# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # ####################################################################### data_d:\as10js1\squeze _database_code_depnum_ccdc_archive 'CCDC 902037' #TrackingRef 'compound 11 revised.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H34 Cl4 N2 O2 Ti' _chemical_formula_weight 668.31 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 trigonal _symmetry_space_group_name_H-M R-3 _symmetry_space_group_name_Hall '-R 3' _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 22.5011(13) _cell_length_b 22.5011(13) _cell_length_c 18.1552(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 7960.5(9) _cell_formula_units_Z 9 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 24912 _cell_measurement_theta_min 2.94 _cell_measurement_theta_max 30.59 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.255 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3114 _exptl_absorpt_coefficient_mu 0.573 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.70000 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'Synchrotron ID' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-ID1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q315' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 56709 _diffrn_reflns_av_R_equivalents 0.0832 _diffrn_reflns_av_unetI/netI 0.0374 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.94 _diffrn_reflns_theta_max 30.59 _reflns_number_total 5600 _reflns_number_gt 4234 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 2008)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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. ; loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.000 0.000 0.000 407 35 ' ' 2 0.667 0.333 0.333 405 35 ' ' 3 0.333 0.667 0.167 23 2 ' ' 4 0.333 0.667 0.667 405 35 ' ' 5 0.000 0.000 0.500 23 2 ' ' 6 0.667 0.333 0.833 23 2 ' ' _platon_squeeze_details ; Squeeze was used owing to the inability to refine a molecule of DCM that was badly disordered. Details are below. It is suspected that the large thermal motion of one of the phenyl groups is associated with this solvent disorder. ; _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^)+(0.1293P)^2^+8.9241P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5600 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1054 _refine_ls_R_factor_gt 0.0787 _refine_ls_wR_factor_ref 0.2290 _refine_ls_wR_factor_gt 0.2099 _refine_ls_goodness_of_fit_ref 1.092 _refine_ls_restrained_S_all 1.092 _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 0.5000 0.0000 0.0000 0.0426(2) Uani 1 2 d S . . Cl1 Cl 0.46043(4) 0.07616(4) -0.03010(4) 0.0540(2) Uani 1 1 d . . . Cl2 Cl 0.53874(4) 0.05846(4) 0.11429(4) 0.0540(2) Uani 1 1 d . . . O1 O 0.41472(11) -0.05804(10) 0.04293(12) 0.0527(5) Uani 1 1 d . . . N1 N 0.35195(14) -0.00330(12) 0.12342(13) 0.0467(5) Uani 1 1 d . . . H1 H 0.3879(18) 0.0068(18) 0.094(2) 0.053 Uiso 1 1 d . . . C1 C 0.36219(14) -0.11957(13) 0.05816(15) 0.0423(5) Uani 1 1 d . . . C2 C 0.31013(13) -0.12504(13) 0.10428(14) 0.0404(5) Uani 1 1 d . . . C3 C 0.25558(16) -0.19016(15) 0.12282(18) 0.0523(7) Uani 1 1 d . . . H3 H 0.2208 -0.1939 0.1553 0.063 Uiso 1 1 calc R . . C4 C 0.25195(16) -0.24852(15) 0.0945(2) 0.0565(7) Uani 1 1 d . . . H4 H 0.2149 -0.2925 0.1072 0.068 Uiso 1 1 calc R . . C5 C 0.30283(18) -0.24259(15) 0.0472(2) 0.0590(8) Uani 1 1 d . . . H5 H 0.2997 -0.2829 0.0265 0.071 Uiso 1 1 calc R . . C6 C 0.35805(17) -0.17942(15) 0.02952(19) 0.0546(7) Uani 1 1 d . . . H6 H 0.3932 -0.1764 -0.0020 0.065 Uiso 1 1 calc R . . C7 C 0.30907(15) -0.06632(15) 0.13438(15) 0.0461(6) Uani 1 1 d . . . H7 H 0.2718 -0.0759 0.1663 0.055 Uiso 1 1 calc R . . C8 C 0.34612(18) 0.05675(16) 0.15211(17) 0.0532(7) Uani 1 1 d . . . C9 C 0.3136(3) 0.0408(2) 0.2284(2) 0.0822(13) Uani 1 1 d . . . H9A H 0.2665 0.0022 0.2251 0.123 Uiso 1 1 calc R . . H9B H 0.3130 0.0812 0.2476 0.123 Uiso 1 1 calc R . . H9C H 0.3403 0.0287 0.2615 0.123 Uiso 1 1 calc R . . C10 C 0.4185(2) 0.11639(18) 0.1581(2) 0.0661(9) Uani 1 1 d . . . H10A H 0.4398 0.1272 0.1092 0.099 Uiso 1 1 calc R . . H10B H 0.4451 0.1042 0.1913 0.099 Uiso 1 1 calc R . . H10C H 0.4174 0.1565 0.1776 0.099 Uiso 1 1 calc R . . C11 C 0.30417(18) 0.06998(15) 0.09335(19) 0.0561(7) Uani 1 1 d . . . C12 C 0.2352(3) 0.0327(3) 0.0904(5) 0.130(3) Uani 1 1 d . . . H12 H 0.2115 -0.0025 0.1258 0.156 Uiso 1 1 calc R . . C13 C 0.1974(3) 0.0441(3) 0.0372(5) 0.145(3) Uani 1 1 d . . . H13 H 0.1486 0.0198 0.0390 0.174 Uiso 1 1 calc R . . C14 C 0.2310(3) 0.0904(3) -0.0175(3) 0.0943(15) Uani 1 1 d . . . H14 H 0.2059 0.0956 -0.0566 0.113 Uiso 1 1 calc R . . C15 C 0.2991(3) 0.1285(3) -0.0159(3) 0.0923(14) Uani 1 1 d . . . H15 H 0.3225 0.1625 -0.0526 0.111 Uiso 1 1 calc R . . C16 C 0.3356(2) 0.1187(3) 0.0386(2) 0.0772(11) Uani 1 1 d . . . H16 H 0.3842 0.1463 0.0388 0.093 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 0.0531(4) 0.0334(3) 0.0439(4) 0.0084(2) 0.0121(3) 0.0237(3) Cl1 0.0765(5) 0.0462(4) 0.0521(4) 0.0073(3) 0.0055(3) 0.0403(4) Cl2 0.0698(5) 0.0509(4) 0.0495(4) -0.0003(3) 0.0016(3) 0.0364(4) O1 0.0594(12) 0.0350(9) 0.0623(12) 0.0074(8) 0.0214(10) 0.0226(9) N1 0.0595(14) 0.0454(12) 0.0431(11) -0.0014(9) 0.0042(10) 0.0323(11) C1 0.0480(13) 0.0368(12) 0.0440(13) 0.0011(10) 0.0058(11) 0.0226(11) C2 0.0427(12) 0.0385(12) 0.0394(12) -0.0031(9) -0.0007(10) 0.0199(10) C3 0.0460(14) 0.0473(15) 0.0585(17) -0.0044(13) 0.0079(12) 0.0194(12) C4 0.0476(15) 0.0389(13) 0.072(2) -0.0040(13) 0.0022(14) 0.0131(12) C5 0.0639(18) 0.0346(13) 0.077(2) -0.0110(13) 0.0038(16) 0.0234(13) C6 0.0608(17) 0.0403(13) 0.0634(18) -0.0040(12) 0.0153(14) 0.0259(13) C7 0.0518(14) 0.0498(14) 0.0419(13) -0.0065(11) -0.0014(11) 0.0293(12) C8 0.073(2) 0.0477(15) 0.0521(15) -0.0073(12) 0.0002(14) 0.0400(15) C9 0.128(4) 0.073(2) 0.060(2) -0.0059(18) 0.023(2) 0.061(3) C10 0.079(2) 0.0540(18) 0.075(2) -0.0203(16) -0.0154(18) 0.0402(17) C11 0.0679(19) 0.0403(14) 0.0682(19) -0.0071(13) -0.0028(15) 0.0331(14) C12 0.070(3) 0.092(3) 0.216(8) 0.078(4) -0.003(4) 0.032(3) C13 0.079(3) 0.097(4) 0.228(9) 0.054(5) -0.040(4) 0.021(3) C14 0.112(4) 0.067(3) 0.108(4) -0.007(2) -0.027(3) 0.048(3) C15 0.115(4) 0.113(4) 0.072(3) 0.024(3) 0.014(3) 0.074(4) C16 0.078(2) 0.091(3) 0.076(2) 0.015(2) 0.011(2) 0.052(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 O1 1.868(2) . ? Ti1 O1 1.868(2) 10_655 ? Ti1 Cl1 2.3567(7) 10_655 ? Ti1 Cl1 2.3567(7) . ? Ti1 Cl2 2.3768(8) 10_655 ? Ti1 Cl2 2.3768(8) . ? O1 C1 1.324(3) . ? N1 C7 1.270(4) . ? N1 C8 1.514(3) . ? N1 H1 0.90(4) . ? C1 C2 1.395(4) . ? C1 C6 1.402(4) . ? C2 C3 1.403(4) . ? C2 C7 1.441(4) . ? C3 C4 1.374(4) . ? C3 H3 0.9500 . ? C4 C5 1.383(5) . ? C4 H4 0.9500 . ? C5 C6 1.379(4) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C10 1.509(5) . ? C8 C9 1.523(5) . ? C8 C11 1.549(5) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 C12 1.347(6) . ? C11 C16 1.383(5) . ? C12 C13 1.394(8) . ? C12 H12 0.9500 . ? C13 C14 1.362(9) . ? C13 H13 0.9500 . ? C14 C15 1.330(8) . ? C14 H14 0.9500 . ? C15 C16 1.374(7) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? 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 O1 180.0(2) . 10_655 ? O1 Ti1 Cl1 91.40(6) . 10_655 ? O1 Ti1 Cl1 88.60(6) 10_655 10_655 ? O1 Ti1 Cl1 88.60(6) . . ? O1 Ti1 Cl1 91.40(6) 10_655 . ? Cl1 Ti1 Cl1 180.00(3) 10_655 . ? O1 Ti1 Cl2 90.75(7) . 10_655 ? O1 Ti1 Cl2 89.25(7) 10_655 10_655 ? Cl1 Ti1 Cl2 88.13(3) 10_655 10_655 ? Cl1 Ti1 Cl2 91.87(3) . 10_655 ? O1 Ti1 Cl2 89.25(7) . . ? O1 Ti1 Cl2 90.75(7) 10_655 . ? Cl1 Ti1 Cl2 91.87(3) 10_655 . ? Cl1 Ti1 Cl2 88.13(3) . . ? Cl2 Ti1 Cl2 180.00(4) 10_655 . ? C1 O1 Ti1 152.35(18) . . ? C7 N1 C8 125.9(3) . . ? C7 N1 H1 117(2) . . ? C8 N1 H1 117(2) . . ? O1 C1 C2 119.3(2) . . ? O1 C1 C6 121.5(2) . . ? C2 C1 C6 119.2(2) . . ? C1 C2 C3 119.6(2) . . ? C1 C2 C7 123.0(2) . . ? C3 C2 C7 117.4(2) . . ? C4 C3 C2 120.8(3) . . ? C4 C3 H3 119.6 . . ? C2 C3 H3 119.6 . . ? C3 C4 C5 119.3(3) . . ? C3 C4 H4 120.4 . . ? C5 C4 H4 120.4 . . ? C6 C5 C4 121.3(3) . . ? C6 C5 H5 119.3 . . ? C4 C5 H5 119.3 . . ? C5 C6 C1 119.8(3) . . ? C5 C6 H6 120.1 . . ? C1 C6 H6 120.1 . . ? N1 C7 C2 127.8(3) . . ? N1 C7 H7 116.1 . . ? C2 C7 H7 116.1 . . ? C10 C8 N1 106.4(3) . . ? C10 C8 C9 108.8(3) . . ? N1 C8 C9 110.4(3) . . ? C10 C8 C11 111.6(3) . . ? N1 C8 C11 105.5(2) . . ? C9 C8 C11 113.8(3) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C8 C10 H10A 109.5 . . ? C8 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C8 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C12 C11 C16 116.1(4) . . ? C12 C11 C8 122.1(4) . . ? C16 C11 C8 121.8(3) . . ? C11 C12 C13 122.2(5) . . ? C11 C12 H12 118.9 . . ? C13 C12 H12 118.9 . . ? C14 C13 C12 119.3(6) . . ? C14 C13 H13 120.4 . . ? C12 C13 H13 120.4 . . ? C15 C14 C13 119.9(5) . . ? C15 C14 H14 120.1 . . ? C13 C14 H14 120.1 . . ? C14 C15 C16 120.0(5) . . ? C14 C15 H15 120.0 . . ? C16 C15 H15 120.0 . . ? C15 C16 C11 122.4(5) . . ? C15 C16 H16 118.8 . . ? C11 C16 H16 118.8 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O1 Ti1 O1 C1 129(42) 10_655 . . . ? Cl1 Ti1 O1 C1 -37.9(4) 10_655 . . . ? Cl1 Ti1 O1 C1 142.1(4) . . . . ? Cl2 Ti1 O1 C1 50.3(4) 10_655 . . . ? Cl2 Ti1 O1 C1 -129.7(4) . . . . ? Ti1 O1 C1 C2 175.1(3) . . . . ? Ti1 O1 C1 C6 -4.3(6) . . . . ? O1 C1 C2 C3 -177.7(3) . . . . ? C6 C1 C2 C3 1.7(4) . . . . ? O1 C1 C2 C7 2.5(4) . . . . ? C6 C1 C2 C7 -178.1(3) . . . . ? C1 C2 C3 C4 -1.7(5) . . . . ? C7 C2 C3 C4 178.0(3) . . . . ? C2 C3 C4 C5 0.0(5) . . . . ? C3 C4 C5 C6 1.8(6) . . . . ? C4 C5 C6 C1 -1.8(6) . . . . ? O1 C1 C6 C5 179.4(3) . . . . ? C2 C1 C6 C5 0.0(5) . . . . ? C8 N1 C7 C2 175.5(3) . . . . ? C1 C2 C7 N1 1.6(5) . . . . ? C3 C2 C7 N1 -178.1(3) . . . . ? C7 N1 C8 C10 153.5(3) . . . . ? C7 N1 C8 C9 35.6(4) . . . . ? C7 N1 C8 C11 -87.8(3) . . . . ? C10 C8 C11 C12 -163.6(5) . . . . ? N1 C8 C11 C12 81.2(5) . . . . ? C9 C8 C11 C12 -40.0(6) . . . . ? C10 C8 C11 C16 19.5(4) . . . . ? N1 C8 C11 C16 -95.6(4) . . . . ? C9 C8 C11 C16 143.1(4) . . . . ? C16 C11 C12 C13 -2.3(10) . . . . ? C8 C11 C12 C13 -179.4(7) . . . . ? C11 C12 C13 C14 5.5(13) . . . . ? C12 C13 C14 C15 -5.9(12) . . . . ? C13 C14 C15 C16 3.2(9) . . . . ? C14 C15 C16 C11 -0.1(8) . . . . ? C12 C11 C16 C15 -0.4(7) . . . . ? C8 C11 C16 C15 176.7(4) . . . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 30.59 _diffrn_measured_fraction_theta_full 0.983 _refine_diff_density_max 0.737 _refine_diff_density_min -0.394 _refine_diff_density_rms 0.082 data_d:\14js99\re\re _database_code_depnum_ccdc_archive 'CCDC 902038' #TrackingRef 'web_deposit_cif_file_1_MichaelGardiner_1348050215.compound 12.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H28 Cl2 N2 O2 Ti' _chemical_formula_weight 567.34 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 monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.1820(12) _cell_length_b 25.1880(16) _cell_length_c 14.674(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.750(3) _cell_angle_gamma 90.00 _cell_volume 2654.3(8) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 30319 _cell_measurement_theta_min 1.61 _cell_measurement_theta_max 24.11 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.420 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1176 _exptl_absorpt_coefficient_mu 0.555 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Low data completion ratio is due to the limitations of the instrument available at the Australian Synchrotron operating under rotation data collection with a fixed detector and affects some high angle data. