# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 186/1706 data_2b _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C20 H22 Cl N O4 Ti' _chemical_formula_weight 423.74 _chemical_melting_point ? _chemical_compound_source ? 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' 'Cl' 'Cl' 0.1484 0.1585 '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 ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, z' 'x, -y+1/2, z+1/2' '-x+1/2, -y, z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, -z' '-x, y-1/2, -z-1/2' 'x-1/2, y, -z-1/2' _cell_length_a 8.7570(10) _cell_length_b 16.150(8) _cell_length_c 27.766(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3926.8(21) _cell_formula_units_Z 8 _cell_measurement_temperature 453(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.433 _exptl_crystal_density_method ? _exptl_crystal_F_000 1760 _exptl_absorpt_coefficient_mu 0.597 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 453(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device ? _diffrn_measurement_method ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3607 _diffrn_reflns_av_R_equivalents 0.0184 _diffrn_reflns_av_sigmaI/netI 0.0446 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -1 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 2.52 _diffrn_reflns_theta_max 24.96 _reflns_number_total 3455 _reflns_number_observed 2406 _reflns_observed_criterion >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0677P)^2^+0.0000P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3455 _refine_ls_number_parameters 244 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0708 _refine_ls_R_factor_obs 0.0394 _refine_ls_wR_factor_all 0.1123 _refine_ls_wR_factor_obs 0.1043 _refine_ls_goodness_of_fit_all 1.032 _refine_ls_goodness_of_fit_obs 1.167 _refine_ls_restrained_S_all 1.032 _refine_ls_restrained_S_obs 1.167 _refine_ls_shift/esd_max 0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti1 Ti 0.11572(6) 0.68900(3) 0.09523(2) 0.0235(2) Uani 1 d . . Cl1 Cl 0.34585(9) 0.61842(5) 0.08132(3) 0.0388(2) Uani 1 d . . O4 O 0.0085(2) 0.58200(11) 0.09777(7) 0.0290(5) Uani 1 d . . O3 O -0.0921(2) 0.73291(12) 0.11490(8) 0.0303(5) Uani 1 d . . O2 O 0.0868(2) 0.71296(12) 0.03248(7) 0.0295(5) Uani 1 d . . O1 O 0.1803(2) 0.70491(12) 0.15960(7) 0.0288(5) Uani 1 d . . N1 N 0.1985(2) 0.81509(14) 0.08974(8) 0.0222(5) Uani 1 d . . C18 C -0.2219(3) 0.6984(2) 0.12131(10) 0.0301(7) Uani 1 d . . C11 C 0.2529(3) 0.8626(2) 0.12303(9) 0.0233(6) Uani 1 d . . H11 H 0.2722(3) 0.9193(2) 0.11458(9) 0.080 Uiso 1 d R . C1 C 0.2555(3) 0.7572(2) 0.18703(10) 0.0254(6) Uani 1 d . . C10 C 0.2872(3) 0.8384(2) 0.17161(10) 0.0220(6) Uani 1 d . . C17 C -0.2447(4) 0.6136(2) 0.11769(12) 0.0340(7) Uani 1 d . . H17 H -0.3454(4) 0.5922(2) 0.12319(12) 0.080 Uiso 1 d R . C4 C 0.3981(3) 0.8677(2) 0.25152(11) 0.0293(7) Uani 1 d . . C7 C 0.4406(4) 1.0343(2) 0.22838(12) 0.0376(8) Uani 1 d . . H7 H 0.4572(4) 1.0913(2) 0.22019(12) 0.080 Uiso 1 d R . C12 C 0.1688(3) 0.8534(2) 0.04096(10) 0.0252(6) Uani 1 d . . C8 C 0.3768(3) 0.9817(2) 0.19481(11) 0.0315(7) Uani 1 d . . H8 H 0.3472(3) 1.0027(2) 0.16386(11) 0.080 Uiso 1 d R . C20 C -0.1579(4) 0.4684(2) 0.10317(14) 0.0445(9) Uani 1 d . . H20A H -0.0648(4) 0.4405(2) 0.09490(14) 0.080 Uiso 1 d R . H20B H -0.1935(4) 0.4488(2) 0.13384(14) 0.080 Uiso 1 d R . H20C H -0.2338(4) 0.4573(2) 0.07905(14) 0.080 Uiso 1 d R . C16 C -0.1292(3) 0.5593(2) 0.10635(11) 0.0291(7) Uani 1 d . . C3 C 0.3762(3) 0.7835(2) 0.26378(11) 0.0342(7) Uani 1 d . . H3 H 0.4112(3) 0.7638(2) 0.29447(11) 0.080 Uiso 1 d R . C5 C 0.4593(4) 0.9242(2) 0.28548(11) 0.0380(8) Uani 1 d . . H5 H 0.4848(4) 0.9046(2) 0.31711(11) 0.080 Uiso 1 d R . C6 C 0.4826(4) 1.0055(2) 0.27404(13) 0.0415(8) Uani 1 d . . H6 H 0.5262(4) 1.0425(2) 0.29732(13) 0.080 Uiso 1 d R . C2 C 0.3054(3) 0.7302(2) 0.23289(10) 0.0318(7) Uani 1 d . . H2 H 0.2885(3) 0.6737(2) 0.24221(10) 