) C66 0.0308(13) 0.0409(15) 0.0389(15) 0.0003(12) 0.0060(11) 0.0022(11) C67 0.071(2) 0.0463(18) 0.0519(19) 0.0102(15) 0.0110(16) 0.0121(15) C68 0.072(2) 0.0441(19) 0.080(3) -0.0072(18) -0.0120(19) -0.0097(16) C71 0.0338(14) 0.0388(16) 0.0559(18) 0.0024(14) 0.0071(13) -0.0057(12) C72 0.0410(16) 0.0343(16) 0.072(2) -0.0036(15) 0.0225(15) -0.0079(12) C73 0.0363(16) 0.0297(15) 0.096(3) -0.0003(16) 0.0220(16) -0.0024(12) C74 0.0324(15) 0.0316(15) 0.090(3) 0.0033(16) 0.0010(15) -0.0047(11) C75 0.0345(14) 0.0362(16) 0.0634(19) 0.0052(14) -0.0006(13) -0.0041(12) C76 0.0317(14) 0.0351(15) 0.0503(17) 0.0031(13) 0.0032(12) -0.0031(11) C77 0.085(3) 0.052(2) 0.074(2) 0.0034(18) 0.045(2) 0.0041(17) C78 0.0444(18) 0.0448(19) 0.119(3) 0.007(2) -0.0077(19) 0.0061(14) C91 0.151(12) 0.087(9) 0.070(8) 0.020(7) -0.068(8) -0.023(9) C92 0.161(15) 0.089(9) 0.059(8) -0.026(6) -0.053(8) 0.048(9) C93 0.19(2) 0.077(10) 0.100(11) -0.042(9) -0.082(11) 0.073(11) C94 0.206(17) 0.105(12) 0.060(7) -0.016(7) -0.051(9) 0.079(13) C95 0.130(13) 0.072(7) 0.046(6) -0.005(5) -0.031(6) 0.045(6) C96 0.106(8) 0.062(6) 0.070(7) 0.004(5) -0.037(6) 0.014(6) C97 0.179(12) 0.108(8) 0.086(7) 0.027(6) -0.022(8) -0.043(8) _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 O1 1.7932(17) . ? Ti1 O2 1.7986(17) . ? Ti1 O3 1.8082(17) . ? Ti1 O4A 2.0016(17) . ? Ti1 N1 2.216(2) . ? Ti2 O5 1.7988(18) . ? Ti2 O7 1.799(2) . ? Ti2 O6 1.8109(18) . ? Ti2 O8A 2.017(2) . ? Ti2 N2 2.213(2) . ? F1 C4 1.334(3) . ? F2 C4 1.321(3) . ? F3 C4 1.328(3) . ? F4 C8 1.319(4) . ? F5 C8 1.318(4) . ? F6 C8 1.309(4) . ? N1 C2 1.499(3) . ? N1 C3 1.499(3) . ? N1 C1 1.505(3) . ? N2 C5 1.504(3) . ? N2 C6 1.505(3) . ? N2 C7 1.506(3) . ? O1 C11 1.374(3) . ? O2 C21 1.373(3) . ? O3 C31 1.372(3) . ? O4A S1 1.4797(18) . ? O4B S1 1.417(2) . ? O4C S1 1.425(2) . ? O5 C51 1.372(3) . ? O6 C61 1.370(3) . ? O7 C71 1.371(3) . ? O8A S2 1.463(2) . ? O8B S2 1.423(2) . ? O8C S2 1.423(2) . ? S1 C4 1.817(3) . ? S2 C8 1.812(4) . ? C1 C16 1.516(4) . ? C2 C26 1.507(4) . ? C3 C36 1.506(3) . ? C5 C56 1.508(4) . ? C6 C66 1.493(4) . ? C7 C76 1.503(4) . ? C11 C12 1.391(4) . ? C11 C16 1.395(4) . ? C12 C13 1.394(4) . ? C12 C17 1.498(4) . ? C13 C14 1.382(5) . ? C14 C15 1.402(4) . ? C14 C18 1.520(4) . ? C15 C16 1.393(4) . ? C21 C22 1.386(4) . ? C21 C26 1.397(4) . ? C22 C23 1.391(4) . ? C22 C27 1.501(4) . ? C23 C24 1.378(4) . ? C24 C25 1.400(4) . ? C24 C28 1.515(4) . ? C25 C26 1.394(4) . ? C31 C36 1.393(4) . ? C31 C32 1.394(4) . ? C32 C33 1.390(4) . ? C32 C37 1.506(4) . ? C33 C34 1.388(4) . ? C34 C35 1.384(4) . ? C34 C38 