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71067 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron BM' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-BM1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q210' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 23158 _diffrn_reflns_av_R_equivalents 0.0887 _diffrn_reflns_av_sigmaI/netI 0.1140 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.61 _diffrn_reflns_theta_max 24.11 _reflns_number_total 3535 _reflns_number_gt 3227 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 1998)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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^)+(0.0857P)^2^+3.2506P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3535 _refine_ls_number_parameters 334 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0735 _refine_ls_R_factor_gt 0.0696 _refine_ls_wR_factor_ref 0.1733 _refine_ls_wR_factor_gt 0.1695 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.049 _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 0.40026(8) 0.40302(2) 0.17221(4) 0.0142(2) Uani 1 1 d . . . Cl1 Cl 0.66834(11) 0.41290(3) 0.25806(5) 0.0204(3) Uani 1 1 d . . . Cl2 Cl 0.52593(12) 0.40470(3) 0.02731(5) 0.0208(3) Uani 1 1 d . . . O1 O 0.4162(3) 0.32844(9) 0.17737(15) 0.0201(5) Uani 1 1 d . . . O2 O 0.3373(3) 0.47429(8) 0.17379(15) 0.0168(5) Uani 1 1 d . . . N1 N 0.2412(4) 0.39192(11) 0.29786(19) 0.0181(6) Uani 1 1 d . . . N2 N 0.1277(4) 0.39516(10) 0.10640(18) 0.0154(6) Uani 1 1 d . . . C1 C 0.4124(5) 0.29092(13) 0.2393(2) 0.0208(8) Uani 1 1 d . . . C2 C 0.3191(5) 0.29833(13) 0.3217(2) 0.0201(7) Uani 1 1 d . . . C3 C 0.3107(5) 0.25687(15) 0.3852(3) 0.0269(8) Uani 1 1 d . . . H3 H 0.2414 0.2614 0.4394 0.032 Uiso 1 1 calc R . . C4 C 0.4017(6) 0.20972(15) 0.3698(3) 0.0297(9) Uani 1 1 d . . . H4 H 0.3992 0.1821 0.4139 0.036 Uiso 1 1 calc R . . C5 C 0.4978(5) 0.20304(15) 0.2885(3) 0.0299(9) Uani 1 1 d . . . H5 H 0.5613 0.1706 0.2777 0.036 Uiso 1 1 calc R . . C6 C 0.5027(5) 0.24269(14) 0.2232(3) 0.0248(8) Uani 1 1 d . . . H6 H 0.5669 0.2372 0.1678 0.030 Uiso 1 1 calc R . . C7 C 0.2298(5) 0.34824(13) 0.3435(2) 0.0193(7) Uani 1 1 d . . . H7 H 0.1556 0.3489 0.3966 0.023 Uiso 1 1 calc R . . C8 C 0.1429(5) 0.43723(13) 0.3373(2) 0.0202(7) Uani 1 1 d . . . H8A H 0.0470 0.4240 0.3796 0.024 Uiso 1 1 calc R . . H8B H 0.0786 0.4572 0.2880 0.024 Uiso 1 1 calc R . . C9 C 0.2756(5) 0.47497(13) 0.3893(2) 0.0212(7) Uani 1 1 d . . . H9A H 0.3949 0.4773 0.3565 0.025 Uiso 1 1 calc R . . H9B H 0.2202 0.5109 0.3909 0.025 Uiso 1 1 calc R . . C10 C 0.3127(5) 0.45626(13) 0.4854(2) 0.0199(7) Uani 1 1 d . . . C11 C 0.2201(5) 0.47929(14) 0.5589(2) 0.0231(8) Uani 1 1 d . . . H11 H 0.1394 0.5086 0.5481 0.028 Uiso 1 1 calc R . . C12 C 0.2432(5) 0.46049(15) 0.6469(2) 0.0257(8) Uani 1 1 d . . . H12 H 0.1813 0.4773 0.6959 0.031 Uiso 1 1 calc R . . C13 C 0.3565(5) 0.41725(15) 0.6630(2) 0.0260(8) Uani 1 1 d . . . H13 H 0.3696 0.4033 0.7229 0.031 Uiso 1 1 calc R . . C14 C 0.4514(5) 0.39414(16) 0.5915(3) 0.0286(9) Uani 1 1 d . . . H14 H 0.5308 0.3646 0.6027 0.034 Uiso 1 1 calc R . . C15 C 0.4309(5) 0.41401(14) 0.5036(2) 0.0242(8) Uani 1 1 d . . . H15 H 0.4989 0.3984 0.4553 0.029 Uiso 1 1 calc R . . C16 C 0.1946(5) 0.50719(13) 0.1587(2) 0.0158(7) Uani 1 1 d . . . C17 C 0.0272(5) 0.48750(13) 0.1209(2) 0.0168(7) Uani 1 1 d . . . C18 C -0.1216(5) 0.52247(13) 0.1059(2) 0.0187(7) Uani 1 1 d . . . H18 H -0.2345 0.5096 0.0797 0.022 Uiso 1 1 calc R . . C19 C -0.1064(5) 0.57532(14) 0.1287(2) 0.0225(8) Uani 1 1 d . . . H19 H -0.2083 0.5987 0.1185 0.027 Uiso 1 1 calc R . . C20 C 0.0597(6) 0.59431(13) 0.1670(3) 0.0243(8) Uani 1 1 d . . . H20 H 0.0701 0.6307 0.1830 0.029 Uiso 1 1 calc R . . C21 C 0.2092(5) 0.56073(13) 0.1818(2) 0.0211(8) Uani 1 1 d . . . H21 H 0.3217 0.5741 0.2076 0.025 Uiso 1 1 calc R . . C22 C 0.0077(5) 0.43283(13) 0.0937(2) 0.0172(7) Uani 1 1 d . . . H22 H -0.1051 0.4234 0.0632 0.021 Uiso 1 1 calc R . . C23 C 0.0758(5) 0.34338(13) 0.0660(2) 0.0180(7) Uani 1 1 d . . . H23A H 0.1906 0.3235 0.0514 0.022 Uiso 1 1 calc R . . H23B H 0.0063 0.3495 0.0083 0.022 Uiso 1 1 calc R . . C24 C -0.0435(5) 0.30977(13) 0.1294(2) 0.0196(7) Uani 1 1 d . . . H24A H 0.0224 0.3047 0.1884 0.024 Uiso 1 1 calc R . . H24B H -0.1626 0.3282 0.1411 0.024 Uiso 1 1 calc R . . C25 C -0.0814(5) 0.25647(13) 0.0855(2) 0.0189(7) Uani 1 1 d . . . C26 C -0.1940(5) 0.25321(14) 0.0081(3) 0.0247(8) Uani 1 1 d . . . H26 H -0.2497 0.2845 -0.0161 0.030 Uiso 1 1 calc R . . C27 C -0.2260(5) 0.20468(16) -0.0343(3) 0.0310(9) Uani 1 1 d . . . H27 H -0.3022 0.2029 -0.0876 0.037 Uiso 1 1 calc R . . C28 C -0.1475(5) 0.15920(15) 0.0007(3) 0.0324(9) Uani 1 1 d . . . H28 H -0.1700 0.1260 -0.0281 0.039 Uiso 1 1 calc R . . C29 C -0.0368(5) 0.16186(15) 0.0771(3) 0.0341(9) Uani 1 1 d . . . H29 H 0.0168 0.1303 0.1015 0.041 Uiso 1 1 calc R . . C30 C -0.0021(5) 0.21011(14) 0.1194(3) 0.0273(8) Uani 1 1 d . . . H30 H 0.0766 0.2115 0.1719 0.033 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 0.0154(4) 0.0123(4) 0.0148(4) -0.0005(2) -0.0032(3) 0.0009(2) Cl1 0.0176(5) 0.0238(5) 0.0197(5) -0.0032(3) -0.0054(4) 0.0024(3) Cl2 0.0204(5) 0.0259(5) 0.0160(5) -0.0023(3) -0.0006(4) -0.0022(3) O1 0.0206(13) 0.0189(13) 0.0207(12) -0.0023(9) -0.0025(10) 0.0020(9) O2 0.0175(12) 0.0148(11) 0.0182(12) -0.0010(9) -0.0031(10) 0.0008(9) N1 0.0194(15) 0.0207(15) 0.0142(14) -0.0031(11) -0.0072(12) 0.0002(11) N2 0.0200(15) 0.0132(13) 0.0129(13) 0.0004(10) -0.0005(12) -0.0014(11) C1 0.0175(18) 0.0200(18) 0.0249(18) -0.0038(14) -0.0070(15) -0.0026(13) C2 0.0206(18) 0.0153(17) 0.0242(18) 0.0037(14) -0.0047(15) 0.0006(13) C3 0.030(2) 0.025(2) 0.0258(19) 0.0038(15) -0.0041(17) -0.0028(15) C4 0.036(2) 0.0200(19) 0.033(2) 0.0078(16) -0.0053(18) -0.0030(15) C5 0.032(2) 0.0162(18) 0.041(2) 0.0039(16) -0.0058(18) 0.0038(15) C6 0.0263(18) 0.0166(17) 0.0315(19) -0.0029(15) -0.0011(16) -0.0009(14) C7 0.0209(18) 0.0203(17) 0.0165(16) -0.0002(13) -0.0037(14) -0.0014(13) C8 0.0212(18) 0.0222(18) 0.0172(17) 0.0025(13) -0.0009(14) 0.0014(14) C9 0.0247(18) 0.0170(17) 0.0219(18) -0.0019(13) -0.0013(15) 0.0003(13) C10 0.0204(18) 0.0203(18) 0.0189(17) -0.0029(13) -0.0011(15) -0.0048(13) C11 0.0247(19) 0.0224(18) 0.0222(18) -0.0017(14) 0.0001(15) 0.0020(14) C12 0.030(2) 0.028(2) 0.0192(18) -0.0059(14) -0.0007(16) -0.0040(15) C13 0.025(2) 0.033(2) 0.0194(18) 0.0009(15) -0.0047(16) -0.0020(16) C14 0.025(2) 0.034(2) 0.026(2) 0.0010(16) -0.0064(17) 0.0055(15) C15 0.026(2) 0.028(2) 0.0191(18) -0.0017(14) -0.0022(16) 0.0042(15) C16 0.0210(17) 0.0146(16) 0.0118(15) 0.0030(12) -0.0016(13) 0.0017(13) C17 0.0212(18) 0.0179(17) 0.0112(15) 0.0024(12) -0.0006(14) 0.0021(13) C18 0.0209(19) 0.0214(18) 0.0138(16) 0.0031(13) -0.0036(14) 0.0033(13) C19 0.028(2) 0.0219(18) 0.0177(17) 0.0046(14) 0.0046(15) 0.0088(15) C20 0.036(2) 0.0147(17) 0.0224(18) 0.0016(13) -0.0001(17) 0.0023(14) C21 0.0277(19) 0.0159(17) 0.0197(17) -0.0003(13) -0.0050(15) -0.0003(14) C22 0.0183(16) 0.0194(17) 0.0139(16) 0.0010(13) -0.0030(13) -0.0015(14) C23 0.0218(17) 0.0156(16) 0.0165(16) -0.0022(13) -0.0038(14) -0.0026(13) C24 0.0202(18) 0.0178(17) 0.0209(17) 0.0016(14) -0.0002(14) -0.0016(13) C25 0.0171(16) 0.0166(17) 0.0229(17) -0.0008(13) 0.0008(14) -0.0026(13) C26 0.0239(18) 0.0211(18) 0.0289(19) -0.0013(15) -0.0056(16) -0.0003(14) C27 0.025(2) 0.035(2) 0.033(2) -0.0083(17) -0.0034(18) -0.0069(16) C28 0.025(2) 0.023(2) 0.049(2) -0.0136(17) 0.0058(19) -0.0066(15) C29 0.031(2) 0.0146(18) 0.057(3) 0.0037(18) 0.001(2) 0.0001(14) C30 0.0258(19) 0.0221(19) 0.034(2) 0.0059(16) -0.0053(17) 0.0005(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 O2 1.851(2) . ? Ti1 O1 1.884(2) . ? Ti1 N2 2.181(3) . ? Ti1 N1 2.200(3) . ? Ti1 Cl1 2.3006(10) . ? Ti1 Cl2 2.3211(11) . ? O1 C1 1.311(4) . ? O2 C16 1.334(4) . ? N1 C7 1.291(4) . ? N1 C8 1.466(4) . ? N2 C22 1.293(4) . ? N2 C23 1.478(4) . ? C1 C6 1.398(5) . ? C1 C2 1.403(5) . ? C2 C3 1.401(5) . ? C2 C7 1.449(5) . ? C3 C4 1.376(5) . ? C3 H3 0.9500 . ? C4 C5 1.397(6) . ? C4 H4 0.9500 . ? C5 C6 1.384(5) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C9 1.541(5) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 C10 1.508(5) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 C15 1.385(5) . ? C10 C11 1.400(5) . ? C11 C12 1.383(5) . ? C11 H11 0.9500 . ? C12 C13 1.378(5) . ? C12 H12 0.9500 . ? C13 C14 1.386(5) . ? C13 H13 0.9500 . ? C14 C15 1.390(5) . ? C14 H14 0.9500 . ? C15 H15 0.9500 . ? C16 C21 1.394(5) . ? C16 C17 1.408(5) . ? C17 C18 1.400(5) . ? C17 C22 1.440(5) . ? C18 C19 1.377(5) . ? C18 H18 0.9500 . ? C19 C20 1.397(5) . ? C19 H19 0.9500 . ? C20 C21 1.381(5) . ? C20 H20 0.9500 . ? C21 H21 0.9500 . ? C22 H22 0.9500 . ? C23 C24 1.528(5) . ? C23 H23A 0.9900 . ? C23 H23B 0.9900 . ? C24 C25 1.512(5) . ? C24 H24A 0.9900 . ? C24 H24B 0.9900 . ? C25 C26 1.388(5) . ? C25 C30 1.388(5) . ? C26 C27 1.390(5) . ? C26 H26 0.9500 . ? C27 C28 1.374(6) . ? C27 H27 0.9500 . ? C28 C29 1.368(6) . ? C28 H28 0.9500 . ? C29 C30 1.386(5) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? 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 168.88(11) . . ? O2 Ti1 N2 82.85(10) . . ? O1 Ti1 N2 88.91(10) . . ? O2 Ti1 N1 89.03(11) . . ? O1 Ti1 N1 82.61(10) . . ? N2 Ti1 N1 83.49(10) . . ? O2 Ti1 Cl1 95.23(7) . . ? O1 Ti1 Cl1 92.06(8) . . ? N2 Ti1 Cl1 172.94(8) . . ? N1 Ti1 Cl1 89.70(8) . . ? O2 Ti1 Cl2 95.27(8) . . ? O1 Ti1 Cl2 91.77(8) . . ? N2 Ti1 Cl2 87.34(8) . . ? N1 Ti1 Cl2 169.32(8) . . ? Cl1 Ti1 Cl2 99.61(4) . . ? C1 O1 Ti1 138.1(2) . . ? C16 O2 Ti1 141.9(2) . . ? C7 N1 C8 115.1(3) . . ? C7 N1 Ti1 125.5(2) . . ? C8 N1 Ti1 119.4(2) . . ? C22 N2 C23 115.2(3) . . ? C22 N2 Ti1 126.1(2) . . ? C23 N2 Ti1 118.5(2) . . ? O1 C1 C6 119.7(3) . . ? O1 C1 C2 121.1(3) . . ? C6 C1 C2 119.2(3) . . ? C3 C2 C1 120.0(3) . . ? C3 C2 C7 118.5(3) . . ? C1 C2 C7 121.6(3) . . ? C4 C3 C2 120.7(4) . . ? C4 C3 H3 119.7 . . ? C2 C3 H3 119.7 . . ? C3 C4 C5 119.0(3) . . ? C3 C4 H4 120.5 . . ? C5 C4 H4 120.5 . . ? C6 C5 C4 121.4(3) . . ? C6 C5 H5 119.3 . . ? C4 C5 H5 119.3 . . ? C5 C6 C1 119.6(4) . . ? C5 C6 H6 120.2 . . ? C1 C6 H6 120.2 . . ? N1 C7 C2 126.4(3) . . ? N1 C7 H7 116.8 . . ? C2 C7 H7 116.8 . . ? N1 C8 C9 112.2(3) . . ? N1 C8 H8A 109.2 . . ? C9 C8 H8A 109.2 . . ? N1 C8 H8B 109.2 . . ? C9 C8 H8B 109.2 . . ? H8A C8 H8B 107.9 . . ? C10 C9 C8 111.7(3) . . ? C10 C9 H9A 109.3 . . ? C8 C9 H9A 109.3 . . ? C10 C9 H9B 109.3 . . ? C8 C9 H9B 109.3 . . ? H9A C9 H9B 107.9 . . ? C15 C10 C11 117.8(3) . . ? C15 C10 C9 121.3(3) . . ? C11 C10 C9 120.8(3) . . ? C12 C11 C10 121.7(3) . . ? C12 C11 H11 119.2 . . ? C10 C11 H11 119.2 . . ? C13 C12 C11 119.6(3) . . ? C13 C12 H12 120.2 . . ? C11 C12 H12 120.2 . . ? C12 C13 C14 119.8(3) . . ? C12 C13 H13 120.1 . . ? C14 C13 H13 120.1 . . ? C13 C14 C15 120.3(4) . . ? C13 C14 H14 119.9 . . ? C15 C14 H14 119.9 . . ? C10 C15 C14 120.8(4) . . ? C10 C15 H15 119.6 . . ? C14 C15 H15 119.6 . . ? O2 C16 C21 120.3(3) . . ? O2 C16 C17 119.8(3) . . ? C21 C16 C17 119.9(3) . . ? C18 C17 C16 119.1(3) . . ? C18 C17 C22 119.2(3) . . ? C16 C17 C22 121.7(3) . . ? C19 C18 C17 120.8(3) . . ? C19 C18 H18 119.6 . . ? C17 C18 H18 119.6 . . ? C18 C19 C20 119.6(3) . . ? C18 C19 H19 120.2 . . ? C20 C19 H19 120.2 . . ? C21 C20 C19 120.8(3) . . ? C21 C20 H20 119.6 . . ? C19 C20 H20 119.6 . . ? C20 C21 C16 119.9(3) . . ? C20 C21 H21 120.1 . . ? C16 C21 H21 120.1 . . ? N2 C22 C17 126.8(3) . . ? N2 C22 H22 116.6 . . ? C17 C22 H22 116.6 . . ? N2 C23 C24 112.6(3) . . ? N2 C23 H23A 109.1 . . ? C24 C23 H23A 109.1 . . ? N2 C23 H23B 109.1 . . ? C24 C23 H23B 109.1 . . ? H23A C23 H23B 107.8 . . ? C25 C24 C23 109.4(3) . . ? C25 C24 H24A 109.8 . . ? C23 C24 H24A 109.8 . . ? C25 C24 H24B 109.8 . . ? C23 C24 H24B 109.8 . . ? H24A C24 H24B 108.2 . . ? C26 C25 C30 118.4(3) . . ? C26 C25 C24 120.0(3) . . ? C30 C25 C24 121.6(3) . . ? C25 C26 C27 120.7(3) . . ? C25 C26 H26 119.7 . . ? C27 C26 H26 119.7 . . ? C28 C27 C26 120.1(4) . . ? C28 C27 H27 120.0 . . ? C26 C27 H27 120.0 . . ? C29 C28 C27 119.8(3) . . ? C29 C28 H28 120.1 . . ? C27 C28 H28 120.1 . . ? C28 C29 C30 120.6(4) . . ? C28 C29 H29 119.7 . . ? C30 C29 H29 119.7 . . ? C29 C30 C25 120.4(4) . . ? C29 C30 H30 119.8 . . ? C25 C30 H30 119.8 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 Ti1 O1 C1 -68.0(7) . . . . ? N2 Ti1 O1 C1 -110.0(3) . . . . ? N1 Ti1 O1 C1 -26.5(3) . . . . ? Cl1 Ti1 O1 C1 63.0(3) . . . . ? Cl2 Ti1 O1 C1 162.6(3) . . . . ? O1 Ti1 O2 C16 -32.4(7) . . . . ? N2 Ti1 O2 C16 10.0(3) . . . . ? N1 Ti1 O2 C16 -73.6(3) . . . . ? Cl1 Ti1 O2 C16 -163.2(3) . . . . ? Cl2 Ti1 O2 C16 96.6(3) . . . . ? O2 Ti1 N1 C7 -176.0(3) . . . . ? O1 Ti1 N1 C7 11.4(3) . . . . ? N2 Ti1 N1 C7 101.1(3) . . . . ? Cl1 Ti1 N1 C7 -80.8(3) . . . . ? Cl2 Ti1 N1 C7 70.1(5) . . . . ? O2 Ti1 N1 C8 1.8(2) . . . . ? O1 Ti1 N1 C8 -170.9(2) . . . . ? N2 Ti1 N1 C8 -81.2(2) . . . . ? Cl1 Ti1 N1 C8 97.0(2) . . . . ? Cl2 Ti1 N1 C8 -112.2(4) . . . . ? O2 Ti1 N2 C22 -4.9(3) . . . . ? O1 Ti1 N2 C22 167.6(3) . . . . ? N1 Ti1 N2 C22 84.9(3) . . . . ? Cl1 Ti1 N2 C22 69.6(7) . . . . ? Cl2 Ti1 N2 C22 -100.6(3) . . . . ? O2 Ti1 N2 C23 170.4(2) . . . . ? O1 Ti1 N2 C23 -17.0(2) . . . . ? N1 Ti1 N2 C23 -99.7(2) . . . . ? Cl1 Ti1 N2 C23 -115.0(6) . . . . ? Cl2 Ti1 N2 C23 74.8(2) . . . . ? Ti1 O1 C1 C6 -153.5(3) . . . . ? Ti1 O1 C1 C2 26.5(5) . . . . ? O1 C1 C2 C3 177.4(3) . . . . ? C6 C1 C2 C3 -2.6(5) . . . . ? O1 C1 C2 C7 -2.5(5) . . . . ? C6 C1 C2 C7 177.4(3) . . . . ? C1 C2 C3 C4 3.6(5) . . . . ? C7 C2 C3 C4 -176.5(3) . . . . ? C2 C3 C4 C5 -2.1(6) . . . . ? C3 C4 C5 C6 -0.2(6) . . . . ? C4 C5 C6 C1 1.1(6) . . . . ? O1 C1 C6 C5 -179.7(3) . . . . ? C2 C1 C6 C5 0.3(5) . . . . ? C8 N1 C7 C2 -177.6(3) . . . . ? Ti1 N1 C7 C2 0.3(5) . . . . ? C3 C2 C7 N1 172.0(3) . . . . ? C1 C2 C7 N1 -8.1(5) . . . . ? C7 N1 C8 C9 100.4(3) . . . . ? Ti1 N1 C8 C9 -77.6(3) . . . . ? N1 C8 C9 C10 -83.8(4) . . . . ? C8 C9 C10 C15 75.6(4) . . . . ? C8 C9 C10 C11 -100.9(4) . . . . ? C15 C10 C11 C12 -0.7(5) . . . . ? C9 C10 C11 C12 175.8(3) . . . . ? C10 C11 C12 C13 -1.5(6) . . . . ? C11 C12 C13 C14 2.3(6) . . . . ? C12 C13 C14 C15 -0.8(6) . . . . ? C11 C10 C15 C14 2.2(5) . . . . ? C9 C10 C15 C14 -174.3(3) . . . . ? C13 C14 C15 C10 -1.5(6) . . . . ? Ti1 O2 C16 C21 171.0(3) . . . . ? Ti1 O2 C16 C17 -7.7(5) . . . . ? O2 C16 C17 C18 179.6(3) . . . . ? C21 C16 C17 C18 0.9(5) . . . . ? O2 C16 C17 C22 -3.0(5) . . . . ? C21 C16 C17 C22 178.3(3) . . . . ? C16 C17 C18 C19 -0.8(5) . . . . ? C22 C17 C18 C19 -178.3(3) . . . . ? C17 C18 C19 C20 0.2(5) . . . . ? C18 C19 C20 C21 0.3(5) . . . . ? C19 C20 C21 C16 -0.2(5) . . . . ? O2 C16 C21 C20 -179.1(3) . . . . ? C17 C16 C21 C20 -0.4(5) . . . . ? C23 N2 C22 C17 -176.2(3) . . . . ? Ti1 N2 C22 C17 -0.7(5) . . . . ? C18 C17 C22 N2 -176.6(3) . . . . ? C16 C17 C22 N2 6.1(5) . . . . ? C22 N2 C23 C24 -86.7(3) . . . . ? Ti1 N2 C23 C24 97.4(3) . . . . ? N2 C23 C24 C25 -176.9(3) . . . . ? C23 C24 C25 C26 -68.0(4) . . . . ? C23 C24 C25 C30 110.3(4) . . . . ? C30 C25 C26 C27 -0.1(5) . . . . ? C24 C25 C26 C27 178.3(3) . . . . ? C25 C26 C27 C28 0.6(6) . . . . ? C26 C27 C28 C29 -0.4(6) . . . . ? C27 C28 C29 C30 -0.4(6) . . . . ? C28 C29 C30 C25 0.9(6) . . . . ? C26 C25 C30 C29 -0.7(5) . . . . ? C24 C25 C30 C29 -179.0(3) . . . . ? _diffrn_measured_fraction_theta_max 0.836 _diffrn_reflns_theta_full 24.11 _diffrn_measured_fraction_theta_full 0.836 _refine_diff_density_max 0.463 _refine_diff_density_min -1.142 _refine_diff_density_rms 0.106 data_d:\23js50\pna21 _database_code_depnum_ccdc_archive 'CCDC 902039' #TrackingRef 'web_deposit_cif_file_2_MichaelGardiner_1348050215.compound 13.