0.080 Uiso 1 d R . C15 C 0.0155(4) 0.8979(2) 0.04351(11) 0.0336(7) Uani 1 d . . H15A H 0.0237(4) 0.9448(2) 0.06459(11) 0.080 Uiso 1 d R . H15B H -0.0131(4) 0.9163(2) 0.01189(11) 0.080 Uiso 1 d R . H15C H -0.0606(4) 0.8606(2) 0.05564(11) 0.080 Uiso 1 d R . C13 C 0.1604(4) 0.7776(2) 0.00760(11) 0.0317(7) Uani 1 d . . H13 H 0.1043(4) 0.7909(2) -0.02108(11) 0.080 Uiso 1 d R . H13 H 0.2614(4) 0.7606(2) -0.00149(11) 0.080 Uiso 1 d R . C19 C -0.3544(4) 0.7546(2) 0.13289(14) 0.0425(8) Uani 1 d . . H19A H -0.3193(4) 0.8108(2) 0.13417(14) 0.080 Uiso 1 d R . H19B H -0.4312(4) 0.7493(2) 0.10841(14) 0.080 Uiso 1 d R . H19C H -0.3968(4) 0.7393(2) 0.16352(14) 0.080 Uiso 1 d R . C14 C 0.2958(4) 0.9113(2) 0.02398(11) 0.0358(8) Uani 1 d . . H14A H 0.3004(4) 0.9585(2) 0.04491(11) 0.080 Uiso 1 d R . H14B H 0.3918(4) 0.8826(2) 0.02470(11) 0.080 Uiso 1 d R . H14C H 0.2747(4) 0.9292(2) -0.00830(11) 0.080 Uiso 1 d R . C9 C 0.3548(3) 0.8970(2) 0.20518(10) 0.0257(6) Uani 1 d . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.0224(3) 0.0199(3) 0.0282(3) -0.0005(2) 0.0019(2) -0.0019(2) Cl1 0.0258(4) 0.0338(4) 0.0568(5) -0.0082(4) 0.0053(4) 0.0023(3) O4 0.0235(11) 0.0220(10) 0.0416(12) 0.0008(9) 0.0008(9) -0.0023(8) O3 0.0247(11) 0.0266(11) 0.0395(12) -0.0030(10) 0.0061(9) 0.0006(9) O2 0.0354(12) 0.0257(10) 0.0274(11) -0.0037(9) -0.0021(9) -0.0047(9) O1 0.0337(11) 0.0252(11) 0.0276(10) 0.0048(9) 0.0004(9) -0.0028(9) N1 0.0204(12) 0.0220(12) 0.0240(12) 0.0018(10) 0.0032(9) 0.0016(10) C18 0.027(2) 0.037(2) 0.026(2) 0.0016(13) 0.0004(12) 0.0031(14) C11 0.0232(14) 0.0213(14) 0.0255(15) 0.0006(12) 0.0026(12) 0.0010(12) C1 0.0197(14) 0.030(2) 0.027(2) -0.0012(12) 0.0035(12) 0.0035(12) C10 0.0194(14) 0.0242(14) 0.0224(14) 0.0014(12) 0.0028(11) 0.0029(11) C17 0.0227(15) 0.034(2) 0.046(2) 0.0030(15) 0.0006(14) -0.0022(13) C4 0.0204(14) 0.038(2) 0.0298(15) 0.0007(14) -0.0041(12) 0.0055(13) C7 0.035(2) 0.033(2) 0.044(2) -0.006(2) -0.004(2) -0.0006(14) C12 0.032(2) 0.0262(15) 0.0175(13) 0.0016(12) 0.0001(12) -0.0018(12) C8 0.031(2) 0.030(2) 0.033(2) -0.0045(13) -0.0050(14) -0.0008(13) C20 0.032(2) 0.030(2) 0.072(2) 0.007(2) -0.005(2) -0.0073(14) C16 0.029(2) 0.028(2) 0.031(2) 0.0063(13) -0.0077(13) -0.0035(13) C3 0.029(2) 0.047(2) 0.027(2) 0.0081(13) -0.0017(13) 0.0047(14) C5 0.031(2) 0.057(2) 0.026(2) -0.003(2) -0.0047(14) 0.007(2) C6 0.034(2) 0.044(2) 0.047(2) -0.015(2) -0.011(2) 0.002(2) C2 0.031(2) 0.034(2) 0.030(2) 0.0109(14) 0.0013(13) 0.0023(14) C15 0.038(2) 0.030(2) 0.033(2) 0.0015(14) -0.0070(15) 0.0042(14) C13 0.042(2) 0.027(2) 0.025(2) 0.0003(13) 0.0022(14) -0.0052(14) C19 0.027(2) 0.042(2) 0.058(2) -0.004(2) 0.007(2) 0.0051(15) C14 0.047(2) 0.032(2) 0.028(2) 0.0004(14) 0.0038(15) -0.0080(14) C9 0.0215(14) 0.031(2) 0.0243(15) -0.0008(12) 0.0022(12) 0.0055(12) _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 O2 1.803(2) . ? Ti1 O1 1.892(2) . ? Ti1 O4 1.968(2) . ? Ti1 O3 2.028(2) . ? Ti1 N1 2.167(2) . ? Ti1 Cl1 2.3473(10) . ? O4 C16 1.283(4) . ? O3 C18 1.278(4) . ? O2 C13 1.408(3) . ? O1 C1 1.314(3) . ? N1 C11 1.293(3) . ? N1 C12 1.511(3) . ? C18 C17 1.387(4) . ? C18 C19 1.507(4) . ? C11 C10 1.436(4) . ? C1 C10 1.407(4) . ? C1 C2 1.415(4) . ? C10 C9 1.455(4) . ? C17 C16 1.376(4) . ? C4 C3 1.415(4) . ? C4 C5 1.418(4) . ? C4 C9 1.422(4) . ? C7 C8 1.380(4) . ? C7 C6 1.399(5) . ? C12 C15 1.525(4) . ? C12 C14 1.527(4) . ? C12 C13 1.537(4) . ? C8 C9 1.410(4) . ? C20 C16 1.492(4) . ? C3 C2 1.365(4) . ? C5 C6 1.365(5) . ? 