1.514(4) . ? C35 C36 1.388(4) . ? C51 C56 1.390(4) . ? C51 C52 1.400(4) . ? C52 C53 1.397(4) . ? C52 C57 1.497(4) . ? C53 C54 1.382(4) . ? C54 C55 1.400(4) . ? C54 C58 1.508(4) . ? C55 C56 1.390(4) . ? C61 C66 1.392(4) . ? C61 C62 1.393(4) . ? C62 C63 1.390(4) . ? C62 C67 1.503(4) . ? C63 C64 1.386(4) . ? C64 C65 1.390(4) . ? C64 C68 1.514(4) . ? C65 C66 1.389(4) . ? C71 C72 1.389(4) . ? C71 C76 1.402(4) . ? C72 C73 1.388(5) . ? C72 C77 1.506(5) . ? C73 C74 1.390(5) . ? C74 C75 1.389(4) . ? C74 C78 1.509(5) . ? C75 C76 1.383(4) . ? C91 C92 1.3900 . ? C91 C96 1.3900 . ? C91 C97 1.434(15) . ? C92 C93 1.3900 . ? C93 C94 1.3900 . ? C94 C95 1.3900 . ? C95 C96 1.3900 . ? 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 Ti1 O2 116.34(9) . . ? O1 Ti1 O3 118.03(9) . . ? O2 Ti1 O3 122.74(9) . . ? O1 Ti1 O4A 97.34(8) . . ? O2 Ti1 O4A 96.17(8) . . ? O3 Ti1 O4A 93.61(7) . . ? O1 Ti1 N1 85.05(8) . . ? O2 Ti1 N1 83.94(8) . . ? O3 Ti1 N1 84.05(7) . . ? O4A Ti1 N1 177.25(7) . . ? O5 Ti2 O7 114.34(9) . . ? O5 Ti2 O6 120.05(9) . . ? O7 Ti2 O6 122.38(9) . . ? O5 Ti2 O8A 100.67(8) . . ? O7 Ti2 O8A 95.52(9) . . ? O6 Ti2 O8A 92.07(9) . . ? O5 Ti2 N2 84.54(8) . . ? O7 Ti2 N2 84.41(8) . . ? O6 Ti2 N2 83.16(8) . . ? O8A Ti2 N2 174.26(8) . . ? C2 N1 C3 108.13(19) . . ? C2 N1 C1 108.62(19) . . ? C3 N1 C1 108.4(2) . . ? C2 N1 Ti1 111.75(15) . . ? C3 N1 Ti1 110.64(14) . . ? C1 N1 Ti1 109.21(15) . . ? C5 N2 C6 108.74(19) . . ? C5 N2 C7 109.40(19) . . ? C6 N2 C7 107.42(19) . . ? C5 N2 Ti2 109.25(15) . . ? C6 N2 Ti2 110.68(15) . . ? C7 N2 Ti2 111.30(15) . . ? C11 O1 Ti1 141.94(17) . . ? C21 O2 Ti1 143.15(16) . . ? C31 O3 Ti1 142.62(16) . . ? S1 O4A Ti1 158.14(12) . . ? C51 O5 Ti2 141.71(17) . . ? C61 O6 Ti2 143.16(17) . . ? C71 O7 Ti2 142.04(18) . . ? S2 O8A Ti2 149.78(14) . . ? O4B S1 O4C 117.84(14) . . ? O4B S1 O4A 114.02(12) . . ? O4C S1 O4A 111.61(12) . . ? O4B S1 C4 104.71(13) . . ? O4C S1 C4 105.02(14) . . ? O4A S1 C4 101.51(12) . . ? O8B S2 O8C 118.57(16) . . ? O8B S2 O8A 111.90(14) . . ? O8C S2 O8A 112.61(14) . . ? O8B S2 C8 105.76(17) . . ? O8C S2 C8 104.13(16) . . ? O8A S2 C8 101.83(15) . . ? N1 C1 C16 113.1(2) . . ? N1 C2 C26 113.0(2) . . ? N1 C3 C36 114.5(2) . . ? F2 C4 F3 108.3(2) . . ? F2 C4 F1 107.8(3) . . ? F3 C4 F1 108.2(2) . . ? F2 C4 S1 112.4(2) . . ? F3 C4 S1 110.1(2) . . ? F1 C4 S1 109.98(19) . . ? N2 C5 C56 113.1(2) . . ? C66 C6 N2 113.5(2) . . ? C76 C7 N2 112.7(2) . . ? F6 C8 F5 108.4(3) . . ? F6 C8 F4 107.5(3) . . ? F5 C8 F4 107.7(3) . . ? F6 C8 S2 112.2(2) . . ? F5 C8 S2 110.6(2) . . ? F4 C8 S2 110.2(3) . . ? O1 