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H32 Cl3 N O2 Ti' _chemical_formula_weight 520.76 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 orthorhombic _symmetry_space_group_name_H-M 'P n a 21' _symmetry_space_group_name_Hall 'P 2c -2n' _symmetry_Int_Tables_number 33 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z' _cell_length_a 28.069(3) _cell_length_b 8.6610(12) _cell_length_c 20.8230(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 5062.2(9) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 61892 _cell_measurement_theta_min 1.45 _cell_measurement_theta_max 28.04 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.08 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.367 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2176 _exptl_absorpt_coefficient_mu 0.676 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71085 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron BM' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-BM1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q210' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 80972 _diffrn_reflns_av_R_equivalents 0.0643 _diffrn_reflns_av_sigmaI/netI 0.0298 _diffrn_reflns_limit_h_min -37 _diffrn_reflns_limit_h_max 37 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 1.45 _diffrn_reflns_theta_max 28.04 _reflns_number_total 12185 _reflns_number_gt 11468 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 1998)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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. The largest residual density was within 1A of a Ti centre. ; _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^)+(0.1637P)^2^+13.8159P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.52(4) _refine_ls_number_reflns 12185 _refine_ls_number_parameters 559 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0993 _refine_ls_R_factor_gt 0.0957 _refine_ls_wR_factor_ref 0.2533 _refine_ls_wR_factor_gt 0.2496 _refine_ls_goodness_of_fit_ref 1.079 _refine_ls_restrained_S_all 1.078 _refine_ls_shift/su_max 0.006 _refine_ls_shift/su_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.48074(4) 0.69933(11) 0.38017(5) 0.0246(2) Uani 1 1 d . . . Ti2 Ti 0.25532(4) 0.81449(11) 0.09935(5) 0.0261(2) Uani 1 1 d . . . Cl1 Cl 0.46685(6) 0.53980(18) 0.46703(6) 0.0353(3) Uani 1 1 d . . . Cl2 Cl 0.46637(6) 0.92907(19) 0.43132(9) 0.0407(4) Uani 1 1 d . . . Cl3 Cl 0.50876(5) 0.80911(17) 0.28664(7) 0.0329(3) Uani 1 1 d . . . Cl4 Cl 0.23103(6) 0.69648(19) 0.19272(8) 0.0388(4) Uani 1 1 d . . . Cl5 Cl 0.27211(6) 0.59071(19) 0.04482(10) 0.0455(4) Uani 1 1 d . . . Cl6 Cl 0.26510(5) 0.98231(17) 0.01431(7) 0.0329(3) Uani 1 1 d . . . O1 O 0.42091(15) 0.6736(5) 0.3530(2) 0.0298(9) Uani 1 1 d . . . O2 O 0.55239(15) 0.7248(5) 0.4211(2) 0.0297(8) Uani 1 1 d . . . O3 O 0.31583(14) 0.8471(5) 0.12487(19) 0.0253(8) Uani 1 1 d . . . O4 O 0.18369(15) 0.7779(5) 0.06035(19) 0.0284(8) Uani 1 1 d . . . N1 N 0.49352(16) 0.4701(6) 0.3296(2) 0.0247(9) Uani 1 1 d . . . N2 N 0.24105(16) 1.0395(6) 0.1525(2) 0.0245(9) Uani 1 1 d . . . C1 C 0.3890(2) 0.5609(7) 0.3436(3) 0.0275(11) Uani 1 1 d . . . C2 C 0.4065(2) 0.4159(8) 0.3266(3) 0.0315(12) Uani 1 1 d . . . C3 C 0.3752(3) 0.2935(11) 0.3140(4) 0.053(2) Uani 1 1 d . . . H3 H 0.3869 0.1957 0.3006 0.064 Uiso 1 1 calc R . . C4 C 0.3264(3) 0.3194(11) 0.3216(4) 0.052(2) Uani 1 1 d . . . H4 H 0.3046 0.2366 0.3157 0.063 Uiso 1 1 calc R . . C5 C 0.3096(2) 0.4632(10) 0.3377(3) 0.0425(17) Uani 1 1 d . . . H5 H 0.2762 0.4772 0.3414 0.051 Uiso 1 1 calc R . . C6 C 0.3392(2) 0.5899(8) 0.3489(3) 0.0321(12) Uani 1 1 d . . . C7 C 0.3197(2) 0.7467(9) 0.3663(3) 0.0403(15) Uani 1 1 d . . . C8 C 0.2657(3) 0.7466(12) 0.3704(4) 0.052(2) Uani 1 1 d . . . H8A H 0.2545 0.8501 0.3819 0.077 Uiso 1 1 calc R . . H8B H 0.2554 0.6727 0.4033 0.077 Uiso 1 1 calc R . . H8C H 0.2523 0.7167 0.3288 0.077 Uiso 1 1 calc R . . C9 C 0.3346(3) 0.8664(13) 0.3163(6) 0.076(4) Uani 1 1 d . . . H9A H 0.3218 0.9677 0.3282 0.113 Uiso 1 1 calc R . . H9B H 0.3220 0.8365 0.2741 0.113 Uiso 1 1 calc R . . H9C H 0.3694 0.8717 0.3143 0.113 Uiso 1 1 calc R . . C10 C 0.3383(3) 0.7917(9) 0.4326(4) 0.0433(16) Uani 1 1 d . . . H10A H 0.3259 0.8936 0.4443 0.065 Uiso 1 1 calc R . . H10B H 0.3732 0.7950 0.4318 0.065 Uiso 1 1 calc R . . H10C H 0.3277 0.7153 0.4642 0.065 Uiso 1 1 calc R . . C11 C 0.4570(2) 0.3841(7) 0.3177(3) 0.0266(11) Uani 1 1 d . . . H11 H 0.4641 0.2851 0.3006 0.032 Uiso 1 1 calc R . . C12 C 0.5392(2) 0.3842(7) 0.3150(3) 0.0266(11) Uani 1 1 d . . . C13 C 0.5826(2) 0.4941(8) 0.3192(3) 0.0327(12) Uani 1 1 d . . . H13A H 0.5795 0.5755 0.2868 0.049 Uiso 1 1 calc R . . H13B H 0.6119 0.4356 0.3115 0.049 Uiso 1 1 calc R . . H13C H 0.5838 0.5408 0.3621 0.049 Uiso 1 1 calc R . . C14 C 0.5461(3) 0.2610(9) 0.3658(3) 0.0391(14) Uani 1 1 d . . . H14A H 0.5460 0.3089 0.4084 0.059 Uiso 1 1 calc R . . H14B H 0.5767 0.2087 0.3588 0.059 Uiso 1 1 calc R . . H14C H 0.5202 0.1855 0.3630 0.059 Uiso 1 1 calc R . . C15 C 0.53889(19) 0.3254(7) 0.2449(2) 0.0226(10) Uani 1 1 d . . . C16 C 0.52537(19) 0.4242(7) 0.1960(3) 0.0245(10) Uani 1 1 d . . . H16 H 0.5146 0.5256 0.2057 0.029 Uiso 1 1 calc R . . C17 C 0.5276(2) 0.3742(8) 0.1323(3) 0.0306(12) Uani 1 1 d . . . H17 H 0.5179 0.4419 0.0988 0.037 Uiso 1 1 calc R . . C18 C 0.5437(2) 0.2275(8) 0.1172(3) 0.0332(12) Uani 1 1 d . . . H18 H 0.5463 0.1960 0.0736 0.040 Uiso 1 1 calc R . . C19 C 0.5555(2) 0.1292(8) 0.1655(4) 0.0427(17) Uani 1 1 d . . . H19 H 0.5653 0.0271 0.1552 0.051 Uiso 1 1 calc R . . C20 C 0.5537(2) 0.1757(6) 0.2317(3) 0.0280(11) Uani 1 1 d . . . H20 H 0.5622 0.1066 0.2652 0.034 Uiso 1 1 calc R . . C21 C 0.5691(3) 0.6759(13) 0.4837(4) 0.063(3) Uani 1 1 d . . . H21A H 0.5628 0.5645 0.4901 0.075 Uiso 1 1 calc R . . H21B H 0.5526 0.7345 0.5180 0.075 Uiso 1 1 calc R . . C22 C 0.6214(3) 0.7073(16) 0.4854(7) 0.090(5) Uani 1 1 d . . . H22A H 0.6315 0.7402 0.5289 0.109 Uiso 1 1 calc R . . H22B H 0.6397 0.6141 0.4731 0.109 Uiso 1 1 calc R . . C23 C 0.6284(4) 0.8265(18) 0.4407(8) 0.113(7) Uani 1 1 d . . . H23A H 0.6565 0.8028 0.4137 0.135 Uiso 1 1 calc R . . H23B H 0.6346 0.9246 0.4636 0.135 Uiso 1 1 calc R . . C24 C 0.5852(3) 0.8437(8) 0.3991(4) 0.0438(17) Uani 1 1 d . . . H24A H 0.5710 0.9476 0.4043 0.053 Uiso 1 1 calc R . . H24B H 0.5935 0.8281 0.3534 0.053 Uiso 1 1 calc R . . C25 C 0.34627(19) 0.9646(7) 0.1345(3) 0.0249(10) Uani 1 1 d . . . C26 C 0.3274(2) 1.1079(8) 0.1528(3) 0.0320(13) Uani 1 1 d . . . C27 C 0.3576(2) 1.2333(9) 0.1612(4) 0.0419(16) Uani 1 1 d . . . H27 H 0.3447 1.3318 0.1711 0.050 Uiso 1 1 calc R . . C28 C 0.4062(3) 1.2152(11) 0.1551(5) 0.059(3) Uani 1 1 d . . . H28 H 0.4270 1.3001 0.1621 0.071 Uiso 1 1 calc R . . C29 C 0.4242(2) 1.0723(9) 0.1389(3) 0.0373(14) Uani 1 1 d . . . H29 H 0.4578 1.0617 0.1357 0.045 Uiso 1 1 calc R . . C30 C 0.3962(2) 0.9421(8) 0.1267(3) 0.0312(12) Uani 1 1 d . . . C31 C 0.4162(2) 0.7845(9) 0.1065(5) 0.0479(18) Uani 1 1 d . . . C32 C 0.4714(3) 0.7957(11) 0.1010(6) 0.059(2) Uani 1 1 d . . . H32A H 0.4849 0.8194 0.1433 0.088 Uiso 1 1 calc R . . H32B H 0.4798 0.8776 0.0707 0.088 Uiso 1 1 calc R . . H32C H 0.4841 0.6970 0.0858 0.088 Uiso 1 1 calc R . . C33 C 0.4040(3) 0.6635(14) 0.1557(8) 0.099(5) Uani 1 1 d . . . H33A H 0.4171 0.6936 0.1975 0.148 Uiso 1 1 calc R . . H33B H 0.4176 0.5641 0.1427 0.148 Uiso 1 1 calc R . . H33C H 0.3693 0.6541 0.1590 0.148 Uiso 1 1 calc R . . C34 C 0.3971(3) 0.7471(12) 0.0385(6) 0.064(3) Uani 1 1 d . . . H34A H 0.4062 0.8299 0.0088 0.096 Uiso 1 1 calc R . . H34B H 0.3623 0.7386 0.0399 0.096 Uiso 1 1 calc R . . H34C H 0.4108 0.6492 0.0237 0.096 Uiso 1 1 calc R . . C35 C 0.2772(2) 1.1289(7) 0.1637(3) 0.0287(11) Uani 1 1 d . . . H35 H 0.2691 1.2255 0.1823 0.034 Uiso 1 1 calc R . . C36 C 0.1936(2) 1.1177(7) 0.1690(2) 0.0254(10) Uani 1 1 d . . . C37 C 0.1860(3) 1.2433(9) 0.1177(3) 0.0427(17) Uani 1 1 d . . . H37A H 0.2127 1.3162 0.1188 0.064 Uiso 1 1 calc R . . H37B H 0.1563 1.2986 0.1264 0.064 Uiso 1 1 calc R . . H37C H 0.1843 1.1952 0.0752 0.064 Uiso 1 1 calc R . . C38 C 0.1527(2) 1.0060(9) 0.1676(3) 0.0349(13) Uani 1 1 d . . . H38A H 0.1576 0.9260 0.2002 0.052 Uiso 1 1 calc R . . H38B H 0.1508 0.9580 0.1251 0.052 Uiso 1 1 calc R . . H38C H 0.1229 1.0613 0.1766 0.052 Uiso 1 1 calc R . . C39 C 0.1959(2) 1.1843(7) 0.2376(3) 0.0286(12) Uani 1 1 d . . . C40 C 0.2092(2) 1.0907(8) 0.2893(3) 0.0316(12) Uani 1 1 d . . . H40 H 0.2199 0.9883 0.2817 0.038 Uiso 1 1 calc R . . C41 C 0.2069(2) 1.1468(9) 0.3520(3) 0.0361(13) Uani 1 1 d . . . H41 H 0.2160 1.0824 0.3869 0.043 Uiso 1 1 calc R . . C42 C 0.1915(2) 1.2946(9) 0.3636(3) 0.0422(17) Uani 1 1 d . . . H42 H 0.1900 1.3325 0.4063 0.051 Uiso 1 1 calc R . . C43 C 0.1778(2) 1.3907(8) 0.3117(4) 0.0394(15) Uani 1 1 d . . . H43 H 0.1667 1.4926 0.3193 0.047 Uiso 1 1 calc R . . C44 C 0.1809(2) 1.3341(7) 0.2503(3) 0.0345(13) Uani 1 1 d . . . H44 H 0.1725 1.3994 0.2154 0.041 Uiso 1 1 calc R . . C45 C 0.1679(3) 0.8207(11) -0.0057(4) 0.053(2) Uani 1 1 d . . . H45A H 0.1927 0.7935 -0.0376 0.064 Uiso 1 1 calc R . . H45B H 0.1616 0.9330 -0.0084 0.064 Uiso 1 1 calc R . . C46 C 0.1233(3) 0.7313(9) -0.0182(4) 0.0437(16) Uani 1 1 d . . . H46A H 0.1300 0.6389 -0.0447 0.052 Uiso 1 1 calc R . . H46B H 0.0995 0.7960 -0.0407 0.052 Uiso 1 1 calc R . . C47 C 0.1056(3) 0.6856(11) 0.0470(4) 0.0507(19) Uani 1 1 d . . . H47A H 0.0857 0.5914 0.0448 0.061 Uiso 1 1 calc R . . H47B H 0.0870 0.7698 0.0670 0.061 Uiso 1 1 calc R . . C48 C 0.1522(3) 0.6555(9) 0.0840(4) 0.0441(17) Uani 1 1 d . . . H48A H 0.1472 0.6642 0.1309 0.053 Uiso 1 1 calc R . . H48B H 0.1652 0.5520 0.0741 0.053 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 0.0246(5) 0.0245(4) 0.0246(4) -0.0009(4) 0.0013(4) -0.0030(3) Ti2 0.0250(5) 0.0224(4) 0.0310(5) 0.0001(4) 0.0015(4) -0.0023(3) Cl1 0.0477(8) 0.0380(7) 0.0201(6) 0.0002(5) 0.0012(6) -0.0145(6) Cl2 0.0380(8) 0.0311(7) 0.0529(10) -0.0121(7) 0.0094(7) -0.0019(6) Cl3 0.0331(7) 0.0352(7) 0.0304(6) 0.0101(6) -0.0002(5) -0.0043(5) Cl4 0.0351(7) 0.0387(8) 0.0426(8) 0.0161(7) -0.0031(6) -0.0072(6) Cl5 0.0382(8) 0.0286(7) 0.0698(12) -0.0135(7) 0.0033(8) 0.0002(6) Cl6 0.0397(7) 0.0339(7) 0.0251(6) -0.0008(5) 0.0057(5) -0.0077(6) O1 0.029(2) 0.0268(19) 0.034(2) 0.0077(16) 0.0062(17) 0.0000(16) O2 0.031(2) 0.0275(19) 0.031(2) 0.0016(16) -0.0034(16) -0.0058(16) O3 0.0237(18) 0.0246(18) 0.0275(18) -0.0024(15) 0.0028(14) -0.0014(15) O4 0.033(2) 0.028(2) 0.0244(19) 0.0020(15) 0.0010(15) -0.0098(16) N1 0.018(2) 0.036(3) 0.020(2) 0.0011(17) 0.0025(16) -0.0022(18) N2 0.025(2) 0.028(2) 0.021(2) -0.0005(17) -0.0003(17) 0.0030(18) C1 0.031(3) 0.034(3) 0.018(2) 0.000(2) 0.0004(19) -0.006(2) C2 0.027(3) 0.038(3) 0.030(3) -0.008(2) 0.002(2) -0.005(2) C3 0.031(3) 0.064(5) 0.064(5) -0.037(4) 0.009(3) -0.020(3) C4 0.029(3) 0.072(6) 0.056(4) -0.036(4) 0.013(3) -0.021(3) C5 0.020(3) 0.074(5) 0.033(3) -0.018(3) 0.003(2) -0.005(3) C6 0.026(3) 0.051(4) 0.019(2) 0.002(2) 0.002(2) 0.002(3) C7 0.036(3) 0.045(4) 0.040(4) 0.012(3) 0.007(3) 0.009(3) C8 0.035(3) 0.075(5) 0.045(4) 0.020(4) 0.004(3) 0.008(4) C9 0.042(4) 0.077(6) 0.108(8) 0.064(6) 0.029(5) 0.019(4) C10 0.035(3) 0.041(4) 0.053(4) -0.010(3) 0.008(3) 0.005(3) C11 0.027(2) 0.032(3) 0.021(2) -0.009(2) 0.001(2) -0.004(2) C12 0.026(2) 0.028(3) 0.026(2) -0.001(2) 0.002(2) 0.000(2) C13 0.021(2) 0.047(3) 0.030(3) -0.010(3) -0.001(2) 0.000(2) C14 0.050(4) 0.043(3) 0.024(3) 0.008(3) 0.006(2) 0.011(3) C15 0.022(2) 0.029(3) 0.017(2) -0.0003(19) 0.0014(18) 0.0030(19) C16 0.022(2) 0.030(3) 0.021(2) 0.000(2) 0.0027(19) -0.001(2) C17 0.024(2) 0.045(3) 0.023(2) -0.007(2) 