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 O2 Ti1 O1 157.79(9) . . ? O2 Ti1 O4 98.98(9) . . ? O1 Ti1 O4 103.19(8) . . ? O2 Ti1 O3 93.40(9) . . ? O1 Ti1 O3 88.08(9) . . ? O4 Ti1 O3 82.48(8) . . ? O2 Ti1 N1 77.13(8) . . ? O1 Ti1 N1 80.73(8) . . ? O4 Ti1 N1 170.86(8) . . ? O3 Ti1 N1 89.45(8) . . ? O2 Ti1 Cl1 93.76(7) . . ? O1 Ti1 Cl1 87.98(7) . . ? O4 Ti1 Cl1 89.38(7) . . ? O3 Ti1 Cl1 169.91(7) . . ? N1 Ti1 Cl1 99.07(7) . . ? C16 O4 Ti1 135.0(2) . . ? C18 O3 Ti1 133.1(2) . . ? C13 O2 Ti1 124.7(2) . . ? C1 O1 Ti1 141.7(2) . . ? C11 N1 C12 117.5(2) . . ? C11 N1 Ti1 129.1(2) . . ? C12 N1 Ti1 113.0(2) . . ? O3 C18 C17 123.3(3) . . ? O3 C18 C19 116.9(3) . . ? C17 C18 C19 119.9(3) . . ? N1 C11 C10 125.9(3) . . ? O1 C1 C10 121.4(2) . . ? O1 C1 C2 118.6(3) . . ? C10 C1 C2 120.0(3) . . ? C1 C10 C11 119.9(2) . . ? C1 C10 C9 119.5(2) . . ? C11 C10 C9 120.6(2) . . ? C16 C17 C18 122.7(3) . . ? C3 C4 C5 120.7(3) . . ? C3 C4 C9 120.1(3) . . ? C5 C4 C9 119.2(3) . . ? C8 C7 C6 120.9(3) . . ? N1 C12 C15 107.6(2) . . ? N1 C12 C14 113.7(2) . . ? C15 C12 C14 111.5(2) . . ? N1 C12 C13 102.9(2) . . ? C15 C12 C13 111.2(2) . . ? C14 C12 C13 109.7(2) . . ? C7 C8 C9 121.0(3) . . ? O4 C16 C17 123.4(3) . . ? O4 C16 C20 115.4(3) . . ? C17 C16 C20 121.2(3) . . ? C2 C3 C4 121.1(3) . . ? C6 C5 C4 121.4(3) . . ? C5 C6 C7 119.4(3) . . ? C3 C2 C1 120.7(3) . . ? O2 C13 C12 108.5(2) . . ? C8 C9 C4 118.1(3) . . ? C8 C9 C10 123.8(3) . . ? C4 C9 C10 118.1(3) . . ? _refine_diff_density_max 0.397 _refine_diff_density_min -0.326 _refine_diff_density_rms 0.064 data_3b _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C30 H30 N2 O4 Ti' _chemical_formula_weight 530.46 _chemical_melting_point ? _chemical_compound_source ? 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 ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 13.769(2) _cell_length_b 10.985(2) _cell_length_c 17.0552(15) _cell_angle_alpha 90.00 _cell_angle_beta 102.384(10) _cell_angle_gamma 90.00 _cell_volume 2519.8(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.398 _exptl_crystal_density_method ? _exptl_crystal_F_000 1112 _exptl_absorpt_coefficient_mu 0.380 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 ? _diffrn_measurement_method ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4613 _diffrn_reflns_av_R_equivalents 0.0190 _diffrn_reflns_av_sigmaI/netI 0.0478 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.14 _diffrn_reflns_theta_max 24.97 _reflns_number_total 4419 _reflns_number_observed 3143 _reflns_observed_criterion >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0480P)^2^+0.2750P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4419 _refine_ls_number_parameters 344 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0642 _refine_ls_R_factor_obs 0.0370 _refine_ls_wR_factor_all 0.0911 _refine_ls_wR_factor_obs 0.0848 _refine_ls_goodness_of_fit_all 0.998 _refine_ls_goodness_of_fit_obs 1.119 _refine_ls_restrained_S_all 0.998 _refine_ls_restrained_S_obs 1.119 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti1 Ti 0.46284(3) 0.06167(4) 0.67974(2) 0.02329(12) Uani 1 d . . O3 O 0.49002(12) 0.19459(15) 0.75581(9) 0.0280(4) Uani 1 d . . O1 O 0.37740(11) 0.16436(15) 0.60382(9) 0.0269(4) Uani 1 d . . O2 O 0.57805(12) -0.0217(2) 0.72639(9) 0.0316(4) Uani 1 d . . O4 O 0.39727(12) -0.07484(15) 0.63046(9) 0.0302(4) Uani 1 d . . N2 N 0.37260(13) 0.0063(2) 0.76395(10) 0.0200(4) Uani 1 d . . N1 N 0.56503(13) 0.1150(2) 0.60614(10) 0.0199(4) Uani 1 d . . C25 C 0.4367(2) 0.1430(2) 0.87497(13) 0.0215(5) Uani 1 d . . C10 C 0.4644(2) 0.2584(2) 0.51429(12) 0.0211(5) Uani 1 d . . C21 C 0.4500(2) 0.2363(2) 1.12082(14) 0.0317(6) Uani 1 d . . H21 H 0.4524(2) 0.2575(2) 1.17398(14) 0.038 Uiso 1 calc R . C24 C 0.4393(2) 0.1720(2) 0.95854(13) 0.0217(5) Uani 1 d . . C12 C 0.6671(2) 0.0627(2) 0.63496(13) 0.0249(5) Uani 1 d . . C16 C 0.4893(2) 0.2161(2) 0.83127(13) 0.0231(5) Uani 1 d . . C20 C 0.4948(2) 0.3077(2) 1.07351(13) 0.0291(6) Uani 1 d . . H20 H 0.5279(2) 0.3779(2) 1.09505(13) 0.035 Uiso 1 calc R . C19 C 0.4919(2) 0.2778(2) 0.99301(14) 0.0238(5) Uani 1 d . . C26 C 0.3763(2) 0.0449(2) 0.83616(13) 0.0215(5) Uani 1 d . . H26 H 0.3321(17) 0.0050(21) 0.8676(13) 0.026 Uiso 1 d . . C6 C 0.4532(3) 0.5371(2) 0.3392(2) 0.0511(9) Uani 1 d . . H6 H 0.4510(3) 0.6006(2) 0.3028(2) 0.061 Uiso 1 calc R . C17 C 0.5422(2) 