C11 C12 119.2(3) . . ? O1 C11 C16 118.1(2) . . ? C12 C11 C16 122.7(2) . . ? C11 C12 C13 116.4(3) . . ? C11 C12 C17 121.1(3) . . ? C13 C12 C17 122.5(3) . . ? C14 C13 C12 123.4(3) . . ? C13 C14 C15 118.4(3) . . ? C13 C14 C18 121.8(3) . . ? C15 C14 C18 119.8(3) . . ? C16 C15 C14 120.4(3) . . ? C15 C16 C11 118.8(3) . . ? C15 C16 C1 120.7(3) . . ? C11 C16 C1 120.5(2) . . ? O2 C21 C22 119.4(2) . . ? O2 C21 C26 118.0(2) . . ? C22 C21 C26 122.6(2) . . ? C21 C22 C23 116.8(3) . . ? C21 C22 C27 121.1(3) . . ? C23 C22 C27 122.0(3) . . ? C24 C23 C22 123.0(3) . . ? C23 C24 C25 118.6(3) . . ? C23 C24 C28 121.0(3) . . ? C25 C24 C28 120.4(3) . . ? C26 C25 C24 120.5(3) . . ? C25 C26 C21 118.3(3) . . ? C25 C26 C2 121.4(2) . . ? C21 C26 C2 120.3(2) . . ? O3 C31 C36 118.8(2) . . ? O3 C31 C32 119.7(2) . . ? C36 C31 C32 121.4(2) . . ? C33 C32 C31 117.6(2) . . ? C33 C32 C37 122.0(2) . . ? C31 C32 C37 120.4(2) . . ? C34 C33 C32 122.6(3) . . ? C35 C34 C33 117.9(3) . . ? C35 C34 C38 120.7(3) . . ? C33 C34 C38 121.4(3) . . ? C34 C35 C36 121.7(3) . . ? C35 C36 C31 118.7(2) . . ? C35 C36 C3 120.8(2) . . ? C31 C36 C3 120.4(2) . . ? O5 C51 C56 118.3(2) . . ? O5 C51 C52 119.3(2) . . ? C56 C51 C52 122.4(2) . . ? C53 C52 C51 116.1(3) . . ? C53 C52 C57 122.9(3) . . ? C51 C52 C57 120.9(3) . . ? C54 C53 C52 123.5(3) . . ? C53 C54 C55 118.3(3) . . ? C53 C54 C58 121.9(3) . . ? C55 C54 C58 119.8(3) . . ? C56 C55 C54 120.6(3) . . ? C55 C56 C51 119.0(2) . . ? C55 C56 C5 120.4(2) . . ? C51 C56 C5 120.5(2) . . ? O6 C61 C66 118.2(2) . . ? O6 C61 C62 119.8(2) . . ? C66 C61 C62 122.0(2) . . ? C63 C62 C61 117.0(3) . . ? C63 C62 C67 122.2(3) . . ? C61 C62 C67 120.7(3) . . ? C64 C63 C62 123.0(3) . . ? C63 C64 C65 118.0(3) . . ? C63 C64 C68 121.6(3) . . ? C65 C64 C68 120.4(3) . . ? C66 C65 C64 121.3(3) . . ? C65 C66 C61 118.7(3) . . ? C65 C66 C6 121.4(2) . . ? C61 C66 C6 119.8(2) . . ? O7 C71 C72 119.6(3) . . ? O7 C71 C76 118.5(2) . . ? C72 C71 C76 121.8(3) . . ? C73 C72 C71 117.1(3) . . ? C73 C72 C77 123.5(3) . . ? C71 C72 C77 119.4(3) . . ? C72 C73 C74 122.8(3) . . ? C75 C74 C73 118.4(3) . . ? C75 C74 C78 120.3(3) . . ? C73 C74 C78 121.3(3) . . ? C76 C75 C74 120.9(3) . . ? C75 C76 C71 118.9(3) . . ? C75 C76 C7 122.0(3) . . ? C71 C76 C7 119.1(2) . . ? C92 C91 C96 120.0 . . ? C92 C91 C97 118.3(9) . . ? C96 C91 C97 121.7(9) . . ? C93 C92 C91 120.0 . . ? C92 C93 C94 120.0 . . ? C95 C94 C93 120.0 . . ? C94 C95 C96 120.0 . . ? C95 C96 C91 120.0 . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.502 _refine_diff_density_min -0.373 _refine_diff_density_rms 0.049