0.000(2) -0.003(2) C18 0.029(3) 0.041(3) 0.029(3) -0.009(2) 0.001(2) -0.001(2) C19 0.020(2) 0.033(3) 0.076(5) -0.022(3) 0.005(3) -0.005(2) C20 0.026(3) 0.020(2) 0.038(3) 0.002(2) 0.008(2) -0.006(2) C21 0.041(4) 0.096(7) 0.051(5) 0.044(5) -0.018(3) -0.017(4) C22 0.039(4) 0.115(10) 0.118(10) 0.073(9) -0.026(5) -0.020(5) C23 0.075(7) 0.130(11) 0.134(12) 0.072(10) -0.069(8) -0.075(8) C24 0.038(3) 0.033(3) 0.060(4) 0.012(3) -0.018(3) -0.017(3) C25 0.019(2) 0.032(3) 0.024(2) 0.001(2) 0.0033(18) -0.005(2) C26 0.030(3) 0.041(3) 0.025(3) -0.015(2) 0.010(2) -0.011(2) C27 0.033(3) 0.046(4) 0.046(4) -0.024(3) 0.015(3) -0.009(3) C28 0.035(4) 0.072(6) 0.072(6) -0.039(5) 0.017(4) -0.023(4) C29 0.026(3) 0.047(4) 0.038(3) -0.009(3) 0.001(2) -0.008(3) C30 0.023(3) 0.039(3) 0.031(3) 0.000(2) 0.004(2) -0.003(2) C31 0.023(3) 0.042(4) 0.078(5) 0.016(4) 0.001(3) 0.010(3) C32 0.023(3) 0.061(5) 0.091(7) 0.024(5) 0.009(4) 0.010(3) C33 0.028(4) 0.085(7) 0.184(14) 0.083(9) 0.015(6) 0.017(4) C34 0.046(4) 0.060(5) 0.085(7) -0.034(5) 0.016(4) 0.006(4) C35 0.030(3) 0.026(3) 0.030(3) -0.005(2) 0.010(2) -0.002(2) C36 0.023(2) 0.036(3) 0.017(2) -0.002(2) 0.0003(18) 0.005(2) C37 0.056(4) 0.053(4) 0.018(2) 0.010(3) 0.004(2) 0.031(4) C38 0.024(3) 0.055(4) 0.026(3) -0.010(3) 0.001(2) -0.007(3) C39 0.020(2) 0.029(3) 0.037(3) -0.002(2) 0.014(2) -0.002(2) C40 0.023(3) 0.037(3) 0.035(3) -0.001(2) 0.000(2) -0.002(2) C41 0.024(3) 0.053(4) 0.031(3) -0.003(3) -0.003(2) -0.004(3) C42 0.026(3) 0.068(5) 0.032(3) -0.025(3) 0.002(2) -0.008(3) C43 0.032(3) 0.039(3) 0.047(4) -0.016(3) 0.004(3) 0.000(3) C44 0.031(3) 0.026(3) 0.046(4) -0.011(3) 0.002(3) 0.004(2) C45 0.058(5) 0.059(5) 0.043(4) 0.015(4) -0.015(4) -0.021(4) C46 0.044(4) 0.039(3) 0.048(4) 0.001(3) -0.014(3) 0.004(3) C47 0.041(4) 0.062(5) 0.049(4) 0.015(4) -0.006(3) -0.015(3) C48 0.045(4) 0.039(3) 0.048(4) 0.012(3) -0.004(3) -0.023(3) _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 1.786(5) . ? Ti1 O2 2.195(4) . ? Ti1 N1 2.275(5) . ? Ti1 Cl2 2.2926(18) . ? Ti1 Cl3 2.3056(17) . ? Ti1 Cl1 2.3091(17) . ? Ti2 O3 1.802(4) . ? Ti2 O4 2.191(4) . ? Ti2 N2 2.277(5) . ? Ti2 Cl5 2.2952(19) . ? Ti2 Cl4 2.2998(18) . ? Ti2 Cl6 2.3073(18) . ? O1 C1 1.338(7) . ? O2 C21 1.449(8) . ? O2 C24 1.456(8) . ? O3 C25 1.344(7) . ? O4 C48 1.465(7) . ? O4 C45 1.492(8) . ? N1 C11 1.292(7) . ? N1 C12 1.515(7) . ? N2 C35 1.297(8) . ? N2 C36 1.533(7) . ? C1 C2 1.394(9) . ? C1 C6 1.425(8) . ? C2 C3 1.402(9) . ? C2 C11 1.454(8) . ? C3 C4 1.397(10) . ? C3 H3 0.9500 . ? C4 C5 1.373(12) . ? C4 H4 0.9500 . ? C5 C6 1.396(10) . ? C5 H5 0.9500 . ? C6 C7 1.509(10) . ? C7 C8 1.519(10) . ? C7 C10 1.525(11) . ? C7 C9 1.528(10) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11 0.9500 . ? C12 C14 1.515(8) . ? C12 C15 1.546(8) . ? C12 C13 1.547(8) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C15 C16 1.383(8) . ? C15 C20 1.388(8) . ? C16 C17 1.397(8) . ? C16 H16 0.9500 . ? C17 C18 1.385(9) . ? C17 H17 0.9500 . ? C18 C19 1.360(11) . ? C18 H18 0.9500 . ? C19 C20 1.438(10) . ? C19 H19 0.9500 . ? C20 H20 0.9500 . ? C21 C22 1.495(12) . ? C21 H21A 0.9900 . ? C21 H21B 0.9900 . ? C22 C23 1.404(15) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 C24 1.497(11) . ? C23 H23A 0.9900 . ? C23 H23B 0.9900 . ? C24 H24A 0.9900 . ? C24 H24B 0.9900 . ? C25 C26 1.402(9) . ? C25 C30 1.424(7) . ? C26 C27 1.387(9) . ? C26 C35 1.439(8) . ? C27 C28 1.379(10) . ? C27 H27 0.9500 . ? C28 C29 1.380(12) . ? C28 H28 0.9500 . ? C29 C30 1.397(9) . ? C29 H29 0.9500 . ? C30 C31 1.535(10) . ? C31 C33 1.507(13) . ? C31 C34 1.548(15) . ? C31 C32 1.554(9) . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? C33 H33A 0.9800 . ? C33 H33B 0.9800 . ? C33 H33C 0.9800 . ? C34 H34A 0.9800 . ? C34 H34B 0.9800 . ? C34 H34C 0.9800 . ? C35 H35 0.9500 . ? C36 C38 1.502(9) . ? C36 C37 1.540(8) . ? C36 C39 1.541(8) . ? C37 H37A 0.9800 . ? C37 H37B 0.9800 . ? C37 H37C 0.9800 . ? C38 H38A 0.9800 . ? C38 H38B 0.9800 . ? C38 H38C 0.9800 . ? C39 C44 1.389(8) . ? C39 C40 1.399(9) . ? C40 C41 1.395(9) . ? C40 H40 0.9500 . ? C41 C42 1.372(11) . ? C41 H41 0.9500 . ? C42 C43 1.416(11) . ? C42 H42 0.9500 . ? C43 C44 1.371(9) . ? C43 H43 0.9500 . ? C44 H44 0.9500 . ? C45 C46 1.495(11) . ? C45 H45A 0.9900 . ? C45 H45B 0.9900 . ? C46 C47 1.498(12) . ? C46 H46A 0.9900 . ? C46 H46B 0.9900 . ? C47 C48 1.540(11) . ? C47 H47A 0.9900 . ? C47 H47B 0.9900 . ? C48 H48A 0.9900 . ? C48 H48B 0.9900 . ? 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 175.47(19) . . ? O1 Ti1 N1 83.85(19) . . ? O2 Ti1 N1 97.04(17) . . ? O1 Ti1 Cl2 95.17(15) . . ? O2 Ti1 Cl2 83.90(13) . . ? N1 Ti1 Cl2 178.92(13) . . ? O1 Ti1 Cl3 96.00(15) . . ? O2 Ti1 Cl3 88.51(12) . . ? N1 Ti1 Cl3 85.14(12) . . ? Cl2 Ti1 Cl3 95.42(7) . . ? O1 Ti1 Cl1 90.85(14) . . ? O2 Ti1 Cl1 84.88(12) . . ? N1 Ti1 Cl1 82.35(12) . . ? Cl2 Ti1 Cl1 97.23(7) . . ? Cl3 Ti1 Cl1 165.01(8) . . ? O3 Ti2 O4 175.38(18) . . ? O3 Ti2 N2 83.57(18) . . ? O4 Ti2 N2 98.21(17) . . ? O3 Ti2 Cl5 94.87(14) . . ? O4 Ti2 Cl5 83.27(13) . . ? N2 Ti2 Cl5 178.12(14) . . ? O3 Ti2 Cl4 95.73(14) . . ? O4 Ti2 Cl4 88.69(12) . . ? N2 Ti2 Cl4 85.24(13) . . ? Cl5 Ti2 Cl4 95.96(8) . . ? O3 Ti2 Cl6 90.87(14) . . ? O4 Ti2 Cl6 85.18(12) . . ? N2 Ti2 Cl6 81.67(13) . . ? Cl5 Ti2 Cl6 97.34(8) . . ? Cl4 Ti2 Cl6 164.59(8) . . ? C1 O1 Ti1 140.0(4) . . ? C21 O2 C24 106.5(5) . . ? C21 O2 Ti1 128.0(4) . . ? C24 O2 Ti1 122.0(4) . . ? C25 O3 Ti2 139.7(4) . . ? C48 O4 C45 108.1(5) . . ? C48 O4 Ti2 122.2(4) . . ? C45 O4 Ti2 125.3(4) . . ? C11 N1 C12 110.5(5) . . ? C11 N1 Ti1 117.8(4) . . ? C12 N1 Ti1 131.0(4) . . ? C35 N2 C36 112.1(5) . . ? C35 N2 Ti2 117.4(4) . . ? C36 N2 Ti2 129.8(4) . . ? O1 C1 C2 117.3(5) . . ? O1 C1 C6 121.1(6) . . ? C2 C1 C6 121.6(6) . . ? C1 C2 C3 120.6(6) . . ? C1 C2 C11 123.1(5) . . ? C3 C2 C11 116.3(6) . . ? C4 C3 C2 118.1(7) . . ? C4 C3 H3 120.9 . . ? C2 C3 H3 120.9 . . ? C5 C4 C3 120.7(7) . . ? C5 C4 H4 119.7 . . ? C3 C4 H4 119.7 . . ? C4 C5 C6 123.3(6) . . ? C4 C5 H5 118.4 . . ? C6 C5 H5 118.4 . . ? C5 C6 C1 115.7(6) . . ? C5 C6 C7 122.1(6) . . ? C1 C6 C7 122.3(6) . . ? C6 C7 C8 112.0(7) . . ? C6 C7 C10 108.8(5) . . ? C8 C7 C10 106.9(6) . . ? C6 C7 C9 110.3(7) . . ? C8 C7 C9 108.2(6) . . ? C10 C7 C9 110.5(8) . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 H10A 109.5 . . ? C7 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 C2 129.7(6) . . ? N1 C11 H11 115.1 . . ? C2 C11 H11 115.1 . . ? N1 C12 C14 108.3(5) . . ? N1 C12 C15 110.3(4) . . ? C14 C12 C15 115.3(5) . . ? N1 C12 C13 110.6(5) . . ? C14 C12 C13 107.0(5) . . ? C15 C12 C13 105.2(5) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C16 C15 C20 121.0(5) . . ? C16 C15 C12 119.5(5) . . ? C20 C15 C12 119.5(5) . . ? C15 C16 C17 119.7(6) . . ? C15 C16 H16 120.2 . . ? C17 C16 H16 120.2 . . ? C18 C17 C16 121.0(6) . . ? C18 C17 H17 119.5 . . ? C16 C17 H17 119.5 . . ? C19 C18 C17 119.1(6) . . ? C19 C18 H18 120.4 . . ? C17 C18 H18 120.4 . . ? C18 C19 C20 121.7(6) . . ? C18 C19 H19 119.2 . . ? C20 C19 H19 119.2 . . ? C15 C20 C19 117.5(6) . . ? C15 C20 H20 121.2 . . ? C19 C20 H20 121.2 . . ? O2 C21 C22 106.7(7) . . ? O2 C21 H21A 110.4 . . ? C22 C21 H21A 110.4 . . ? O2 C21 H21B 110.4 . . ? C22 C21 H21B 110.4 . . ? H21A C21 H21B 108.6 . . ? C23 C22 C21 104.7(8) . . ? C23 C22 H22A 110.8 . . ? C21 C22 H22A 110.8 . . ? C23 C22 H22B 110.8 . . ? C21 C22 H22B 110.8 . . ? H22A C22 H22B 108.9 . . ? C22 C23 C24 110.1(8) . . ? C22 C23 H23A 109.6 . . ? C24 C23 H23A 109.6 . . ? C22 C23 H23B 109.6 . . ? C24 C23 H23B 109.6 . . ? H23A C23 H23B 108.2 . . ? O2 C24 C23 105.1(6) . . ? O2 C24 H24A 110.7 . . ? C23 C24 H24A 110.7 . . ? O2 C24 H24B 110.7 . . ? C23 C24 H24B 110.7 . . ? H24A C24 H24B 108.8 . . ? O3 C25 C26 118.1(5) . . ? O3 C25 C30 120.3(5) . . ? C26 C25 C30 121.6(5) . . ? C27 C26 C25 119.8(6) . . ? C27 C26 C35 118.6(6) . . ? C25 C26 C35 121.6(5) . . ? C28 C27 C26 120.2(7) . . ? C28 C27 H27 119.9 . . ? C26 C27 H27 119.9 . . ? C27 C28 C29 119.1(7) . . ? C27 C28 H28 120.4 . . ? C29 C28 H28 120.4 . . ? C28 C29 C30 124.3(6) . . ? C28 C29 H29 117.9 . . ? C30 C29 H29 117.9 . . ? C29 C30 C25 115.0(6) . . ? C29 C30 C31 124.1(6) . . ? C25 C30 C31 120.9(6) . . ? C33 C31 C30 110.3(8) . . ? C33 C31 C34 113.4(9) . . ? C30 C31 C34 108.1(6) . . ? C33 C31 C32 108.7(6) . . ? C30 C31 C32 109.3(7) . . ? C34 C31 C32 107.0(8) . . ? C31 C32 H32A 109.5 . . ? C31 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C31 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C31 C33 H33A 109.5 . . ? C31 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? C31 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? C31 C34 H34A 109.5 . . ? C31 C34 H34B 109.5 . . ? H34A C34 H34B 109.5 . . ? C31 C34 H34C 109.5 . . ? H34A C34 H34C 109.5 . . ? H34B C34 H34C 109.5 . . ? N2 C35 C26 131.5(5) . . ? N2 C35 H35 114.2 . . ? C26 C35 H35 114.2 . . ? C38 C36 N2 112.1(5) . . ? C38 C36 C37 109.6(5) . . ? N2 C36 C37 106.0(5) . . ? C38 C36 C39 107.0(5) . . ? N2 C36 C39 109.7(4) . . ? C37 C36 C39 112.6(5) . . ? C36 C37 H37A 109.5 . . ? C36 C37 H37B 109.5 . . ? H37A C37 H37B 109.5 . . ? C36 C37 H37C 109.5 . . ? H37A C37 H37C 109.5 . . ? H37B C37 H37C 109.5 . . ? C36 C38 H38A 109.5 . . ? C36 C38 H38B 109.5 . . ? H38A C38 H38B 109.5 . . ? C36 C38 H38C 109.5 . . ? H38A C38 H38C 109.5 . . ? H38B C38 H38C 109.5 . . ? C44 C39 C40 118.4(6) . . ? C44 C39 C36 120.9(6) . . ? C40 C39 C36 120.5(5) . . ? C41 C40 C39 120.5(6) . . ? C41 C40 H40 119.8 . . ? C39 C40 H40 119.8 . . ? C42 C41 C40 120.2(7) . . ? C42 C41 H41 119.9 . . ? C40 C41 H41 119.9 . . ? C41 C42 C43 120.0(6) . . ? C41 C42 H42 120.0 . . ? C43 C42 H42 120.0 . . ? C44 C43 C42 119.0(6) . . ? C44 C43 H43 120.5 . . ? C42 C43 H43 120.5 . . ? C43 C44 C39 122.0(7) . . ? C43 C44 H44 119.0 . . ? C39 C44 H44 119.0 . . ? O4 C45 C46 106.3(6) . . ? O4 C45 H45A 110.5 . . ? C46 C45 H45A 110.5 . . ? O4 C45 H45B 110.5 . . ? C46 C45 H45B 110.5 . . ? H45A C45 H45B 108.7 . . ? C45 C46 C47 104.8(6) . . ? C45 C46 H46A 110.8 . . ? C47 C46 H46A 110.8 . . ? C45 C46 H46B 110.8 . . ? C47 C46 H46B 110.8 . . ? H46A C46 H46B 108.9 . . ? C46 C47 C48 102.6(6) . . ? C46 C47 H47A 111.3 . . ? C48 C47 H47A 111.3 . . ? C46 C47 H47B 111.3 . . ? C48 C47 H47B 111.3 . . ? H47A C47 H47B 109.2 . . ? O4 C48 C47 102.8(6) . . ? O4 C48 H48A 111.2 . . ? C47 C48 H48A 111.2 . . ? O4 C48 H48B 111.2 . . ? C47 C48 H48B 111.2 . . ? H48A C48 H48B 109.1 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 Ti1 O1 C1 -65(3) . . . . ? N1 Ti1 O1 C1 36.2(6) . . . . ? Cl2 Ti1 O1 C1 -143.3(6) . . . . ? Cl3 Ti1 O1 C1 120.6(6) . . . . ? Cl1 Ti1 O1 C1 -46.0(6) . . . . ? O1 Ti1 O2 C21 8(3) . . . . ? N1 Ti1 O2 C21 -92.6(7) . . . . ? Cl2 Ti1 O2 C21 86.9(7) . . . . ? Cl3 Ti1 O2 C21 -177.5(7) . . . . ? Cl1 Ti1 O2 C21 -10.9(7) . . . . ? O1 Ti1 O2 C24 -148(2) . . . . ? N1 Ti1 O2 C24 111.4(5) . . . . ? Cl2 Ti1 O2 C24 -69.1(5) . . . . ? Cl3 Ti1 O2 C24 26.5(5) . . . . ? Cl1 Ti1 O2 C24 -167.0(5) . . . . ? O4 Ti2 O3 C25 77(2) . . . . ? N2 Ti2 O3 C25 -35.5(5) . . . . ? Cl5 Ti2 O3 C25 143.5(5) . . . . ? Cl4 Ti2 O3 C25 -120.0(5) . . . . ? Cl6 Ti2 O3 C25 46.0(5) . . . . ? O3 Ti2 O4 C48 139(2) . . . . ? N2 Ti2 O4 C48 -109.0(5) . . . . ? Cl5 Ti2 O4 C48 72.1(5) . . . . ? Cl4 Ti2 O4 C48 -24.0(5) . . . . ? Cl6 Ti2 O4 C48 170.1(5) . . . . ? O3 Ti2 O4 C45 -15(2) . . . . ? N2 Ti2 O4 C45 97.2(6) . . . . ? Cl5 Ti2 O4 C45 -81.6(6) . . . . ? Cl4 Ti2 O4 C45 -177.8(6) . . . . ? Cl6 Ti2 O4 C45 16.4(6) . . . . ? O1 Ti1 N1 C11 -19.4(4) . . . . ? O2 Ti1 N1 C11 156.1(4) . . . . ? Cl2 Ti1 N1 C11 5(8) . . . . ? Cl3 Ti1 N1 C11 -116.0(4) . . . . ? Cl1 Ti1 N1 C11 72.3(4) . . . . ? O1 Ti1 N1 C12 171.0(5) . . . . ? O2 Ti1 N1 C12 -13.4(5) . . . . ? Cl2 Ti1 N1 C12 -164(7) . . . . ? Cl3 Ti1 N1 C12 74.5(4) . . . . ? Cl1 Ti1 N1 C12 -97.3(4) . . . . ? O3 Ti2 N2 C35 19.4(4) . . . . ? O4 Ti2 N2 C35 -156.3(4) . . . . ? Cl5 Ti2 N2 C35 -14(5) . . . . ? Cl4 Ti2 N2 C35 115.8(4) . . . . ? Cl6 Ti2 N2 C35 -72.4(4) . . . . ? O3 Ti2 N2 C36 -171.4(5) . . . . ? O4 Ti2 N2 C36 12.9(5) . . . . ? Cl5 Ti2 N2 C36 155(4) . . . . ? Cl4 Ti2 N2 C36 -75.1(4) . . . . ? Cl6 Ti2 N2 C36 96.8(4) . . . . ? Ti1 O1 C1 C2 -31.2(9) . . . . ? Ti1 O1 C1 C6 150.8(5) . . . . ? O1 C1 C2 C3 -177.9(7) . . . . ? C6 C1 C2 C3 0.1(10) . . . . ? O1 C1 C2 C11 -1.1(9) . . . . ? C6 C1 C2 C11 176.9(5) . . . . ? C1 C2 C3 C4 -2.7(12) . . . . ? C11 C2 C3 C4 -179.7(8) . . . . ? C2 C3 C4 C5 3.4(14) . . . . ? C3 C4 C5 C6 -1.6(14) . . . . ? C4 C5 C6 C1 -1.0(10) . . . . ? C4 C5 C6 C7 179.8(7) . . . . ? O1 C1 C6 C5 179.7(5) . . . . ? C2 C1 C6 C5 1.7(9) . . . . ? O1 C1 C6 C7 -1.2(8) . . . . ? C2 C1 C6 C7 -179.1(6) . . . . ? C5 C6 C7 C8 0.6(9) . . . . ? C1 C6 C7 C8 -178.6(6) . . . . ? C5 C6 C7 C10 118.6(7) . . . . ? C1 C6 C7 C10 -60.6(8) . . . . ? C5 C6 C7 C9 -120.0(8) . . . . ? C1 C6 C7 C9 60.9(9) . . . . ? C12 N1 C11 C2 177.7(6) . . . . ? Ti1 N1 C11 C2 6.1(8) . . . . ? C1 C2 C11 N1 8.1(10) . . . . ? C3 C2 C11 N1 -174.9(7) . . . . ? C11 N1 C12 C14 -71.6(6) . . . . ? Ti1 N1 