0.3196(2) 0.86788(14) 0.0284(6) Uani 1 d . . H17 H 0.5770(2) 0.3676(2) 0.83837(14) 0.034 Uiso 1 calc R . C13 C 0.6457(2) -0.0522(2) 0.67872(14) 0.0291(5) Uani 1 d . . H13A H 0.6177(2) -0.1146(2) 0.64024(14) 0.035 Uiso 1 calc R . H13B H 0.7067(2) -0.0833(2) 0.71205(14) 0.035 Uiso 1 calc R . C11 C 0.5535(2) 0.1930(2) 0.54795(13) 0.0232(5) Uani 1 d . . H11 H 0.6124(17) 0.2084(21) 0.5246(13) 0.028 Uiso 1 d . . C28 C 0.3523(2) -0.1590(2) 0.67318(14) 0.0286(5) Uani 1 d . . H28A H 0.4023(2) -0.2122(2) 0.70431(14) 0.034 Uiso 1 calc R . H28B H 0.3052(2) -0.2086(2) 0.63618(14) 0.034 Uiso 1 calc R . C27 C 0.2988(2) -0.0897(2) 0.72892(13) 0.0240(5) Uani 1 d . . C18 C 0.5429(2) 0.3494(2) 0.94527(14) 0.0274(5) Uani 1 d . . H18 H 0.5775(2) 0.4182(2) 0.96752(14) 0.033 Uiso 1 calc R . C1 C 0.3783(2) 0.2364(2) 0.54288(13) 0.0229(5) Uani 1 d . . C29 C 0.2682(2) -0.1755(2) 0.78919(14) 0.0283(6) Uani 1 d . . H29A H 0.3265(2) -0.2061(11) 0.8251(6) 0.042 Uiso 1 calc R . H29B H 0.2311(10) -0.2423(8) 0.7612(2) 0.042 Uiso 1 calc R . H29C H 0.2277(9) -0.1325(4) 0.8193(6) 0.042 Uiso 1 calc R . C9 C 0.4629(2) 0.3484(2) 0.45269(13) 0.0250(5) Uani 1 d . . C4 C 0.3714(2) 0.4065(2) 0.41851(13) 0.0315(6) Uani 1 d . . C3 C 0.2841(2) 0.3716(2) 0.44398(15) 0.0365(6) Uani 1 d . . H5 H 0.2234(2) 0.4047(2) 0.41835(15) 0.044 Uiso 1 calc R . C15 C 0.7203(2) 0.0316(3) 0.56771(15) 0.0360(6) Uani 1 d . . H15A H 0.6742(4) -0.0057(14) 0.5241(4) 0.054 Uiso 1 calc R . H15B H 0.7739(8) -0.0238(12) 0.5875(3) 0.054 Uiso 1 calc R . H15C H 0.7463(11) 0.1047(3) 0.5492(7) 0.054 Uiso 1 calc R . C22 C 0.4009(2) 0.1312(2) 1.08840(14) 0.0346(6) Uani 1 d . . H22 H 0.3717(2) 0.0811(2) 1.12071(14) 0.042 Uiso 1 calc R . C2 C 0.2866(2) 0.2915(2) 0.50456(14) 0.0313(6) Uani 1 d . . H2 H 0.2284(2) 0.2723(2) 0.52126(14) 0.038 Uiso 1 calc R . C8 C 0.5483(2) 0.3863(2) 0.42629(14) 0.0335(6) Uani 1 d . . H8 H 0.6090(2) 0.3488(2) 0.44674(14) 0.040 Uiso 1 calc R . C30 C 0.2078(2) -0.0239(2) 0.67941(15) 0.0321(6) Uani 1 d . . H30A H 0.1768(7) 0.0237(12) 0.7144(2) 0.048 Uiso 1 calc R . H30B H 0.1612(6) -0.0828(2) 0.6519(8) 0.048 Uiso 1 calc R . H30C H 0.2283(2) 0.0285(11) 0.6409(7) 0.048 Uiso 1 calc R . C23 C 0.3949(2) 0.1004(2) 1.00943(14) 0.0319(6) Uani 1 d . . H23 H 0.3605(2) 0.0303(2) 0.98917(14) 0.038 Uiso 1 calc R . C7 C 0.5431(2) 0.4778(2) 0.3709(2) 0.0457(8) Uani 1 d . . H7 H 0.6004(2) 0.5009(2) 0.3540(2) 0.055 Uiso 1 calc R . C14 C 0.7267(2) 0.1533(2) 0.69349(15) 0.0325(6) Uani 1 d . . H14A H 0.7324(10) 0.2285(5) 0.6661(3) 0.049 Uiso 1 calc R . H14B H 0.7919(4) 0.1209(7) 0.7146(7) 0.049 Uiso 1 calc R . H14C H 0.6936(6) 0.1677(11) 0.7367(5) 0.049 Uiso 1 calc R . C5 C 0.3697(2) 0.5009(2) 0.36204(14) 0.0423(7) Uani 1 d . . H5 H 0.3097(2) 0.5390(2) 0.34010(14) 0.051 Uiso 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 0.0258(2) 0.0261(2) 0.0189(2) 0.0034(2) 0.0071(2) -0.0014(2) O3 0.0333(9) 0.0291(9) 0.0235(9) 0.0006(7) 0.0102(7) -0.0087(8) O1 0.0220(8) 0.0324(9) 0.0273(9) 0.0057(7) 0.0076(7) 0.0014(7) O2 0.0365(10) 0.0330(10) 0.0256(9) 0.0093(7) 0.0074(7) 0.0047(8) O4 0.0397(10) 0.0315(10) 0.0215(8) -0.0020(7) 0.0110(7) -0.0050(8) N2 0.0218(10) 0.0175(10) 0.0202(9) 0.0019(8) 0.0035(8) 0.0004(8) N1 0.0180(10) 0.0228(10) 0.0178(9) -0.0006(8) 0.0015(8) 0.0027(8) C25 0.0203(12) 0.0200(12) 0.0243(12) 0.0008(10) 0.0054(10) -0.0006(9) C10 0.0272(12) 0.0183(12) 0.0172(11) -0.0005(9) 0.0034(9) 0.0025(10) C21 0.0300(14) 0.044(2) 0.0220(12) -0.0071(11) 0.0063(11) 0.0015(12) C24 0.0201(11) 0.0212(12) 0.0232(12) 0.0019(10) 0.0035(9) 0.0024(9) C12 0.0206(11) 0.0283(13) 0.0247(12) 0.0012(11) 0.0022(9) 0.0044(11) C16 0.0200(12) 0.0235(13) 0.0256(12) 0.0017(10) 0.0045(10) 0.0021(10) C20 0.0247(13) 0.0326(14) 0.0277(13) -0.0086(11) 0.0005(11) -0.0008(11) C19 0.0178(11) 0.0250(12) 0.0271(12) -0.0017(10) 0.0011(9) 0.0029(10) C26 0.0212(11) 0.0209(12) 0.0238(12) 0.0040(10) 0.0081(9) 0.0008(10) C6 0.104(3) 0.023(2) 0.0221(13) 0.0042(11) 0.005(2) -0.002(2) C17 0.0255(13) 0.0294(14) 0.0299(13) 0.0046(11) 0.0049(10) -0.0073(11) C13 0.0294(13) 0.0251(13) 0.0281(12) 0.0016(11) -0.0040(10) 0.0031(11) C11 0.0254(13) 0.0253(13) 0.0206(12) -0.0004(10) 0.0086(10) -0.0019(10) C28 0.0346(14) 0.0245(13) 0.0261(12) 0.0002(10) 0.0053(11) -0.0028(11) C27 0.0240(12) 0.0237(13) 0.0237(12) 0.0009(10) 0.0036(10) -0.0022(10) C18 0.0233(12) 0.0250(13) 0.0317(13) -0.0013(11) 0.0010(10) -0.0056(10) C1 0.0263(12) 0.0205(12) 0.0208(12) -0.0001(10) 0.0029(10) 0.0020(10) C29 0.0329(14) 0.0231(13) 0.0297(13) -0.0004(10) 0.0085(11) -0.0062(11) C9 0.0397(14) 0.0188(12) 0.0159(11) -0.0035(9) 0.0049(10) 0.0007(11) C4 0.048(2) 0.0232(13) 0.0190(12) -0.0008(10) -0.0028(11) 0.0058(12) C3 0.038(2) 0.035(2) 0.0303(14) -0.0021(12) -0.0073(12) 0.0151(12) C15 0.0283(13) 0.046(2) 0.0338(14) 0.0028(12) 0.0075(11) 0.0148(12) C22 0.041(2) 0.041(2) 0.0244(13) 0.0015(12) 0.0121(12) -0.0069(13) C2 0.0256(13) 0.0339(15) 0.0319(14) -0.0046(12) 0.0004(11) 0.0042(11) C8 0.051(2) 0.0248(13) 0.0276(13) 0.0007(11) 0.0154(12) -0.0024(12) C30 0.0264(13) 0.0317(15) 0.0365(14) 0.0008(12) 0.0029(11) -0.0001(11) C23 0.0386(15) 0.0302(14) 0.0277(13) -0.0038(11) 0.0091(11) -0.0084(12) C7 0.076(2) 0.033(2) 0.0325(15) -0.0013(13) 0.0207(15) -0.016(2) C14 0.0284(13) 0.0337(15) 0.0315(13) 0.0024(11) -0.0023(11) 0.0013(11) C5 0.071(2) 0.0268(14) 0.0218(13) 0.0021(11) -0.0067(13) 0.0027(15) _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 1.856(2) . ? Ti1 O2 1.857(2) . ? Ti1 O1 1.918(2) . ? Ti1 O3 1.936(2) . ? Ti1 N1 2.158(2) . ? Ti1 N2 2.178(2) . ? O3 C16 1.311(3) . ? O1 C1 1.309(3) . ? O2 C13 1.402(3) . ? O4 C28 1.401(3) . ? N2 C26 1.293(3) . ? N2 C27 1.497(3) . ? N1 C11 1.295(3) . ? N1 C12 1.500(3) . ? C25 C16 1.398(3) . ? C25 C26 1.433(3) . ? C25 C24 1.454(3) . ? C10 C1 1.396(3) . ? C10 C11 1.432(3) . ? C10 C9 1.439(3) . ? C21 C20 1.363(3) . ? C21 C22 1.391(4) . ? C24 C23 1.405(3) . ? C24 C19 1.428(3) . ? C12 C14 1.520(3) . ? C12 C15 1.527(3) . ? C12 C13 1.527(3) . ? C16 C17 1.421(3) . ? C20 C19 1.404(3) . ? C19 C18 1.421(3) . ? C6 C5 1.351(4) . ? C6 C7 1.401(4) . ? C17 C18 1.358(3) . ? C28 C27 1.526(3) . ? C27 C29 1.520(3) . ? C27 C30 1.534(3) . ? C1 C2 1.426(3) . ? C9 C8 1.410(3) . ? C9 C4 1.422(3) . ? C4 C5 1.412(3) . ? C4 C3 1.415(4) . ? C3 C2 1.352(3) . ? C22 C23 1.374(3) . ? C8 C7 1.371(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O4 Ti1 O2 94.77(8) . . ? O4 Ti1 O1 90.06(7) . . ? O2 Ti1 O1 157.42(7) . . ? O4 Ti1 O3 156.68(7) . . ? O2 Ti1 O3 93.47(7) . . ? O1 Ti1 O3 90.64(7) . . ? O4 Ti1 N1 105.69(7) . . ? O2 Ti1 N1 77.26(7) . . ? O1 Ti1 N1 80.20(6) . . ? O3 Ti1 N1 97.39(7) . . ? O4 Ti1 N2 77.41(7) . . ? O2 Ti1 N2 97.78(7) . . ? O1 Ti1 N2 104.80(7) . . ? O3 Ti1 N2 79.89(7) . . ? N1 Ti1 N2 174.25(7) . . ? C16 O3 Ti1 138.83(15) . . ? C1 O1 Ti1 141.53(14) . . ? C13 O2 Ti1 118.83(13) . . ? C28 O4 Ti1 121.60(14) . . ? C26 N2 C27 119.7(2) . . ? C26 N2 Ti1 128.7(2) . . ? C27 N2 Ti1 111.60(13) . . ? C11 N1 C12 117.2(2) . . ? C11 N1 Ti1 129.6(2) . . ? C12 N1 Ti1 112.79(13) . . ? C16 C25 C26 120.0(2) . . ? C16 C25 C24 119.4(2) . . ? C26 C25 C24 120.5(2) . . ? C1 C10 C11 119.5(2) . . ? C1 C10 C9 119.6(2) . . ? C11 C10 C9 120.9(2) . . ? C20 C21 C22 119.0(2) . . ? C23 C24 C19 116.8(2) . . ? C23 C24 C25 124.1(2) . . ? C19 C24 C25 119.0(2) . . ? N1 C12 C14 107.5(2) . . ? N1 C12 C15 114.0(2) . . ? C14 C12 C15 111.2(2) . . ? N1 C12 C13 102.2(2) . . ? C14 C12 C13 110.7(2) . . ? C15 C12 C13 110.9(2) . . ? O3 C16 C25 122.3(2) . . ? O3 C16 C17 117.7(2) . . ? C25 C16 C17 120.0(2) . . ? C21 C20 C19 121.5(2) . . ? C20 C19 C18 121.1(2) . . ? C20 C19 C24 119.9(2) . . ? C18 C19 C24 119.0(2) . . ? N2 C26 C25 126.0(2) . . ? C5 C6 C7 119.2(3) . . ? C18 C17 C16 121.1(2) . . ? O2 C13 C12 107.9(2) . . ? N1 C11 C10 126.4(2) . . ? O4 C28 C27 108.7(2) . . ? N2 C27 C29 115.5(2) . . ? N2 C27 C28 102.9(2) . . ? C29 