C12 C14 98.5(6) . . . . ? C11 N1 C12 C15 55.5(6) . . . . ? Ti1 N1 C12 C15 -134.4(4) . . . . ? C11 N1 C12 C13 171.4(5) . . . . ? Ti1 N1 C12 C13 -18.4(7) . . . . ? N1 C12 C15 C16 46.8(7) . . . . ? C14 C12 C15 C16 169.8(5) . . . . ? C13 C12 C15 C16 -72.6(6) . . . . ? N1 C12 C15 C20 -135.3(5) . . . . ? C14 C12 C15 C20 -12.3(8) . . . . ? C13 C12 C15 C20 105.3(6) . . . . ? C20 C15 C16 C17 -1.5(8) . . . . ? C12 C15 C16 C17 176.4(5) . . . . ? C15 C16 C17 C18 -0.7(9) . . . . ? C16 C17 C18 C19 2.7(9) . . . . ? C17 C18 C19 C20 -2.5(9) . . . . ? C16 C15 C20 C19 1.6(8) . . . . ? C12 C15 C20 C19 -176.2(5) . . . . ? C18 C19 C20 C15 0.4(9) . . . . ? C24 O2 C21 C22 -26.1(12) . . . . ? Ti1 O2 C21 C22 175.0(8) . . . . ? O2 C21 C22 C23 25.0(16) . . . . ? C21 C22 C23 C24 -14.4(19) . . . . ? C21 O2 C24 C23 16.9(12) . . . . ? Ti1 O2 C24 C23 177.4(9) . . . . ? C22 C23 C24 O2 -1.1(17) . . . . ? Ti2 O3 C25 C26 29.7(8) . . . . ? Ti2 O3 C25 C30 -150.7(5) . . . . ? O3 C25 C26 C27 -177.8(6) . . . . ? C30 C25 C26 C27 2.6(10) . . . . ? O3 C25 C26 C35 2.5(9) . . . . ? C30 C25 C26 C35 -177.1(6) . . . . ? C25 C26 C27 C28 -3.7(12) . . . . ? C35 C26 C27 C28 176.0(8) . . . . ? C26 C27 C28 C29 1.9(14) . . . . ? C27 C28 C29 C30 1.1(14) . . . . ? C28 C29 C30 C25 -2.1(11) . . . . ? C28 C29 C30 C31 177.9(8) . . . . ? O3 C25 C30 C29 -179.3(5) . . . . ? C26 C25 C30 C29 0.2(9) . . . . ? O3 C25 C30 C31 0.7(9) . . . . ? C26 C25 C30 C31 -179.8(6) . . . . ? C29 C30 C31 C33 118.7(8) . . . . ? C25 C30 C31 C33 -61.3(10) . . . . ? C29 C30 C31 C34 -116.8(8) . . . . ? C25 C30 C31 C34 63.2(8) . . . . ? C29 C30 C31 C32 -0.7(11) . . . . ? C25 C30 C31 C32 179.3(7) . . . . ? C36 N2 C35 C26 -176.7(6) . . . . ? Ti2 N2 C35 C26 -5.7(9) . . . . ? C27 C26 C35 N2 170.9(7) . . . . ? C25 C26 C35 N2 -9.4(11) . . . . ? C35 N2 C36 C38 -169.7(5) . . . . ? Ti2 N2 C36 C38 20.6(7) . . . . ? C35 N2 C36 C37 70.7(6) . . . . ? Ti2 N2 C36 C37 -98.9(6) . . . . ? C35 N2 C36 C39 -51.1(6) . . . . ? Ti2 N2 C36 C39 139.3(4) . . . . ? C38 C36 C39 C44 -105.8(6) . . . . ? N2 C36 C39 C44 132.5(6) . . . . ? C37 C36 C39 C44 14.7(8) . . . . ? C38 C36 C39 C40 68.5(7) . . . . ? N2 C36 C39 C40 -53.2(7) . . . . ? C37 C36 C39 C40 -171.0(6) . . . . ? C44 C39 C40 C41 0.6(9) . . . . ? C36 C39 C40 C41 -173.8(5) . . . . ? C39 C40 C41 C42 0.0(9) . . . . ? C40 C41 C42 C43 0.1(10) . . . . ? C41 C42 C43 C44 -0.9(10) . . . . ? C42 C43 C44 C39 1.6(10) . . . . ? C40 C39 C44 C43 -1.4(9) . . . . ? C36 C39 C44 C43 173.0(6) . . . . ? C48 O4 C45 C46 5.4(9) . . . . ? Ti2 O4 C45 C46 162.2(5) . . . . ? O4 C45 C46 C47 19.5(9) . . . . ? C45 C46 C47 C48 -35.7(9) . . . . ? C45 O4 C48 C47 -27.2(8) . . . . ? Ti2 O4 C48 C47 175.1(5) . . . . ? C46 C47 C48 O4 38.7(8) . . . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 28.04 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 3.374 _refine_diff_density_min -0.825 _refine_diff_density_rms 0.160 data_d:\23js51 _database_code_depnum_ccdc_archive 'CCDC 902040' #TrackingRef 'web_deposit_cif_file_3_MichaelGardiner_1348050215.compound 14.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C25 H34 Cl3 N O2 Ti' _chemical_formula_weight 534.78 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 orthorhombic _symmetry_space_group_name_H-M 'P n a 21' _symmetry_space_group_name_Hall 'P 2c -2n' _symmetry_Int_Tables_number 33 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z' _cell_length_a 25.105(3) _cell_length_b 10.6280(12) _cell_length_c 9.7480(15) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2600.9(6) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 25105 _cell_measurement_theta_min 2.08 _cell_measurement_theta_max 28.05 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.05 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.366 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1120 _exptl_absorpt_coefficient_mu 0.659 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron BM' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-BM1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q210' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 42641 _diffrn_reflns_av_R_equivalents 0.0477 _diffrn_reflns_av_sigmaI/netI 0.0247 _diffrn_reflns_limit_h_min -33 _diffrn_reflns_limit_h_max 33 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 28.05 _reflns_number_total 6238 _reflns_number_gt 5874 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 1998)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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^)+(0.0541P)^2^+1.8374P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.23(3) _refine_ls_number_reflns 6238 _refine_ls_number_parameters 289 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0405 _refine_ls_R_factor_gt 0.0372 _refine_ls_wR_factor_ref 0.0961 _refine_ls_wR_factor_gt 0.0942 _refine_ls_goodness_of_fit_ref 1.070 _refine_ls_restrained_S_all 1.070 _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 0.728204(14) 0.45928(4) 0.73276(5) 0.01362(9) Uani 1 1 d . . . Cl1 Cl 0.74037(3) 0.49027(6) 0.96461(6) 0.02143(12) Uani 1 1 d . . . Cl2 Cl 0.73405(2) 0.45418(6) 0.49661(6) 0.01804(12) Uani 1 1 d . . . Cl3 Cl 0.68188(2) 0.27385(5) 0.74971(7) 0.02327(13) Uani 1 1 d . . . O1 O 0.67044(6) 0.55651(15) 0.7314(2) 0.0174(3) Uani 1 1 d . . . O2 O 0.79909(6) 0.33780(15) 0.7452(2) 0.0161(3) Uani 1 1 d . . . N1 N 0.77384(7) 0.64668(18) 0.7170(2) 0.0136(4) Uani 1 1 d . . . C1 C 0.65212(8) 0.6747(2) 0.7410(3) 0.0153(4) Uani 1 1 d . . . C2 C 0.68994(8) 0.7708(2) 0.7326(3) 0.0152(4) Uani 1 1 d . . . C3 C 0.67272(9) 0.8961(2) 0.7375(3) 0.0193(4) Uani 1 1 d . . . H3 H 0.6979 0.9627 0.7323 0.023 Uiso 1 1 calc R . . C4 C 0.61915(10) 0.9223(2) 0.7500(3) 0.0235(5) Uani 1 1 d . . . H4 H 0.6072 1.0071 0.7510 0.028 Uiso 1 1 calc R . . C5 C 0.58256(10) 0.8246(3) 0.7612(3) 0.0243(5) Uani 1 1 d . . . H5 H 0.5460 0.8451 0.7726 0.029 Uiso 1 1 calc R . . C6 C 0.59697(9) 0.6983(2) 0.7565(3) 0.0192(5) Uani 1 1 d . . . C7 C 0.55671(10) 0.5903(3) 0.7673(3) 0.0247(6) Uani 1 1 d . . . C8 C 0.55897(12) 0.5063(3) 0.6402(3) 0.0343(7) Uani 1 1 d . . . H8A H 0.5513 0.5567 0.5583 0.052 Uiso 1 1 calc R . . H8B H 0.5325 0.4390 0.6486 0.052 Uiso 1 1 calc R . . H8C H 0.5946 0.4694 0.6320 0.052 Uiso 1 1 calc R . . C9 C 0.56830(11) 0.5128(3) 0.8968(4) 0.0302(6) Uani 1 1 d . . . H9A H 0.5663 0.5675 0.9776 0.045 Uiso 1 1 calc R . . H9B H 0.6040 0.4762 0.8902 0.045 Uiso 1 1 calc R . . H9C H 0.5419 0.4453 0.9051 0.045 Uiso 1 1 calc R . . C10 C 0.49951(11) 0.6419(3) 0.7800(4) 0.0360(7) Uani 1 1 d . . . H10A H 0.4969 0.6954 0.8616 0.054 Uiso 1 1 calc R . . H10B H 0.4744 0.5717 0.7881 0.054 Uiso 1 1 calc R . . H10C H 0.4908 0.6916 0.6983 0.054 Uiso 1 1 calc R . . C11 C 0.74731(9) 0.7508(2) 0.7207(2) 0.0146(4) Uani 1 1 d . . . H11 H 0.7682 0.8252 0.7147 0.018 Uiso 1 1 calc R . . C12 C 0.83443(9) 0.6616(2) 0.7062(2) 0.0147(4) Uani 1 1 d . . . C13 C 0.85828(10) 0.6108(3) 0.8397(3) 0.0195(5) Uani 1 1 d . . . H13A H 0.8471 0.5232 0.8528 0.029 Uiso 1 1 calc R . . H13B H 0.8458 0.6618 0.9170 0.029 Uiso 1 1 calc R . . H13C H 0.8972 0.6148 0.8349 0.029 Uiso 1 1 calc R . . C14 C 0.85285(10) 0.7976(2) 0.6889(3) 0.0210(5) Uani 1 1 d . . . H14A H 0.8381 0.8322 0.6038 0.032 Uiso 1 1 calc R . . H14B H 0.8918 0.8002 0.6848 0.032 Uiso 1 1 calc R . . H14C H 0.8405 0.8478 0.7670 0.032 Uiso 1 1 calc R . . C15 C 0.85117(9) 0.5840(2) 0.5795(2) 0.0164(5) Uani 1 1 d . . . H15A H 0.8381 0.4968 0.5917 0.020 Uiso 1 1 calc R . . H15B H 0.8331 0.6194 0.4980 0.020 Uiso 1 1 calc R . . C16 C 0.91043(9) 0.5786(2) 0.5501(3) 0.0175(4) Uani 1 1 d . . . C17 C 0.94206(10) 0.4833(2) 0.6051(3) 0.0230(5) Uani 1 1 d . . . H17 H 0.9267 0.4239 0.6663 0.028 Uiso 1 1 calc R . . C18 C 0.99595(11) 0.4738(3) 0.5713(3) 0.0278(6) Uani 1 1 d . . . H18 H 1.0169 0.4079 0.6089 0.033 Uiso 1 1 calc R . . C19 C 1.01879(10) 0.5602(3) 0.4833(3) 0.0290(6) Uani 1 1 d . . . H19 H 1.0555 0.5540 0.4606 0.035 Uiso 1 1 calc R . . C20 C 0.98802(11) 0.6562(3) 0.4279(3) 0.0248(5) Uani 1 1 d . . . H20 H 1.0036 0.7157 0.3673 0.030 Uiso 1 1 calc R . . C21 C 0.93410(10) 0.6651(2) 0.4614(3) 0.0207(5) Uani 1 1 d . . . H21 H 0.9132 0.7310 0.4233 0.025 Uiso 1 1 calc R . . C22 C 0.81548(11) 0.2778(2) 0.8745(3) 0.0211(5) Uani 1 1 d . . . H22A H 0.7852 0.2326 0.9172 0.025 Uiso 1 1 calc R . . H22B H 0.8291 0.3411 0.9402 0.025 Uiso 1 1 calc R . . C23 C 0.85908(11) 0.1869(3) 0.8332(3) 0.0216(5) Uani 1 1 d . . . H23A H 0.8933 0.2307 0.8170 0.026 Uiso 1 1 calc R . . H23B H 0.8642 0.1202 0.9029 0.026 Uiso 1 1 calc R . . C24 C 0.83615(13) 0.1346(3) 0.7018(3) 0.0311(6) Uani 1 1 d . . . H24A H 0.8089 0.0696 0.7212 0.037 Uiso 1 1 calc R . . H24B H 0.8644 0.0973 0.6439 0.037 Uiso 1 1 calc R . . C25 C 0.81127(11) 0.2488(2) 0.6319(3) 0.0210(5) Uani 1 1 d . . . H25A H 0.8365 0.2870 0.5658 0.025 Uiso 1 1 calc R . . H25B H 0.7784 0.2248 0.5824 0.025 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 0.01193(17) 0.01393(18) 0.01500(18) 0.00029(15) 0.00181(18) 0.00040(13) Cl1 0.0267(3) 0.0231(3) 0.0144(3) -0.0009(2) 0.0043(2) 0.0026(2) Cl2 0.0164(3) 0.0237(3) 0.0140(3) -0.0002(2) -0.0015(2) -0.0002(2) Cl3 0.0205(2) 0.0193(3) 0.0301(3) 0.0016(2) 0.0048(3) -0.0055(2) O1 0.0128(6) 0.0176(8) 0.0216(8) -0.0004(7) 0.0010(8) -0.0006(6) O2 0.0182(7) 0.0161(7) 0.0140(8) 0.0001(7) -0.0004(7) 0.0033(6) N1 0.0127(8) 0.0167(9) 0.0113(9) -0.0011(7) -0.0013(7) 0.0001(7) C1 0.0137(9) 0.0187(10) 0.0135(10) 0.0016(9) -0.0002(9) 0.0035(7) C2 0.0131(9) 0.0199(10) 0.0124(10) 0.0002(9) -0.0006(10) 0.0051(8) C3 0.0193(10) 0.0212(11) 0.0176(10) -0.0009(10) -0.0011(11) 0.0052(8) C4 0.0212(11) 0.0242(11) 0.0250(13) -0.0011(11) 0.0019(11) 0.0093(9) C5 0.0183(11) 0.0307(13) 0.0238(13) 0.0023(11) 0.0018(10) 0.0100(10) C6 0.0122(9) 0.0283(12) 0.0170(12) 0.0047(10) 0.0013(9) 0.0031(8) C7 0.0116(10) 0.0349(14) 0.0276(15) 0.0097(11) 0.0020(9) 0.0010(10) C8 0.0222(13) 0.0463(17) 0.0345(17) -0.0014(13) -0.0030(12) -0.0109(12) C9 0.0156(13) 0.0368(16) 0.0382(16) 0.0139(13) 0.0050(11) 0.0010(11) C10 0.0129(11) 0.0481(18) 0.0470(19) 0.0177(15) 0.0046(11) 0.0030(12) C11 0.0134(9) 0.0165(10) 0.0140(10) 0.0003(8) -0.0019(9) -0.0002(7) C12 0.0098(9) 0.0159(10) 0.0185(12) 0.0000(8) 0.0001(8) 0.0003(7) C13 0.0180(12) 0.0224(12) 0.0183(11) -0.0011(9) -0.0028(9) 0.0023(9) C14 0.0159(11) 0.0166(11) 0.0306(13) -0.0024(9) -0.0013(9) -0.0002(9) C15 0.0110(10) 0.0190(11) 0.0193(12) -0.0014(8) 0.0011(8) 0.0003(8) C16 0.0136(10) 0.0220(11) 0.0168(11) -0.0044(9) 0.0012(9) -0.0003(9) C17 0.0211(11) 0.0248(12) 0.0229(12) -0.0018(11) 0.0007(11) 0.0046(9) C18 0.0210(12) 0.0349(15) 0.0275(14) -0.0043(11) -0.0022(11) 0.0098(11) C19 0.0157(11) 0.0437(15) 0.0275(14) -0.0126(12) 0.0056(11) 0.0018(11) C20 0.0181(12) 0.0352(14) 0.0211(12) -0.0038(10) 0.0052(10) -0.0056(10) C21 0.0183(11) 0.0243(11) 0.0196(12) -0.0009(10) 0.0018(10) -0.0007(9) C22 0.0262(13) 0.0189(12) 0.0182(12) 0.0059(9) 0.0006(10) 0.0047(10) C23 0.0195(12) 0.0195(12) 0.0259(13) 0.0006(10) -0.0037(10) 0.0029(9) C24 0.0355(15) 0.0255(14) 0.0324(16) -0.0064(11) -0.0034(12) 0.0092(11) C25 0.0274(12) 0.0173(10) 0.0183(12) -0.0050(9) 0.0017(10) 0.0027(9) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.7808(16) . ? Ti1 O2 2.2020(16) . ? Ti1 Cl3 2.2944(7) . ? Ti1 N1 2.3028(19) . ? Ti1 Cl1 2.3043(9) . ? Ti1 Cl2 2.3073(8) . ? O1 C1 1.340(3) . ? O2 C22 1.472(3) . ? O2 C25 1.486(3) . ? N1 C11 1.292(3) . ? N1 C12 1.533(3) . ? C1 C2 1.398(3) . ? C1 C6 1.415(3) . ? C2 C3 1.400(3) . ? C2 C11 1.461(3) . ? C3 C4 1.379(3) . ? C3 H3 0.9500 . ? C4 C5 1.391(4) . ? C4 H4 0.9500 . ? C5 C6 1.391(4) . ? C5 H5 0.9500 . ? C6 C7 1.533(4) . ? C7 C8 1.528(4) . ? C7 C9 1.535(4) . ? C7 C10 1.542(4) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11 0.9500 . ? C12 C14 1.527(3) . ? C12 C13 1.531(3) . ? C12 C15 1.543(3) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C15 C16 1.516(3) . ? C15 H15A 0.9900 . ? C15 H15B 0.9900 . ? C16 C17 1.394(4) . ? C16 C21 1.396(4) . ? C17 C18 1.396(4) . ? C17 H17 0.9500 . ? C18 C19 1.381(5) . ? C18 H18 0.9500 . ? C19 C20 1.389(4) . ? C19 H19 0.9500 . ? C20 C21 1.396(3) . ? C20 H20 0.9500 . ? C21 H21 0.9500 . ? C22 C23 1.515(4) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 C24 1.510(4) . ? C23 H23A 0.9900 . ? C23 H23B 0.9900 . ? C24 C25 1.526(4) . ? C24 H24A 0.9900 . ? C24 H24B 0.9900 . ? C25 H25A 0.9900 . ? C25 H25B 0.9900 . ? 