C27 C28 110.6(2) . . ? N2 C27 C30 107.0(2) . . ? C29 C27 C30 110.6(2) . . ? C28 C27 C30 109.8(2) . . ? C17 C18 C19 121.5(2) . . ? O1 C1 C10 122.4(2) . . ? O1 C1 C2 117.5(2) . . ? C10 C1 C2 120.1(2) . . ? C8 C9 C4 117.6(2) . . ? C8 C9 C10 123.6(2) . . ? C4 C9 C10 118.7(2) . . ? C5 C4 C3 121.1(2) . . ? C5 C4 C9 119.6(3) . . ? C3 C4 C9 119.3(2) . . ? C2 C3 C4 121.8(2) . . ? C23 C22 C21 121.1(2) . . ? C3 C2 C1 120.1(2) . . ? C7 C8 C9 120.9(3) . . ? C22 C23 C24 121.6(2) . . ? C8 C7 C6 121.2(3) . . ? C6 C5 C4 121.5(3) . . ? _refine_diff_density_max 0.255 _refine_diff_density_min -0.299 _refine_diff_density_rms 0.050 data_4a _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C31 H28 O6 Ti' _chemical_formula_weight 544.43 _chemical_melting_point ? _chemical_compound_source ? 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' 'Ti' 'Ti' 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 8.2542(13) _cell_length_b 22.121(4) _cell_length_c 14.582(2) _cell_angle_alpha 90.00 _cell_angle_beta 102.340(13) _cell_angle_gamma 90.00 _cell_volume 2601.1(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.390 _exptl_crystal_density_method ? _exptl_crystal_F_000 1136 _exptl_absorpt_coefficient_mu 0.374 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 ? _diffrn_measurement_method ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4896 _diffrn_reflns_av_R_equivalents 0.0180 _diffrn_reflns_av_sigmaI/netI 0.0497 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.33 _diffrn_reflns_theta_max 24.97 _reflns_number_total 4562 _reflns_number_observed 3229 _reflns_observed_criterion >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0509P)^2^+0.0511P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4562 _refine_ls_number_parameters 353 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0677 _refine_ls_R_factor_obs 0.0376 _refine_ls_wR_factor_all 0.0942 _refine_ls_wR_factor_obs 0.0876 _refine_ls_goodness_of_fit_all 1.019 _refine_ls_goodness_of_fit_obs 1.145 _refine_ls_restrained_S_all 1.019 _refine_ls_restrained_S_obs 1.145 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti1 Ti 0.27848(5) 0.11183(2) 0.30273(3) 0.02327(12) Uani 1 d . . O2 O 0.3712(2) 0.04659(7) 0.25996(11) 0.0235(4) Uani 1 d . . O3 O 0.2281(2) 0.15180(7) 0.17612(11) 0.0264(4) Uani 1 d . . O1 O 0.0726(2) 0.07508(7) 0.29231(11) 0.0254(4) Uani 1 d . . C16 C 0.4127(3) -0.12615(12) -0.0825(2) 0.0335(6) Uani 1 d . . H16 H 0.4425(3) -0.14777(12) -0.1310(2) 0.040 Uiso 1 calc R . O5 O 0.3468(2) 0.09111(8) 0.43816(11) 0.0285(4) Uani 1 d . . O6 O 0.5046(2) 0.15347(7) 0.32460(11) 0.0263(4) Uani 1 d . . O4 O 0.1881(2) 0.19024(7) 0.34481(12) 0.0315(4) Uani 1 d . . C15 C 0.2447(3) -0.11927(11) -0.0797(2) 0.0313(6) Uani 1 d . . H15 H 0.1633(3) -0.13685(11) -0.1260(2) 0.038 Uiso 1 calc R . C3 C -0.0727(3) -0.05722(12) 0.3944(2) 0.0316(6) Uani 1 d . . H3 H -0.1176(3) -0.06634(12) 0.4460(2) 0.038 Uiso 1 calc R . C20 C 0.5749(3) -0.00396(11) 0.1958(2) 0.0259(5) Uani 1 d . . H20 H 0.6581(3) 0.01401(11) 0.2406(2) 0.031 Uiso 1 calc R . C4 C -0.0462(3) -0.10390(11) 0.3336(2) 0.0270(6) Uani 1 d . . C6 C -0.0580(4) -0.20944(13) 0.2897(2) 0.0430(7) Uani 1 d . . H6 H -0.0822(4) -0.24939(13) 0.3014(2) 0.052 Uiso 1 calc R . C2 C -0.0338(3) 0.00046(12) 0.3788(2) 0.0285(6) Uani 1 d . . H2 H -0.0515(3) 0.03055(12) 0.4201(2) 0.034 Uiso 1 calc R . C21 C 0.4067(3) 0.00652(10) 0.1973(2) 0.0213(5) Uani 1 d . . C8 C 0.0401(3) -0.13659(11) 0.1926(2) 0.0276(6) Uani 1 d . . H8 H 0.0808(3) -0.12791(11) 0.1393(2) 0.033 Uiso 1 calc R . C13 C 0.3203(3) -0.05886(10) 0.0635(2) 0.0209(5) Uani 1 d . . C12 C 0.2790(3) -0.02214(10) 0.1354(2) 0.0188(5) Uani 1 d . . C14 C 0.2003(3) -0.08668(10) -0.0089(2) 0.0250(5) Uani 1 d . . H14 H 0.0885(3) -0.08264(10) -0.0082(2) 0.030 Uiso 1 calc R . C7 C 0.0036(3) -0.19507(12) 0.2100(2) 0.0353(6) Uani 1 d . . H7 H 0.0196(3) -0.22549(12) 0.1688(2) 0.042 Uiso 1 calc R . C18 