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 177.24(9) . . ? O1 Ti1 Cl3 94.94(5) . . ? O2 Ti1 Cl3 84.38(5) . . ? O1 Ti1 N1 84.42(7) . . ? O2 Ti1 N1 96.24(6) . . ? Cl3 Ti1 N1 179.29(5) . . ? O1 Ti1 Cl1 91.85(7) . . ? O2 Ti1 Cl1 85.57(5) . . ? Cl3 Ti1 Cl1 96.85(3) . . ? N1 Ti1 Cl1 82.86(5) . . ? O1 Ti1 Cl2 93.33(7) . . ? O2 Ti1 Cl2 89.40(5) . . ? Cl3 Ti1 Cl2 94.81(3) . . ? N1 Ti1 Cl2 85.54(5) . . ? Cl1 Ti1 Cl2 166.78(3) . . ? C1 O1 Ti1 145.33(14) . . ? C22 O2 C25 107.67(17) . . ? C22 O2 Ti1 121.81(15) . . ? C25 O2 Ti1 119.91(15) . . ? C11 N1 C12 115.13(19) . . ? C11 N1 Ti1 118.86(15) . . ? C12 N1 Ti1 125.99(14) . . ? O1 C1 C2 116.62(18) . . ? O1 C1 C6 120.6(2) . . ? C2 C1 C6 122.7(2) . . ? C1 C2 C3 118.93(19) . . ? C1 C2 C11 124.6(2) . . ? C3 C2 C11 116.4(2) . . ? C4 C3 C2 119.7(2) . . ? C4 C3 H3 120.1 . . ? C2 C3 H3 120.1 . . ? C3 C4 C5 120.0(2) . . ? C3 C4 H4 120.0 . . ? C5 C4 H4 120.0 . . ? C4 C5 C6 123.1(2) . . ? C4 C5 H5 118.5 . . ? C6 C5 H5 118.5 . . ? C5 C6 C1 115.4(2) . . ? C5 C6 C7 123.3(2) . . ? C1 C6 C7 121.3(2) . . ? C8 C7 C6 110.9(2) . . ? C8 C7 C9 110.3(3) . . ? C6 C7 C9 109.5(2) . . ? C8 C7 C10 107.9(2) . . ? C6 C7 C10 110.7(2) . . ? C9 C7 C10 107.5(2) . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 H10A 109.5 . . ? C7 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 C2 129.4(2) . . ? N1 C11 H11 115.3 . . ? C2 C11 H11 115.3 . . ? C14 C12 C13 108.0(2) . . ? C14 C12 N1 113.93(18) . . ? C13 C12 N1 107.03(18) . . ? C14 C12 C15 109.59(19) . . ? C13 C12 C15 112.67(19) . . ? N1 C12 C15 105.68(17) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C16 C15 C12 116.02(19) . . ? C16 C15 H15A 108.3 . . ? C12 C15 H15A 108.3 . . ? C16 C15 H15B 108.3 . . ? C12 C15 H15B 108.3 . . ? H15A C15 H15B 107.4 . . ? C17 C16 C21 118.3(2) . . ? C17 C16 C15 120.9(2) . . ? C21 C16 C15 120.7(2) . . ? C16 C17 C18 120.9(3) . . ? C16 C17 H17 119.6 . . ? C18 C17 H17 119.6 . . ? C19 C18 C17 120.1(3) . . ? C19 C18 H18 120.0 . . ? C17 C18 H18 120.0 . . ? C18 C19 C20 119.9(2) . . ? C18 C19 H19 120.0 . . ? C20 C19 H19 120.0 . . ? C19 C20 C21 119.9(3) . . ? C19 C20 H20 120.0 . . ? C21 C20 H20 120.0 . . ? C16 C21 C20 120.9(2) . . ? C16 C21 H21 119.6 . . ? C20 C21 H21 119.6 . . ? O2 C22 C23 104.5(2) . . ? O2 C22 H22A 110.9 . . ? C23 C22 H22A 110.9 . . ? O2 C22 H22B 110.9 . . ? C23 C22 H22B 110.9 . . ? H22A C22 H22B 108.9 . . ? C24 C23 C22 100.7(2) . . ? C24 C23 H23A 111.6 . . ? C22 C23 H23A 111.6 . . ? C24 C23 H23B 111.6 . . ? C22 C23 H23B 111.6 . . ? H23A C23 H23B 109.4 . . ? C23 C24 C25 104.0(2) . . ? C23 C24 H24A 110.9 . . ? C25 C24 H24A 110.9 . . ? C23 C24 H24B 110.9 . . ? C25 C24 H24B 110.9 . . ? H24A C24 H24B 109.0 . . ? O2 C25 C24 105.0(2) . . ? O2 C25 H25A 110.8 . . ? C24 C25 H25A 110.8 . . ? O2 C25 H25B 110.8 . . ? C24 C25 H25B 110.8 . . ? H25A C25 H25B 108.8 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 Ti1 O1 C1 92.5(14) . . . . ? Cl3 Ti1 O1 C1 168.2(3) . . . . ? N1 Ti1 O1 C1 -11.5(3) . . . . ? Cl1 Ti1 O1 C1 71.2(3) . . . . ? Cl2 Ti1 O1 C1 -96.6(3) . . . . ? O1 Ti1 O2 C22 2.5(15) . . . . ? Cl3 Ti1 O2 C22 -73.48(16) . . . . ? N1 Ti1 O2 C22 106.18(17) . . . . ? Cl1 Ti1 O2 C22 23.87(16) . . . . ? Cl2 Ti1 O2 C22 -168.37(16) . . . . ? O1 Ti1 O2 C25 142.7(14) . . . . ? Cl3 Ti1 O2 C25 66.78(16) . . . . ? N1 Ti1 O2 C25 -113.57(16) . . . . ? Cl1 Ti1 O2 C25 164.13(16) . . . . ? Cl2 Ti1 O2 C25 -28.11(16) . . . . ? O1 Ti1 N1 C11 3.96(19) . . . . ? O2 Ti1 N1 C11 -173.35(18) . . . . ? Cl3 Ti1 N1 C11 -23(5) . . . . ? Cl1 Ti1 N1 C11 -88.62(18) . . . . ? Cl2 Ti1 N1 C11 97.74(18) . . . . ? O1 Ti1 N1 C12 -177.81(18) . . . . ? O2 Ti1 N1 C12 4.89(17) . . . . ? Cl3 Ti1 N1 C12 156(5) . . . . ? Cl1 Ti1 N1 C12 89.61(16) . . . . ? Cl2 Ti1 N1 C12 -84.02(16) . . . . ? Ti1 O1 C1 C2 12.3(5) . . . . ? Ti1 O1 C1 C6 -168.7(2) . . . . ? O1 C1 C2 C3 177.9(2) . . . . ? C6 C1 C2 C3 -1.1(4) . . . . ? O1 C1 C2 C11 -2.9(4) . . . . ? C6 C1 C2 C11 178.1(2) . . . . ? C1 C2 C3 C4 -0.2(4) . . . . ? C11 C2 C3 C4 -179.4(3) . . . . ? C2 C3 C4 C5 1.6(4) . . . . ? C3 C4 C5 C6 -2.0(4) . . . . ? C4 C5 C6 C1 0.7(4) . . . . ? C4 C5 C6 C7 -179.3(3) . . . . ? O1 C1 C6 C5 -178.2(2) . . . . ? C2 C1 C6 C5 0.8(4) . . . . ? O1 C1 C6 C7 1.9(4) . . . . ? C2 C1 C6 C7 -179.2(2) . . . . ? C5 C6 C7 C8 121.2(3) . . . . ? C1 C6 C7 C8 -58.9(3) . . . . ? C5 C6 C7 C9 -116.9(3) . . . . ? C1 C6 C7 C9 63.0(3) . . . . ? C5 C6 C7 C10 1.4(4) . . . . ? C1 C6 C7 C10 -178.6(3) . . . . ? C12 N1 C11 C2 -179.0(2) . . . . ? Ti1 N1 C11 C2 -0.6(4) . . . . ? C1 C2 C11 N1 -0.8(4) . . . . ? C3 C2 C11 N1 178.3(3) . . . . ? C11 N1 C12 C14 -5.0(3) . . . . ? Ti1 N1 C12 C14 176.66(15) . . . . ? C11 N1 C12 C13 114.3(2) . . . . ? Ti1 N1 C12 C13 -64.0(2) . . . . ? C11 N1 C12 C15 -125.4(2) . . . . ? Ti1 N1 C12 C15 56.3(2) . . . . ? C14 C12 C15 C16 59.5(3) . . . . ? C13 C12 C15 C16 -60.7(3) . . . . ? N1 C12 C15 C16 -177.28(19) . . . . ? C12 C15 C16 C17 90.8(3) . . . . ? C12 C15 C16 C21 -92.7(3) . . . . ? C21 C16 C17 C18 -0.6(4) . . . . ? C15 C16 C17 C18 176.1(2) . . . . ? C16 C17 C18 C19 0.6(4) . . . . ? C17 C18 C19 C20 -0.3(5) . . . . ? C18 C19 C20 C21 0.0(4) . . . . ? C17 C16 C21 C20 0.3(4) . . . . ? C15 C16 C21 C20 -176.3(2) . . . . ? C19 C20 C21 C16 -0.1(4) . . . . ? C25 O2 C22 C23 26.1(2) . . . . ? Ti1 O2 C22 C23 170.50(15) . . . . ? O2 C22 C23 C24 -40.8(3) . . . . ? C22 C23 C24 C25 40.1(3) . . . . ? C22 O2 C25 C24 -0.6(3) . . . . ? Ti1 O2 C25 C24 -145.85(17) . . . . ? C23 C24 C25 O2 -25.1(3) . . . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 28.05 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.563 _refine_diff_density_min -0.621 _refine_diff_density_rms 0.076 data_d:\15js30\re\temp _database_code_depnum_ccdc_archive 'CCDC 902041' #TrackingRef 'compound 15 revised.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C23 H30 Cl3 N O2 Ti' _chemical_formula_weight 506.73 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 orthorhombic _symmetry_space_group_name_H-M 'P b c a' _symmetry_space_group_name_Hall '-P 2ac 2ab' _symmetry_Int_Tables_number 61 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' _cell_length_a 20.373(3) _cell_length_b 16.4210(15) _cell_length_c 13.9580(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4669.6(9) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 42177 _cell_measurement_theta_min 2.15 _cell_measurement_theta_max 26.70 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.442 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2112 _exptl_absorpt_coefficient_mu 0.730 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Low data completion ratio is due to the limitations of the instrument available at the Australian Synchrotron operating under rotation data collection with a fixed detector and affects some high angle data. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.70845 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron BM' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-BM1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q210' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 50366 _diffrn_reflns_av_R_equivalents 0.0899 _diffrn_reflns_av_unetI/netI 0.0339 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.15 _diffrn_reflns_theta_max 24.01 _reflns_number_total 3624 _reflns_number_gt 3310 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 1998)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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. Disorder was apparent in the THF molecule, modelled as a two site arrangement, refined in population and included disorded H atoms. The remaining C atoms with large thermal motion could not be modelled with multiple positions. ; _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^)+(0.0000P)^2^+47.3269P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3624 _refine_ls_number_parameters 281 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0836 _refine_ls_R_factor_gt 0.0786 _refine_ls_wR_factor_ref 0.1741 _refine_ls_wR_factor_gt 0.1720 _refine_ls_goodness_of_fit_ref 1.227 _refine_ls_restrained_S_all 1.227 _refine_ls_shift/su_max 0.000 _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 0.24460(5) 0.20203(6) 0.77432(8) 0.0170(3) Uani 1 1 d . B . Cl1 Cl 0.29274(9) 0.24073(11) 0.91243(12) 0.0298(4) Uani 1 1 d . . . Cl2 Cl 0.16143(8) 0.29514(10) 0.78784(12) 0.0274(4) Uani 1 1 d . . . Cl3 Cl 0.17801(8) 0.10172(10) 0.82370(12) 0.0300(4) Uani 1 1 d . . . O1 O 0.30840(19) 0.1320(2) 0.7472(3) 0.0141(9) Uani 1 1 d . . . O2 O 0.2969(2) 0.2947(2) 0.7051(3) 0.0199(9) Uani 1 1 d . . . N1 N 0.2169(2) 0.1777(3) 0.6279(4) 0.0149(11) Uani 1 1 d . . . C1 C 0.3254(3) 0.0716(4) 0.6885(4) 0.0153(13) Uani 1 1 d . B . C2 C 0.2926(3) 0.0664(4) 0.6019(4) 0.0155(13) Uani 1 1 d . . . C3 C 0.3106(3) 0.0069(4) 0.5377(4) 0.0179(13) Uani 1 1 d . B . H3 H 0.2889 0.0030 0.4776 0.021 Uiso 1 1 calc R . . C4 C 0.3597(3) -0.0465(4) 0.5602(5) 0.0190(14) Uani 1 1 d . . . H4 H 0.3727 -0.0873 0.5158 0.023 Uiso 1 1 calc R B . C5 C 0.3901(3) -0.0406(3) 0.6474(4) 0.0164(13) Uani 1 1 d . B . H5 H 0.4237 -0.0788 0.6623 0.020 Uiso 1 1 calc R . . C6 C 0.3747(3) 0.0173(3) 0.7140(4) 0.0140(12) Uani 1 1 d . . . C7 C 0.4075(3) 0.0216(4) 0.8111(4) 0.0171(13) Uani 1 1 d . B . C8 C 0.4382(3) 0.1039(4) 0.8296(5) 0.0240(15) Uani 1 1 d . . . H8A H 0.4045 0.1463 0.8246 0.036 Uiso 1 1 calc R B . H8B H 0.4727 0.1140 0.7821 0.036 Uiso 1 1 calc R . . H8C H 0.4573 0.1047 0.8940 0.036 Uiso 1 1 calc R . . C9 C 0.3562(3) 0.0037(4) 0.8881(4) 0.0218(14) Uani 1 1 d . . . H9A H 0.3367 -0.0499 0.8763 0.033 Uiso 1 1 calc R B . H9B H 0.3219 0.0454 0.8861 0.033 Uiso 1 1 calc R . . H9C H 0.3772 0.0040 0.9512 0.033 Uiso 1 1 calc R . . C10 C 0.4616(3) -0.0420(4) 0.8201(5) 0.0233(15) Uani 1 1 d . . . H10A H 0.4432 -0.0963 0.8090 0.035 Uiso 1 1 calc R B . H10B H 0.4806 -0.0396 0.8846 0.035 Uiso 1 1 calc R . . H10C H 0.4959 -0.0309 0.7726 0.035 Uiso 1 1 calc R . . C11 C 0.2421(3) 0.1223(3) 0.5762(4) 0.0159(13) Uani 1 1 d . B . H11 H 0.2252 0.1174 0.5130 0.019 Uiso 1 1 calc R . . C12 C 0.1658(3) 0.2258(4) 0.5792(5) 0.0192(14) Uani 1 1 d . B . H12A H 0.1739 0.2255 0.5093 0.023 Uiso 1 1 calc R . . H12B H 0.1677 0.2829 0.6017 0.023 Uiso 1 1 calc R . . C13 C 0.0985(3) 0.1910(4) 0.5994(5) 0.0230(14) Uani 1 1 d . . . H13A H 0.0939 0.1374 0.5677 0.028 Uiso 1 1 calc R B . H13B H 0.0928 0.1833 0.6692 0.028 Uiso 1 1 calc R . . C14 C 0.0471(3) 0.2481(4) 0.5624(5) 0.0217(14) Uani 1 1 d . B . C15 C 0.0438(3) 0.2655(5) 0.4677(5) 0.0319(17) Uani 1 1 d . . . H15 H 0.0732 0.2398 0.4244 0.038 Uiso 1 1 calc R B . C16 C -0.0018(4) 0.3200(5) 0.4339(6) 0.042(2) Uani 1 1 d . B . H16 H -0.0037 0.3315 0.3672 0.051 Uiso 1 1 calc R . . C17 C -0.0434(4) 0.3571(5) 0.4936(6) 0.041(2) Uani 1 1 d . . . H17 H -0.0741 0.3958 0.4700 0.049 Uiso 1 1 calc R B . C18 C -0.0413(3) 0.3389(4) 0.5895(6) 0.0349(19) Uani 1 1 d . B . H18 H -0.0718 0.3635 0.6320 0.042 Uiso 1 1 calc R . . C19 C 0.0044(3) 0.2854(4) 0.6243(5) 0.0226(14) Uani 1 1 d . . . H19 H 0.0065 0.2743 0.6910 0.027 Uiso 1 1 calc R B . C20 C 0.3565(3) 0.2769(4) 0.6521(5) 0.0233(15) Uani 1 1 d . B . H20A H 0.3476 0.2378 0.5996 0.028 Uiso 1 1 calc R A 1 H20B H 0.3904 0.2535 0.6948 0.028 Uiso 1 1 calc R A 1 C21A C 0.3784(5) 0.3567(5) 0.6129(6) 0.050(2) Uani 0.36(3) 1 d P B 2 H21A H 0.4203 0.3733 0.6430 0.060 Uiso 0.36(3) 1 calc PR B 2 H21B H 0.3853 0.3525 0.5428 0.060 Uiso 0.36(3) 1 calc PR B 2 C21B C 0.3784(5) 0.3567(5) 0.6129(6) 0.050(2) Uani 0.64(3) 1 d P B 1 H21C H 0.3615 0.3647 0.5470 0.060 Uiso 0.64(3) 1 calc PR B 1 H21D H 0.4269 0.3600 0.6115 0.060 Uiso 0.64(3) 1 calc PR B 1 C22A C 0.3344(13) 0.4085(15) 0.631(2) 0.026(7) Uani 0.36(3) 1 d P B 2 H22A H 0.3049 0.4139 0.5747 0.032 Uiso 0.36(3) 1 calc PR B 2 H22B H 0.3549 0.4622 0.6429 0.032 Uiso 0.36(3) 1 calc PR B 2 C22B C 0.3497(7) 0.4213(8) 0.6814(17) 0.034(4) Uani 0.64(3) 1 d P B 1 H22C H 0.3817 0.4358 0.7320 0.040 Uiso 0.64(3) 1 calc PR B 1 H22D H 0.3371 0.4712 0.6461 0.040 Uiso 0.64(3) 1 calc PR B 1 C23A C 0.2931(4) 0.3817(4) 0.7215(5) 0.0309(17) Uani 0.36(3) 1 d P B 2 H23A H 0.3141 0.3981 0.7825 0.037 Uiso 0.36(3) 1 calc PR B 2 H23B H 0.2474 0.4021 0.7194 0.037 Uiso 0.36(3) 1 calc PR B 2 C23B C 0.2931(4) 0.3817(4) 0.7215(5) 0.0309(17) Uani 0.64(3) 1 d P B 1 H23C H 0.2527 0.4036 0.6916 0.037 Uiso 0.64(3) 1 calc PR B 1 H23D H 0.2909 0.3926 0.7912 0.037 Uiso 0.64(3) 1 calc PR B 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 0.0221(6) 0.0169(6) 0.0120(6) 0.0007(4) 0.0031(5) 0.0063(5) Cl1 0.0384(9) 0.0348(9) 0.0162(8) -0.0098(7) -0.0035(7) 0.0119(8) Cl2 0.0313(9) 0.0271(9) 0.0238(9) 0.0002(7) 0.0052(7) 0.0134(7) Cl3 0.0279(9) 0.0317(9) 0.0304(10) 0.0164(7) 0.0074(7) 0.0024(7) O1 0.019(2) 0.014(2) 0.010(2) -0.0018(16) -0.0007(16) 0.0033(17) O2 0.023(2) 0.016(2) 0.020(2) -0.0023(18) 0.0028(18) -0.0005(18) N1 0.013(2) 0.017(3) 0.014(3) 0.000(2) 0.005(2) 0.000(2) C1 0.018(3) 0.016(3) 0.011(3) -0.001(2) 0.005(2) 0.000(2) C2 0.015(3) 0.015(3) 0.017(3) 0.002(2) 0.000(2) 0.000(2) C3 0.019(3) 0.020(3) 0.015(3) -0.004(2) -0.001(2) -0.003(3) C4 0.025(3) 0.013(3) 0.019(3) 0.003(2) 0.006(3) 0.000(3) C5 0.017(3) 0.012(3) 0.020(3) 0.003(2) 0.004(3) 0.001(2) C6 0.015(3) 0.013(3) 0.014(3) 0.004(2) 0.001(2) 0.004(2) C7 0.021(3) 0.016(3) 0.015(3) 0.000(2) 0.000(3) 0.002(3) C8 0.023(3) 0.021(3) 0.027(4) -0.002(3) -0.005(3) -0.006(3) C9 0.028(3) 0.024(3) 0.014(3) 0.002(3) -0.002(3) -0.002(3) C10 0.019(3) 0.020(3) 0.031(4) -0.002(3) -0.006(3) 0.008(3) C11 0.020(3) 0.015(3) 0.013(3) 0.004(2) -0.002(2) -0.001(3) C12 