C 0.4908(3) -0.06717(10) 0.0598(2) 0.0240(5) Uani 1 d . . C9 C 0.0180(3) -0.08883(11) 0.2530(2) 0.0222(5) Uani 1 d . . C10 C 0.0550(3) -0.02716(10) 0.2357(2) 0.0208(5) Uani 1 d . . C11 C 0.1033(3) -0.00851(10) 0.1444(2) 0.0200(5) Uani 1 d . . H11A H 0.0281(3) -0.02831(10) 0.0930(2) 0.024 Uiso 1 calc R . H11B H 0.0854(3) 0.03468(10) 0.1365(2) 0.024 Uiso 1 calc R . C19 C 0.6149(3) -0.03989(10) 0.1296(2) 0.0259(6) Uani 1 d . . H19 H 0.7261(3) -0.04695(10) 0.1298(2) 0.031 Uiso 1 calc R . C29 C 0.1596(3) 0.20209(12) 0.1473(2) 0.0333(6) Uani 1 d . . C5 C -0.0825(3) -0.16523(12) 0.3500(2) 0.0371(7) Uani 1 d . . H5 H -0.1235(3) -0.17526(12) 0.4026(2) 0.045 Uiso 1 calc R . C1 C 0.0334(3) 0.01597(11) 0.3004(2) 0.0228(5) Uani 1 d . . C17 C 0.5314(3) -0.10118(11) -0.0142(2) 0.0300(6) Uani 1 d . . H17 H 0.6424(3) -0.10659(11) -0.0161(2) 0.036 Uiso 1 calc R . C23 C 0.6326(3) 0.11233(12) 0.4705(2) 0.0328(6) Uani 1 d . . H23 H 0.7295(35) 0.1089(12) 0.5152(18) 0.039 Uiso 1 d . . C24 C 0.6343(3) 0.14356(11) 0.3879(2) 0.0283(6) Uani 1 d . . C22 C 0.4903(3) 0.09056(11) 0.4943(2) 0.0286(6) Uani 1 d . . C27 C 0.1236(3) 0.23683(12) 0.3006(2) 0.0355(6) Uani 1 d . . C28 C 0.1029(4) 0.24356(12) 0.2040(2) 0.0421(7) Uani 1 d . . H28 H 0.0355(36) 0.2795(13) 0.1736(19) 0.050 Uiso 1 d . . C25 C 0.4976(4) 0.06475(14) 0.5901(2) 0.0423(7) Uani 1 d . . H25A H 0.6113(4) 0.0602(8) 0.6221(5) 0.063 Uiso 1 calc R . H25B H 0.4440(21) 0.0260(4) 0.5844(2) 0.063 Uiso 1 calc R . H25C H 0.4421(21) 0.0915(4) 0.6252(5) 0.063 Uiso 1 calc R . C26 C 0.7931(3) 0.16851(13) 0.3702(2) 0.0409(7) Uani 1 d . . H26A H 0.8311(12) 0.1436(5) 0.3251(10) 0.061 Uiso 1 calc R . H26B H 0.8752(7) 0.1690(8) 0.4278(3) 0.061 Uiso 1 calc R . H26C H 0.7751(6) 0.2089(3) 0.3463(13) 0.061 Uiso 1 calc R . C30 C 0.0730(4) 0.28690(12) 0.3579(2) 0.0519(9) Uani 1 d . . H30A H -0.0305(13) 0.3037(6) 0.3251(7) 0.078 Uiso 1 calc R . H30B H 0.1566(13) 0.3178(5) 0.3678(13) 0.078 Uiso 1 calc R . H30C H 0.0605(25) 0.2712(2) 0.4174(6) 0.078 Uiso 1 calc R . C31 C 0.1435(4) 0.21467(14) 0.0452(2) 0.0516(8) Uani 1 d . . H31A H 0.2517(4) 0.2196(9) 0.0320(3) 0.077 Uiso 1 calc R . H31B H 0.0803(23) 0.2510(5) 0.0288(4) 0.077 Uiso 1 calc R . H31C H 0.0880(24) 0.1815(5) 0.0092(2) 0.077 Uiso 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 0.0227(2) 0.0234(2) 0.0242(2) -0.0009(2) 0.0062(2) -0.0006(2) O2 0.0200(8) 0.0264(9) 0.0240(9) -0.0016(7) 0.0046(7) 0.0009(7) O3 0.0276(9) 0.0227(9) 0.0300(9) 0.0021(7) 0.0088(8) 0.0042(7) O1 0.0214(8) 0.0262(9) 0.0293(9) -0.0034(7) 0.0069(7) 0.0012(7) C16 0.044(2) 0.0323(15) 0.0300(14) -0.0014(11) 0.0206(13) 0.0033(12) O5 0.0261(9) 0.0352(10) 0.0249(9) 0.0026(7) 0.0074(8) -0.0032(8) O6 0.0256(9) 0.0265(9) 0.0274(9) -0.0009(7) 0.0071(8) -0.0046(7) O4 0.0332(10) 0.0271(10) 0.0375(10) -0.0055(8) 0.0148(8) -0.0003(8) C15 0.040(2) 0.0308(14) 0.0236(13) -0.0006(11) 0.0072(11) -0.0047(12) C3 0.0268(14) 0.049(2) 0.0198(13) 0.0050(12) 0.0065(10) -0.0069(12) C20 0.0184(12) 0.0307(13) 0.0269(13) 0.0056(11) 0.0011(10) 0.0001(10) C4 0.0192(12) 0.0371(15) 0.0229(12) 0.0058(11) 0.0009(10) -0.0031(10) C6 0.051(2) 0.0305(15) 0.045(2) 0.0111(13) 0.0033(14) -0.0086(13) C2 0.0227(13) 0.042(2) 0.0216(12) -0.0061(11) 0.0063(10) -0.0010(11) C21 0.0222(12) 0.0204(12) 0.0219(12) 0.0035(10) 0.0064(10) 0.0003(10) C8 0.0241(13) 0.0292(13) 0.0297(14) 0.0020(11) 0.0062(11) 0.0001(11) C13 0.0236(12) 0.0189(12) 0.0211(12) 0.0066(9) 0.0070(10) 0.0024(10) C12 0.0180(11) 0.0180(11) 0.0211(12) 0.0064(9) 0.0055(9) 0.0045(9) C14 0.0248(13) 0.0271(13) 0.0240(13) 0.0044(10) 0.0067(10) 0.0024(10) C7 0.039(2) 0.0271(14) 0.039(2) 0.0017(12) 0.0059(13) -0.0021(12) C18 0.0245(12) 0.0222(12) 0.0278(13) 0.0073(10) 0.0112(10) 0.0033(10) C9 0.0120(11) 0.0289(13) 0.0241(12) 0.0033(10) 0.0001(9) -0.0019(9) C10 0.0113(11) 0.0269(12) 0.0237(12) 0.0020(10) 0.0025(9) -0.0003(9) C11 0.0162(11) 0.0222(12) 0.0209(12) 0.0006(9) 0.0026(9) 