0.012(3) 0.024(3) 0.022(3) 0.005(3) -0.002(2) -0.004(2) C13 0.018(3) 0.019(3) 0.032(4) 0.000(3) 0.000(3) 0.002(3) C14 0.014(3) 0.018(3) 0.033(4) 0.000(3) -0.001(3) 0.000(3) C15 0.026(4) 0.044(5) 0.026(4) -0.008(3) -0.007(3) 0.007(3) C16 0.031(4) 0.059(5) 0.037(5) 0.003(4) -0.014(4) 0.003(4) C17 0.025(4) 0.035(4) 0.062(6) 0.004(4) -0.016(4) 0.003(3) C18 0.021(4) 0.024(4) 0.060(6) -0.007(4) 0.004(3) -0.001(3) C19 0.020(3) 0.019(3) 0.029(4) -0.005(3) 0.003(3) -0.002(3) C20 0.020(3) 0.029(4) 0.021(4) 0.000(3) 0.006(3) -0.003(3) C21A 0.082(7) 0.028(4) 0.039(5) -0.006(4) 0.024(5) -0.028(5) C21B 0.082(7) 0.028(4) 0.039(5) -0.006(4) 0.024(5) -0.028(5) C22A 0.031(13) 0.024(12) 0.024(16) 0.008(11) 0.002(11) -0.004(10) C22B 0.040(8) 0.020(6) 0.042(12) 0.001(6) -0.008(7) -0.010(5) C23A 0.036(4) 0.015(3) 0.041(5) -0.001(3) -0.004(3) -0.001(3) C23B 0.036(4) 0.015(3) 0.041(5) -0.001(3) -0.004(3) -0.001(3) _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 1.776(4) . ? Ti1 O2 2.095(4) . ? Ti1 N1 2.158(5) . ? Ti1 Cl3 2.242(2) . ? Ti1 Cl1 2.254(2) . ? Ti1 Cl2 2.2900(18) . ? O1 C1 1.333(7) . ? O2 C23A 1.448(8) . ? O2 C20 1.452(7) . ? N1 C11 1.270(8) . ? N1 C12 1.472(8) . ? C1 C2 1.383(8) . ? C1 C6 1.390(8) . ? C2 C3 1.374(8) . ? C2 C11 1.425(8) . ? C3 C4 1.368(9) . ? C3 H3 0.9500 . ? C4 C5 1.368(9) . ? C4 H4 0.9500 . ? C5 C6 1.367(8) . ? C5 H5 0.9500 . ? C6 C7 1.513(8) . ? C7 C8 1.511(8) . ? C7 C10 1.524(8) . ? C7 C9 1.526(8) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11 0.9500 . ? C12 C13 1.512(8) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 C14 1.496(9) . ? C13 H13A 0.9900 . ? C13 H13B 0.9900 . ? C14 C15 1.354(10) . ? C14 C19 1.371(9) . ? C15 C16 1.374(10) . ? C15 H15 0.9500 . ? C16 C17 1.337(12) . ? C16 H16 0.9500 . ? C17 C18 1.371(12) . ? C17 H17 0.9500 . ? C18 C19 1.369(10) . ? C18 H18 0.9500 . ? C19 H19 0.9500 . ? C20 C21A 1.489(10) . ? C20 H20A 0.9900 . ? C20 H20B 0.9900 . ? C21A C22A 1.26(2) . ? C21A H21A 0.9900 . ? C21A H21B 0.9900 . ? C22A C23A 1.58(2) . ? C22A H22A 0.9900 . ? C22A H22B 0.9900 . ? C22B H22C 0.9900 . ? C22B H22D 0.9900 . ? C23A H23A 0.9900 . ? C23A H23B 0.9900 . ? 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 89.99(17) . . ? O1 Ti1 N1 82.55(18) . . ? O2 Ti1 N1 80.25(17) . . ? O1 Ti1 Cl3 91.86(14) . . ? O2 Ti1 Cl3 169.58(14) . . ? N1 Ti1 Cl3 89.82(14) . . ? O1 Ti1 Cl1 92.64(14) . . ? O2 Ti1 Cl1 88.18(13) . . ? N1 Ti1 Cl1 167.43(14) . . ? Cl3 Ti1 Cl1 101.98(8) . . ? O1 Ti1 Cl2 172.42(15) . . ? O2 Ti1 Cl2 85.95(12) . . ? N1 Ti1 Cl2 90.44(14) . . ? Cl3 Ti1 Cl2 91.00(7) . . ? Cl1 Ti1 Cl2 93.62(7) . . ? C1 O1 Ti1 143.4(4) . . ? C23A O2 C20 109.0(5) . . ? C23A O2 Ti1 128.0(4) . . ? C20 O2 Ti1 120.9(4) . . ? C11 N1 C12 114.1(5) . . ? C11 N1 Ti1 124.3(4) . . ? C12 N1 Ti1 121.5(4) . . ? O1 C1 C2 117.3(5) . . ? O1 C1 C6 120.5(5) . . ? C2 C1 C6 122.2(5) . . ? C3 C2 C1 119.0(5) . . ? C3 C2 C11 119.1(6) . . ? C1 C2 C11 121.9(6) . . ? C4 C3 C2 120.0(6) . . ? C4 C3 H3 120.0 . . ? C2 C3 H3 120.0 . . ? C5 C4 C3 119.4(6) . . ? C5 C4 H4 120.3 . . ? C3 C4 H4 120.3 . . ? C6 C5 C4 123.3(6) . . ? C6 C5 H5 118.3 . . ? C4 C5 H5 118.3 . . ? C5 C6 C1 116.0(5) . . ? C5 C6 C7 122.7(5) . . ? C1 C6 C7 121.2(5) . . ? C8 C7 C6 112.2(5) . . ? C8 C7 C10 107.4(5) . . ? C6 C7 C10 111.2(5) . . ? C8 C7 C9 109.7(5) . . ? C6 C7 C9 108.6(5) . . ? C10 C7 C9 107.8(5) . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 H10A 109.5 . . ? C7 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 C2 127.7(6) . . ? N1 C11 H11 116.1 . . ? C2 C11 H11 116.1 . . ? N1 C12 C13 110.7(5) . . ? N1 C12 H12A 109.5 . . ? C13 C12 H12A 109.5 . . ? N1 C12 H12B 109.5 . . ? C13 C12 H12B 109.5 . . ? H12A C12 H12B 108.1 . . ? C14 C13 C12 109.5(5) . . ? C14 C13 H13A 109.8 . . ? C12 C13 H13A 109.8 . . ? C14 C13 H13B 109.8 . . ? C12 C13 H13B 109.8 . . ? H13A C13 H13B 108.2 . . ? C15 C14 C19 119.3(6) . . ? C15 C14 C13 120.2(6) . . ? C19 C14 C13 120.5(6) . . ? C14 C15 C16 120.5(7) . . ? C14 C15 H15 119.8 . . ? C16 C15 H15 119.8 . . ? C17 C16 C15 120.7(8) . . ? C17 C16 H16 119.6 . . ? C15 C16 H16 119.6 . . ? C16 C17 C18 119.3(7) . . ? C16 C17 H17 120.4 . . ? C18 C17 H17 120.4 . . ? C19 C18 C17 120.5(7) . . ? C19 C18 H18 119.7 . . ? C17 C18 H18 119.7 . . ? C18 C19 C14 119.7(7) . . ? C18 C19 H19 120.2 . . ? C14 C19 H19 120.2 . . ? O2 C20 C21A 105.0(6) . . ? O2 C20 H20A 110.7 . . ? C21A C20 H20A 110.7 . . ? O2 C20 H20B 110.7 . . ? C21A C20 H20B 110.7 . . ? H20A C20 H20B 108.8 . . ? C22A C21A C20 108.0(12) . . ? C22A C21A H21A 110.1 . . ? C20 C21A H21A 110.1 . . ? C22A C21A H21B 110.1 . . ? C20 C21A H21B 110.1 . . ? H21A C21A H21B 108.4 . . ? C21A C22A C23A 110.4(15) . . ? C21A C22A H22A 109.6 . . ? C23A C22A H22A 109.6 . . ? C21A C22A H22B 109.6 . . ? C23A C22A H22B 109.6 . . ? H22A C22A H22B 108.1 . . ? H22C C22B H22D 109.0 . . ? O2 C23A C22A 96.8(11) . . ? O2 C23A H23A 112.4 . . ? C22A C23A H23A 112.4 . . ? O2 C23A H23B 112.4 . . ? C22A C23A H23B 112.4 . . ? H23A C23A H23B 110.0 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 Ti1 O1 C1 -102.1(6) . . . . ? N1 Ti1 O1 C1 -21.9(6) . . . . ? Cl3 Ti1 O1 C1 67.6(6) . . . . ? Cl1 Ti1 O1 C1 169.7(6) . . . . ? Cl2 Ti1 O1 C1 -44.5(15) . . . . ? O1 Ti1 O2 C23A -154.6(5) . . . . ? N1 Ti1 O2 C23A 122.9(5) . . . . ? Cl3 Ti1 O2 C23A 105.1(8) . . . . ? Cl1 Ti1 O2 C23A -62.0(5) . . . . ? Cl2 Ti1 O2 C23A 31.8(5) . . . . ? O1 Ti1 O2 C20 7.1(4) . . . . ? N1 Ti1 O2 C20 -75.3(4) . . . . ? Cl3 Ti1 O2 C20 -93.2(8) . . . . ? Cl1 Ti1 O2 C20 99.8(4) . . . . ? Cl2 Ti1 O2 C20 -166.5(4) . . . . ? O1 Ti1 N1 C11 9.3(5) . . . . ? O2 Ti1 N1 C11 100.6(5) . . . . ? Cl3 Ti1 N1 C11 -82.6(5) . . . . ? Cl1 Ti1 N1 C11 77.4(9) . . . . ? Cl2 Ti1 N1 C11 -173.6(5) . . . . ? O1 Ti1 N1 C12 -170.7(4) . . . . ? O2 Ti1 N1 C12 -79.4(4) . . . . ? Cl3 Ti1 N1 C12 97.4(4) . . . . ? Cl1 Ti1 N1 C12 -102.6(7) . . . . ? Cl2 Ti1 N1 C12 6.4(4) . . . . ? Ti1 O1 C1 C2 20.9(9) . . . . ? Ti1 O1 C1 C6 -159.9(5) . . . . ? O1 C1 C2 C3 177.3(5) . . . . ? C6 C1 C2 C3 -1.9(9) . . . . ? O1 C1 C2 C11 -0.8(8) . . . . ? C6 C1 C2 C11 180.0(6) . . . . ? C1 C2 C3 C4 0.7(9) . . . . ? C11 C2 C3 C4 178.9(6) . . . . ? C2 C3 C4 C5 0.7(9) . . . . ? C3 C4 C5 C6 -1.0(9) . . . . ? C4 C5 C6 C1 -0.1(9) . . . . ? C4 C5 C6 C7 178.3(6) . . . . ? O1 C1 C6 C5 -177.6(5) . . . . ? C2 C1 C6 C5 1.5(9) . . . . ? O1 C1 C6 C7 3.9(9) . . . . ? C2 C1 C6 C7 -176.9(5) . . . . ? C5 C6 C7 C8 124.3(6) . . . . ? C1 C6 C7 C8 -57.4(7) . . . . ? C5 C6 C7 C10 4.0(8) . . . . ? C1 C6 C7 C10 -177.7(5) . . . . ? C5 C6 C7 C9 -114.4(6) . . . . ? C1 C6 C7 C9 63.9(7) . . . . ? C12 N1 C11 C2 179.4(6) . . . . ? Ti1 N1 C11 C2 -0.6(9) . . . . ? C3 C2 C11 N1 175.9(6) . . . . ? C1 C2 C11 N1 -5.9(10) . . . . ? C11 N1 C12 C13 93.8(6) . . . . ? Ti1 N1 C12 C13 -86.1(6) . . . . ? N1 C12 C13 C14 171.1(5) . . . . ? C12 C13 C14 C15 61.9(8) . . . . ? C12 C13 C14 C19 -115.9(7) . . . . ? C19 C14 C15 C16 0.1(11) . . . . ? C13 C14 C15 C16 -177.7(7) . . . . ? C14 C15 C16 C17 0.3(12) . . . . ? C15 C16 C17 C18 -1.5(12) . . . . ? C16 C17 C18 C19 2.3(11) . . . . ? C17 C18 C19 C14 -1.9(10) . . . . ? C15 C14 C19 C18 0.7(10) . . . . ? C13 C14 C19 C18 178.5(6) . . . . ? C23A O2 C20 C21A -15.9(7) . . . . ? Ti1 O2 C20 C21A 179.2(5) . . . . ? O2 C20 C21A C22A -7(2) . . . . ? C20 C21A C22A C23A 25(3) . . . . ? C20 O2 C23A C22A 27.3(14) . . . . ? Ti1 O2 C23A C22A -169.3(13) . . . . ? C21A C22A C23A O2 -33(3) . . . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 24.01 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.469 _refine_diff_density_min -0.813 _refine_diff_density_rms 0.116 data_d:\14js253a\rev\rev _database_code_depnum_ccdc_archive 'CCDC 902042' #TrackingRef 'compound 16 revised.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C38 H44 Cl2 N2 O2 Ti' _chemical_formula_weight 679.55 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 monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 14.1400(10) _cell_length_b 7.6160(10) _cell_length_c 31.9980(19) _cell_angle_alpha 90.00 _cell_angle_beta 100.824(2) _cell_angle_gamma 90.00 _cell_volume 3384.6(5) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 16017 _cell_measurement_theta_min 1.3 _cell_measurement_theta_max 26.76 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.334 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1432 _exptl_absorpt_coefficient_mu 0.447 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Low data completion ratio is due to the limitations of the instrument available at the Australian Synchrotron operating under rotation data collection with a fixed detector and affects some high angle data. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71067 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron BM' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-BM1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q210' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 18966 _diffrn_reflns_av_R_equivalents 0.0382 _diffrn_reflns_av_unetI/netI 0.0330 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_limit_l_max 36 _diffrn_reflns_theta_min 1.49 _diffrn_reflns_theta_max 24.09 _reflns_number_total 5287 _reflns_number_gt 4501 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 1998)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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^)+(0.0383P)^2^+9.1011P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5287 _refine_ls_number_parameters 406 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0615 _refine_ls_R_factor_gt 0.0507 _refine_ls_wR_factor_ref 0.1203 _refine_ls_wR_factor_gt 0.1153 _refine_ls_goodness_of_fit_ref 1.080 _refine_ls_restrained_S_all 1.080 _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 0.88052(4) 0.73295(8) 0.119154(17) 0.01585(16) Uani 1 1 d . . . Cl1 Cl 0.95153(6) 0.95743(13) 0.16282(3) 0.0317(2) Uani 1 1 d . . . Cl2 Cl 0.81277(6) 0.89940(11) 0.06089(2) 0.01975(19) Uani 1 1 d . . . O1 O 0.99372(15) 0.6890(3) 0.10033(7) 0.0166(5) Uani 1 1 d . . . O2 O 0.76691(15) 0.7374(3) 0.14026(7) 0.0182(5) Uani 1 1 d . . . N1 N 0.83966(18) 0.4815(4) 0.08659(8) 0.0164(6) Uani 1 1 d . . . N2 N 0.9208(2) 0.5475(4) 0.17188(9) 0.0255(7) Uani 1 1 d . . . C1 C 1.0387(2) 0.5829(4) 0.07686(9) 0.0133(6) Uani 1 1 d . . . C2 C 0.9889(2) 0.4326(4) 0.05943(9) 0.0136(6) Uani 1 1 d . . . C3 C 1.0310(2) 0.3172(4) 0.03410(10) 0.0162(7) Uani 1 1 d . . . H3 H 0.9971 0.2161 0.0220 0.019 Uiso 1 1 calc R . . C4 C 1.1222(2) 0.3527(4) 0.02705(10) 0.0179(7) Uani 1 1 d . . . H4 H 1.1515 0.2767 0.0097 0.021 Uiso 1 1 calc R . . C5 C 1.1713(2) 0.4996(4) 0.04542(10) 0.0164(7) Uani 1 1 d . . . H5 H 1.2347 0.5198 0.0406 0.020 Uiso 1 1 calc R . . C6 C 1.1329(2) 0.6186(4) 0.07047(10) 0.0136(6) Uani 1 1 d . . . C7 C 1.1890(2) 0.7799(4) 0.08971(10) 0.0161(7) Uani 1 1 d . . . C8 C 1.1332(2) 0.9476(4) 0.07366(11) 0.0210(7) Uani 1 1 d . . . H8A H 1.1696 1.0507 0.0860 0.032 Uiso 1 1 calc R . . H8B H 1.0702 0.9460 0.0822 0.032 Uiso 1 1 calc R . . H8C H 1.1243 0.9529 0.0426 0.032 Uiso 1 1 calc R . . C9 C 1.2055(2) 0.7730(5) 0.13857(10) 0.0209(7) Uani 1 1 d . . . H9A H 1.2415 0.8772 0.1504 0.031 Uiso 1 1 calc R . . H9B H 1.2422 0.6672 0.1487 0.031 Uiso 1 1 calc R . . H9C H 1.1432 0.7701 0.1478 0.031 Uiso 1 1 calc R . . C10 C 1.2877(2) 0.7918(5) 0.07656(12) 0.0242(8) Uani 1 1 d . . . H10A H 1.3217 0.8967 0.0893 0.036 Uiso 1 1 calc R . . H10B H 1.2790 0.7993 0.0455 0.036 Uiso 1 1 calc R . . H10C H 1.3256 0.6871 0.0865 0.036 Uiso 1 1 calc R . . C11 C 0.8935(2) 0.3902(4) 0.06613(10) 0.0168(7) Uani 1 1 d . . . H11 H 0.8670 0.2828 0.0541 0.020 Uiso 1 1 calc R . . C12 C 0.7453(2) 0.3959(5) 0.08767(11) 0.0205(7) Uani 1 1 d . . . H12A H 0.7256 0.4214 0.1152 0.025 Uiso 1 1 calc R . . H12B H 0.7516 0.2671 0.0851 0.025 Uiso 1 1 calc R . . C13 C 0.6690(2) 0.4641(5) 0.05123(11) 0.0226(8) Uani 1 1 d . . . H13A H 0.6630 0.5929 0.0540 0.027 Uiso 1 1 calc R . . H13B H 0.6897 0.4402 0.0239 0.027 Uiso 1 1 calc R . . C14 C 0.5717(2) 0.3798(4) 0.05056(10) 0.0186(7) Uani 1 1 d . . . C15 C 0.5299(2) 0.2737(5) 0.01690(11) 0.0240(8) Uani 1 1 d . . . H15 H 0.5636 0.2507 -0.0055 0.029 Uiso 1 1 calc R . . C16 C 0.4393(2) 0.2006(5) 0.01560(11) 0.0252(8) Uani 1 1 d . . . H16 H 0.4121 0.1266 -0.0074 0.030 Uiso 1 1 calc R . . C17 C 0.3891(2) 0.2353(5) 0.04758(12) 0.0270(8) Uani 1 1 d . . . H17 H 0.3265 0.1877 0.0463 0.032 Uiso 1 1 calc R . . C18 C 0.4301(2) 0.3399(5) 0.08169(11) 0.0231(8) Uani 1 1 d . . . H18 H 0.3956 0.3631 0.1039 0.028 Uiso 1 1 calc R . . C19 C 0.5211(2) 0.4109(5) 0.08361(11) 0.0218(7) Uani 1 1 d . . . H19 H 0.5493 0.4806 0.1073 0.026 Uiso 1 1 calc R . . C20 C 0.7223(2) 0.6738(4) 0.17046(9) 0.0142(7) Uani 1 1 d . . . C21 C 0.7674(2) 0.5383(4) 0.19667(10) 0.0174(7) Uani 1 1 d . . . C22 C 0.7194(2) 0.4602(4) 0.22609(10) 0.0183(7) Uani 1 1 d . . . H22 H 0.7493 0.3678 0.2437 0.022 Uiso 1 1 calc R . . C23 C 0.6288(2) 0.5164(4) 0.22967(10) 0.0189(7) Uani 1 1 d . . . H23 H 0.5950 0.4600 