0.0007(9) C19 0.0168(12) 0.0308(14) 0.0313(14) 0.0073(11) 0.0075(10) 0.0056(10) C29 0.0308(14) 0.0317(15) 0.0352(15) 0.0032(12) 0.0020(12) -0.0029(12) C5 0.038(2) 0.042(2) 0.0297(14) 0.0108(13) 0.0041(12) -0.0090(13) C1 0.0138(11) 0.0272(13) 0.0268(13) -0.0008(10) 0.0029(10) -0.0009(10) C17 0.0274(14) 0.0306(14) 0.0360(15) 0.0038(11) 0.0160(12) 0.0051(11) C23 0.0255(14) 0.040(2) 0.0303(14) 0.0068(13) 0.0010(11) 0.0039(12) C24 0.0256(14) 0.0249(13) 0.0367(15) -0.0053(11) 0.0118(12) 0.0001(11) C22 0.0311(14) 0.0300(13) 0.0246(13) 0.0008(11) 0.0056(11) 0.0060(11) C27 0.0263(14) 0.0280(14) 0.053(2) -0.0117(13) 0.0103(13) -0.0046(11) C28 0.046(2) 0.0282(15) 0.048(2) -0.0001(13) 0.0014(14) 0.0088(13) C25 0.041(2) 0.055(2) 0.031(2) 0.0104(13) 0.0074(13) 0.0043(14) C26 0.0260(15) 0.044(2) 0.054(2) 0.0052(14) 0.0126(13) -0.0027(12) C30 0.047(2) 0.033(2) 0.081(2) -0.021(2) 0.024(2) -0.0030(14) C31 0.069(2) 0.041(2) 0.041(2) 0.0104(14) 0.005(2) 0.006(2) _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 O2 1.806(2) . ? Ti1 O1 1.861(2) . ? Ti1 O5 1.988(2) . ? Ti1 O3 2.009(2) . ? Ti1 O4 2.034(2) . ? Ti1 O6 2.045(2) . ? O2 C21 1.350(3) . ? O3 C29 1.278(3) . ? O1 C1 1.358(3) . ? C16 C17 1.357(4) . ? C16 C15 1.404(4) . ? O5 C22 1.288(3) . ? O6 C24 1.274(3) . ? O4 C27 1.270(3) . ? C15 C14 1.371(3) . ? C3 C2 1.347(3) . ? C3 C4 1.408(3) . ? C20 C19 1.344(3) . ? C20 C21 1.412(3) . ? C4 C5 1.420(3) . ? C4 C9 1.429(3) . ? C6 C5 1.358(4) . ? C6 C7 1.401(4) . ? C2 C1 1.415(3) . ? C21 C12 1.386(3) . ? C8 C7 1.364(3) . ? C8 C9 1.412(3) . ? C13 C14 1.423(3) . ? C13 C12 1.424(3) . ? C13 C18 1.432(3) . ? C12 C11 1.514(3) . ? C18 C17 1.412(3) . ? C18 C19 1.416(3) . ? C9 C10 1.432(3) . ? C10 C1 1.380(3) . ? C10 C11 1.525(3) . ? C29 C28 1.382(4) . ? C29 C31 1.491(4) . ? C23 C22 1.380(4) . ? C23 C24 1.392(3) . ? C24 C26 1.495(3) . ? C22 C25 1.499(3) . ? C27 C28 1.390(4) . ? C27 C30 1.499(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 O2 Ti1 O1 93.99(7) . . ? O2 Ti1 O5 96.18(7) . . ? O1 Ti1 O5 92.33(7) . . ? O2 Ti1 O3 93.10(7) . . ? O1 Ti1 O3 96.39(7) . . ? O5 Ti1 O3 166.79(7) . . ? O2 Ti1 O4 174.55(7) . . ? O1 Ti1 O4 90.55(7) . . ? O5 Ti1 O4 86.64(7) . . ? O3 Ti1 O4 83.38(7) . . ? O2 Ti1 O6 88.50(7) . . ? O1 Ti1 O6 175.66(7) . . ? O5 Ti1 O6 83.87(7) . . ? O3 Ti1 O6 87.01(7) . . ? O4 Ti1 O6 87.16(7) . . ? C21 O2 Ti1 158.14(15) . . ? C29 O3 Ti1 132.5(2) . . ? C1 O1 Ti1 130.07(14) . . ? C17 C16 C15 119.8(2) . . ? C22 O5 Ti1 131.3(2) . . ? C24 O6 Ti1 129.3(2) . . ? C27 O4 Ti1 132.8(2) . . ? C14 C15 C16 120.2(2) . . ? C2 C3 C4 120.9(2) . . ? C19 C20 C21 120.1(2) . . ? C3 C4 C5 121.9(2) . . ? C3 C4 C9 118.8(2) . . ? C5 C4 C9 119.3(2) . . ? C5 C6 C7 120.3(3) . . ? C3 C2 C1 121.0(2) . . ? O2 C21 C12 119.7(2) . . ? O2 C21 C20 118.4(2) . . ? C12 C21 C20 121.9(2) . . ? C7 C8 C9 122.1(2) . . ? C14 C13 C12 123.7(2) . . ? C14 C13 C18 116.7(2) . . ? C12 C13 C18 119.5(2) . . ? C21 C12 C13 118.1(2) . . ? C21 C12 C11 117.5(2) . . ? C13 C12 C11 124.2(2) . . ? C15 C14 C13 122.0(2) . . ? C8 C7 C6 120.2(3) . . ? C17 C18 C19 121.5(2) . . ? C17 C18 C13 119.5(2) . . ? C19 C18 C13 118.9(2) . . ? C8 C9 C4 117.3(2) . . ? C8 C9 C10 122.8(2) . . ? C4 C9 C10 119.8(2) . . ? C1 C10 C9 118.3(2) . . ? C1 C10 C11 120.4(2) . . ? C9 C10 C11 121.1(2) . . ? C12 C11 C10 117.1(2) . . ? C20 C19 C18 121.2(2) . . ? O3 C29 C28 124.3(2) . . ? O3 C29 C31 115.5(2) . . ? C28 C29 C31 120.3(2) . . ? C6 C5 C4 120.9(3) . . ? O1 C1 C10 122.6(2) . . ? O1 C1 C2 116.4(2) . . ? C10 C1 C2 121.0(2) . . ? C16 C17 C18 121.7(2) . . ? C22 C23 C24 123.8(2) . . ? O6 C24 C23 123.4(2) . . ? O6 C24 C26 116.3(2) . . ? C23 C24 C26 120.3(2) . . ? O5 C22 C23 123.6(2) . . ? O5 C22 C25 116.4(2) . . ? C23 C22 C25 120.0(2) . . ? O4 C27 C28 123.2(2) . . ? O4 C27 C30 117.0(3) . . ? C28 C27 C30 119.8(3) . . ? C29 C28 C27 123.5(3) . . ? _refine_diff_density_max 0.243 _refine_diff_density_min -0.311 _refine_diff_density_rms 0.050