0.2489 0.023 Uiso 1 1 calc R . . C24 C 0.5868(2) 0.6568(4) 0.20481(10) 0.0163(7) Uani 1 1 d . . . H24 H 0.5249 0.6959 0.2082 0.020 Uiso 1 1 calc R . . C25 C 0.6318(2) 0.7422(4) 0.17524(9) 0.0140(6) Uani 1 1 d . . . C26 C 0.5903(2) 0.9069(4) 0.15143(10) 0.0160(7) Uani 1 1 d . . . C27 C 0.6615(3) 1.0604(5) 0.16316(11) 0.0246(8) Uani 1 1 d . . . H27A H 0.6353 1.1663 0.1479 0.037 Uiso 1 1 calc R . . H27B H 0.7232 1.0305 0.1552 0.037 Uiso 1 1 calc R . . H27C H 0.6714 1.0817 0.1939 0.037 Uiso 1 1 calc R . . C28 C 0.5706(2) 0.8811(5) 0.10287(10) 0.0191(7) Uani 1 1 d . . . H28A H 0.5442 0.9897 0.0889 0.029 Uiso 1 1 calc R . . H28B H 0.5243 0.7854 0.0952 0.029 Uiso 1 1 calc R . . H28C H 0.6309 0.8517 0.0936 0.029 Uiso 1 1 calc R . . C29 C 0.4959(2) 0.9618(5) 0.16412(11) 0.0265(8) Uani 1 1 d . . . H29A H 0.4711 1.0674 0.1483 0.040 Uiso 1 1 calc R . . H29B H 0.5071 0.9866 0.1947 0.040 Uiso 1 1 calc R . . H29C H 0.4488 0.8666 0.1575 0.040 Uiso 1 1 calc R . . C30 C 0.8662(2) 0.4855(5) 0.19610(11) 0.0256(8) Uani 1 1 d . . . H30 H 0.8928 0.3963 0.2156 0.031 Uiso 1 1 calc R . . C31 C 1.0231(3) 0.4928(6) 0.17810(12) 0.0360(10) Uani 1 1 d . . . H31A H 1.0626 0.6010 0.1817 0.043 Uiso 1 1 calc R . . H31B H 1.0330 0.4370 0.1513 0.043 Uiso 1 1 calc R . . C32 C 1.0640(2) 0.3715(5) 0.21369(11) 0.0278(8) Uani 1 1 d . . . H32A H 1.0297 0.2575 0.2104 0.033 Uiso 1 1 calc R . . H32B H 1.0575 0.4231 0.2414 0.033 Uiso 1 1 calc R . . C33 C 1.1695(2) 0.3465(5) 0.21137(11) 0.0249(8) Uani 1 1 d . . . C34 C 1.1957(2) 0.2617(5) 0.17718(10) 0.0211(7) Uani 1 1 d . . . H34 H 1.1472 0.2129 0.1558 0.025 Uiso 1 1 calc R . . C35 C 1.2911(2) 0.2463(5) 0.17340(11) 0.0233(8) Uani 1 1 d . . . H35 H 1.3076 0.1866 0.1497 0.028 Uiso 1 1 calc R . . C36 C 1.3631(2) 0.3184(5) 0.20438(12) 0.0279(8) Uani 1 1 d . . . H36 H 1.4288 0.3082 0.2019 0.033 Uiso 1 1 calc R . . C37 C 1.3385(3) 0.4041(5) 0.23852(13) 0.0333(9) Uani 1 1 d . . . H37 H 1.3871 0.4533 0.2598 0.040 Uiso 1 1 calc R . . C38 C 1.2420(3) 0.4188(5) 0.24187(12) 0.0304(9) Uani 1 1 d . . . H38 H 1.2254 0.4794 0.2654 0.037 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 0.0081(3) 0.0239(3) 0.0159(3) -0.0040(2) 0.0032(2) 0.0013(2) Cl1 0.0185(4) 0.0445(6) 0.0315(5) -0.0224(4) 0.0030(4) -0.0007(4) Cl2 0.0191(4) 0.0218(4) 0.0190(4) -0.0015(3) 0.0053(3) 0.0011(3) O1 0.0109(11) 0.0207(12) 0.0190(11) -0.0069(9) 0.0047(9) 0.0002(9) O2 0.0132(11) 0.0251(13) 0.0172(11) 0.0042(10) 0.0055(9) 0.0048(9) N1 0.0099(13) 0.0214(15) 0.0178(14) 0.0039(11) 0.0023(11) -0.0018(11) N2 0.0153(14) 0.0432(19) 0.0195(15) 0.0046(13) 0.0068(12) 0.0122(13) C1 0.0114(15) 0.0141(16) 0.0142(15) 0.0005(12) 0.0021(12) 0.0033(12) C2 0.0102(15) 0.0150(17) 0.0149(15) 0.0030(12) 0.0008(12) 0.0009(12) C3 0.0192(16) 0.0119(17) 0.0162(16) -0.0007(13) -0.0003(13) 0.0026(13) C4 0.0172(16) 0.0207(18) 0.0160(16) 0.0004(13) 0.0038(13) 0.0091(14) C5 0.0124(15) 0.0202(18) 0.0180(16) 0.0040(13) 0.0061(13) 0.0037(13) C6 0.0104(15) 0.0147(16) 0.0158(15) 0.0046(12) 0.0022(12) 0.0025(12) C7 0.0104(15) 0.0152(17) 0.0227(17) 0.0021(13) 0.0036(12) -0.0009(13) C8 0.0197(17) 0.0139(17) 0.0278(19) 0.0007(14) 0.0001(14) 0.0010(14) C9 0.0189(17) 0.0174(18) 0.0248(18) -0.0004(14) 0.0003(14) -0.0051(14) C10 0.0133(16) 0.0237(19) 0.037(2) 0.0010(16) 0.0097(15) -0.0033(14) C11 0.0127(16) 0.0194(18) 0.0172(16) 0.0007(13) -0.0004(13) -0.0015(13) C12 0.0133(16) 0.0246(19) 0.0242(18) 0.0007(14) 0.0050(13) -0.0021(14) C13 0.0144(17) 0.030(2) 0.0233(18) 0.0041(15) 0.0033(14) -0.0048(15) C14 0.0129(16) 0.0195(18) 0.0231(17) 0.0051(14) 0.0022(13) 0.0008(13) C15 0.0213(18) 0.028(2) 0.0223(17) 0.0024(15) 0.0018(14) 0.0026(15) C16 0.0226(18) 0.0214(19) 0.0269(19) 0.0037(15) -0.0072(15) -0.0058(15) C17 0.0100(16) 0.025(2) 0.044(2) 0.0155(17) -0.0010(15) -0.0008(14) C18 0.0179(17) 0.0199(18) 0.034(2) 0.0117(15) 0.0117(15) 0.0090(14) C19 0.0189(17) 0.0208(18) 0.0253(18) 0.0003(14) 0.0033(14) 0.0017(14) C20 0.0150(16) 0.0165(17) 0.0113(15) -0.0006(12) 0.0030(12) 0.0003(13) C21 0.0170(16) 0.0211(18) 0.0137(16) -0.0022(13) 0.0016(13) 0.0066(14) C22 0.0208(17) 0.0162(17) 0.0163(16) 0.0024(13) -0.0007(13) 0.0027(14) C23 0.0200(17) 0.0187(18) 0.0179(16) 0.0028(13) 0.0035(13) -0.0057(14) C24 0.0116(15) 0.0202(18) 0.0176(16) -0.0028(13) 0.0040(13) 0.0015(13) C25 0.0105(15) 0.0173(17) 0.0138(15) -0.0028(13) 0.0014(12) -0.0004(13) C26 0.0121(15) 0.0184(17) 0.0176(16) 0.0022(13) 0.0032(13) 0.0047(13) C27 0.0261(19) 0.0192(19) 0.0256(19) 0.0020(14) -0.0022(15) 0.0003(15) C28 0.0170(17) 0.0225(18) 0.0173(17) 0.0020(14) 0.0020(13) 0.0069(14) C29 0.0212(18) 0.034(2) 0.0269(19) 0.0090(16) 0.0105(15) 0.0126(16) C30 0.0215(18) 0.035(2) 0.0195(18) 0.0051(15) 0.0021(14) 0.0157(16) C31 0.0213(19) 0.055(3) 0.034(2) 0.0128(19) 0.0110(16) 0.0167(19) C32 0.0155(17) 0.045(2) 0.0233(18) -0.0063(16) 0.0033(14) 0.0046(16) C33 0.0147(17) 0.034(2) 0.0246(18) -0.0022(16) 0.0002(14) 0.0071(15) C34 0.0124(16) 0.0264(19) 0.0232(17) -0.0029(15) 0.0002(13) 0.0025(14) C35 0.0189(17) 0.0203(19) 0.0330(19) -0.0012(15) 0.0106(15) 0.0019(14) C36 0.0123(17) 0.026(2) 0.046(2) -0.0002(17) 0.0069(16) 0.0023(15) C37 0.0180(18) 0.035(2) 0.042(2) -0.0125(18) -0.0059(16) 0.0010(16) C38 0.0209(19) 0.040(2) 0.028(2) -0.0107(17) -0.0014(15) 0.0098(17) _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 1.844(2) . ? Ti1 O2 1.856(2) . ? Ti1 N2 2.192(3) . ? Ti1 N1 2.205(3) . ? Ti1 Cl2 2.3087(10) . ? Ti1 Cl1 2.3144(10) . ? O1 C1 1.342(4) . ? O2 C20 1.340(4) . ? N1 C11 1.295(4) . ? N1 C12 1.491(4) . ? N2 C30 1.283(5) . ? N2 C31 1.482(4) . ? C1 C2 1.403(4) . ? C1 C6 1.411(4) . ? C2 C3 1.402(4) . ? C2 C11 1.442(4) . ? C3 C4 1.378(5) . ? C3 H3 0.9500 . ? C4 C5 1.388(5) . ? C4 H4 0.9500 . ? C5 C6 1.387(4) . ? C5 H5 0.9500 . ? C6 C7 1.528(4) . ? C7 C10 1.534(4) . ? C7 C8 1.538(4) . ? C7 C9 1.538(4) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11 0.9500 . ? C12 C13 1.523(5) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 C14 1.515(4) . ? C13 H13A 0.9900 . ? C13 H13B 0.9900 . ? C14 C15 1.387(5) . ? C14 C19 1.403(5) . ? C15 C16 1.390(5) . ? C15 H15 0.9500 . ? C16 C17 1.376(5) . ? C16 H16 0.9500 . ? C17 C18 1.387(5) . ? C17 H17 0.9500 . ? C18 C19 1.386(5) . ? C18 H18 0.9500 . ? C19 H19 0.9500 . ? C20 C21 1.405(4) . ? C20 C25 1.416(4) . ? C21 C22 1.394(5) . ? C21 C30 1.458(5) . ? C22 C23 1.375(5) . ? C22 H22 0.9500 . ? C23 C24 1.397(5) . ? C23 H23 0.9500 . ? C24 C25 1.396(4) . ? C24 H24 0.9500 . ? C25 C26 1.527(4) . ? C26 C29 1.524(4) . ? C26 C28 1.539(4) . ? C26 C27 1.543(5) . ? C27 H27A 0.9800 . ? C27 H27B 0.9800 . ? C27 H27C 0.9800 . ? C28 H28A 0.9800 . ? C28 H28B 0.9800 . ? C28 H28C 0.9800 . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C30 H30 0.9500 . ? C31 C32 1.496(5) . ? C31 H31A 0.9900 . ? C31 H31B 0.9900 . ? C32 C33 1.520(5) . ? C32 H32A 0.9900 . ? C32 H32B 0.9900 . ? C33 C34 1.380(5) . ? C33 C38 1.389(5) . ? C34 C35 1.381(5) . ? C34 H34 0.9500 . ? C35 C36 1.394(5) . ? C35 H35 0.9500 . ? C36 C37 1.373(5) . ? C36 H36 0.9500 . ? C37 C38 1.394(5) . ? C37 H37 0.9500 . ? C38 H38 0.9500 . ? 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 170.41(11) . . ? O1 Ti1 N2 91.04(10) . . ? O2 Ti1 N2 81.35(10) . . ? O1 Ti1 N1 81.63(9) . . ? O2 Ti1 N1 91.15(10) . . ? N2 Ti1 N1 79.12(11) . . ? O1 Ti1 Cl2 95.16(7) . . ? O2 Ti1 Cl2 91.58(7) . . ? N2 Ti1 Cl2 169.70(9) . . ? N1 Ti1 Cl2 93.63(7) . . ? O1 Ti1 Cl1 91.51(7) . . ? O2 Ti1 Cl1 94.23(8) . . ? N2 Ti1 Cl1 89.46(9) . . ? N1 Ti1 Cl1 166.51(8) . . ? Cl2 Ti1 Cl1 98.57(4) . . ? C1 O1 Ti1 145.5(2) . . ? C20 O2 Ti1 144.3(2) . . ? C11 N1 C12 113.0(3) . . ? C11 N1 Ti1 125.3(2) . . ? C12 N1 Ti1 121.6(2) . . ? C30 N2 C31 119.9(3) . . ? C30 N2 Ti1 127.1(2) . . ? C31 N2 Ti1 113.0(2) . . ? O1 C1 C2 117.3(3) . . ? O1 C1 C6 121.6(3) . . ? C2 C1 C6 121.1(3) . . ? C3 C2 C1 120.4(3) . . ? C3 C2 C11 117.1(3) . . ? C1 C2 C11 122.5(3) . . ? C4 C3 C2 119.0(3) . . ? C4 C3 H3 120.5 . . ? C2 C3 H3 120.5 . . ? C3 C4 C5 119.9(3) . . ? C3 C4 H4 120.1 . . ? C5 C4 H4 120.1 . . ? C6 C5 C4 123.5(3) . . ? C6 C5 H5 118.2 . . ? C4 C5 H5 118.2 . . ? C5 C6 C1 116.2(3) . . ? C5 C6 C7 121.8(3) . . ? C1 C6 C7 122.0(3) . . ? C6 C7 C10 111.6(3) . . ? C6 C7 C8 109.7(2) . . ? C10 C7 C8 107.2(3) . . ? C6 C7 C9 110.5(3) . . ? C10 C7 C9 108.0(3) . . ? C8 C7 C9 109.8(3) . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 H10A 109.5 . . ? C7 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N1 C11 C2 127.6(3) . . ? N1 C11 H11 116.2 . . ? C2 C11 H11 116.2 . . ? N1 C12 C13 110.0(3) . . ? N1 C12 H12A 109.7 . . ? C13 C12 H12A 109.7 . . ? N1 C12 H12B 109.7 . . ? C13 C12 H12B 109.7 . . ? H12A C12 H12B 108.2 . . ? C14 C13 C12 112.2(3) . . ? C14 C13 H13A 109.2 . . ? C12 C13 H13A 109.2 . . ? C14 C13 H13B 109.2 . . ? C12 C13 H13B 109.2 . . ? H13A C13 H13B 107.9 . . ? C15 C14 C19 118.7(3) . . ? C15 C14 C13 120.7(3) . . ? C19 C14 C13 120.5(3) . . ? C14 C15 C16 120.8(3) . . ? C14 C15 H15 119.6 . . ? C16 C15 H15 119.6 . . ? C17 C16 C15 120.1(3) . . ? C17 C16 H16 119.9 . . ? C15 C16 H16 119.9 . . ? C16 C17 C18 119.8(3) . . ? C16 C17 H17 120.1 . . ? C18 C17 H17 120.1 . . ? C19 C18 C17 120.4(3) . . ? C19 C18 H18 119.8 . . ? C17 C18 H18 119.8 . . ? C18 C19 C14 120.1(3) . . ? C18 C19 H19 120.0 . . ? C14 C19 H19 120.0 . . ? O2 C20 C21 118.3(3) . . ? O2 C20 C25 120.1(3) . . ? C21 C20 C25 121.6(3) . . ? C22 C21 C20 119.5(3) . . ? C22 C21 C30 118.7(3) . . ? C20 C21 C30 121.6(3) . . ? C23 C22 C21 120.2(3) . . ? C23 C22 H22 119.9 . . ? C21 C22 H22 119.9 . . ? C22 C23 C24 119.6(3) . . ? C22 C23 H23 120.2 . . ? C24 C23 H23 120.2 . . ? C25 C24 C23 122.9(3) . . ? C25 C24 H24 118.5 . . ? C23 C24 H24 118.5 . . ? C24 C25 C20 115.9(3) . . ? C24 C25 C26 122.7(3) . . ? C20 C25 C26 121.3(3) . . ? C29 C26 C25 111.5(3) . . ? C29 C26 C28 107.6(3) . . ? C25 C26 C28 112.2(3) . . ? C29 C26 C27 107.0(3) . . ? C25 C26 C27 109.2(3) . . ? C28 C26 C27 109.2(3) . . ? C26 C27 H27A 109.5 . . ? C26 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C26 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C26 C28 H28A 109.5 . . ? C26 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C26 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C26 C29 H29A 109.5 . . ? C26 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C26 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? N2 C30 C21 126.4(3) . . ? N2 C30 H30 116.8 . . ? C21 C30 H30 116.8 . . ? N2 C31 C32 120.2(3) . . ? N2 C31 H31A 107.3 . . ? C32 C31 H31A 107.3 . . ? N2 C31 H31B 107.3 . . ? C32 C31 H31B 107.3 . . ? H31A C31 H31B 106.9 . . ? C31 C32 C33 106.4(3) . . ? C31 C32 H32A 110.4 . . ? C33 C32 H32A 110.4 . . ? C31 C32 H32B 110.4 . . ? C33 C32 H32B 110.4 . . ? H32A C32 H32B 108.6 . . ? C34 C33 C38 118.0(3) . . ? C34 C33 C32 120.7(3) . . ? C38 C33 C32 121.2(3) . . ? C33 C34 C35 121.4(3) . . ? C33 C34 H34 119.3 . . ? C35 C34 H34 119.3 . . ? C34 C35 C36 120.0(3) . . ? C34 C35 H35 120.0 . . ? C36 C35 H35 120.0 . . ? C37 C36 C35 119.5(3) . . ? C37 C36 H36 120.3 . . ? C35 C36 H36 120.3 . . ? C36 C37 C38 119.9(3) . . ? C36 C37 H37 120.1 . . ? C38 C37 H37 120.1 . . ? C33 C38 C37 121.2(3) . . ? C33 C38 H38 119.4 . . ? C37 C38 H38 119.4 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 Ti1 O1 C1 47.2(8) . . . . ? N2 Ti1 O1 C1 84.5(4) . . . . ? N1 Ti1 O1 C1 5.7(4) . . . . ? Cl2 Ti1 O1 C1 -87.2(4) . . . . ? Cl1 Ti1 O1 C1 174.0(3) . . . . ? O1 Ti1 O2 C20 38.5(8) . . . . ? N2 Ti1 O2 C20 0.6(4) . . . . ? N1 Ti1 O2 C20 79.4(4) . . . . ? Cl2 Ti1 O2 C20 173.1(3) . . . . ? Cl1 Ti1 O2 C20 -88.2(4) . . . . ? O1 Ti1 N1 C11 -1.6(3) . . . . ? O2 Ti1 N1 C11 -175.2(3) . . . . ? N2 Ti1 N1 C11 -94.3(3) . . . . ? Cl2 Ti1 N1 C11 93.1(3) . . . . ? Cl1 Ti1 N1 C11 -61.7(5) . . . . ? O1 Ti1 N1 C12 176.1(2) . . . . ? O2 Ti1 N1 C12 2.5(2) . . . . ? N2 Ti1 N1 C12 83.4(2) . . . . ? Cl2 Ti1 N1 C12 -89.2(2) . . . . ? Cl1 Ti1 N1 C12 116.1(3) . . . . ? O1 Ti1 N2 C30 -167.3(3) . . . . ? O2 Ti1 N2 C30 6.9(3) . . . . ? N1 Ti1 N2 C30 -86.0(3) . . . . ? Cl2 Ti1 N2 C30 -40.2(7) . . . . ? Cl1 Ti1 N2 C30 101.2(3) . . . . ? O1 Ti1 N2 C31 12.3(3) . . . . ? O2 Ti1 N2 C31 -173.6(3) . . . . ? N1 Ti1 N2 C31 93.5(3) . . . . ? Cl2 Ti1 N2 C31 139.3(4) . . . . ? Cl1 Ti1 N2 C31 -79.3(3) . . . . ? Ti1 O1 C1 C2 -5.5(5) . . . . ? Ti1 O1 C1 C6 175.6(3) . . . . ? O1 C1 C2 C3 179.1(3) . . . . ? C6 C1 C2 C3 -1.9(5) . . . . ? O1 C1 C2 C11 -0.3(4) . . . . ? C6 C1 C2 C11 178.6(3) . . . . ? C1 C2 C3 C4 0.7(5) . . . . ? C11 C2 C3 C4 -179.8(3) . . . . ? C2 C3 C4 C5 0.8(5) . . . . ? C3 C4 C5 C6 -1.3(5) . . . . ? C4 C5 C6 C1 0.2(5) . . . . ? C4 C5 C6 C7 -179.3(3) . . . . ? O1 C1 C6 C5 -179.7(3) . . . . ? C2 C1 C6 C5 1.5(4) . . . . ? O1 C1 C6 C7 -0.2(4) . . . . ? C2 C1 C6 C7 -179.0(3) . . . . ? C5 C6 C7 C10 1.7(4) . . . . ? C1 C6 C7 C10 -177.8(3) . . . . ? C5 C6 C7 C8 120.3(3) . . . . ? C1 C6 C7 C8 -59.1(4) . . . . ? C5 C6 C7 C9 -118.5(3) . . . . ? C1 C6 C7 C9 62.0(4) . . . . ? C12 N1 C11 C2 -179.2(3) . . . . ? Ti1 N1 C11 C2 -1.3(5) . . . . ? C3 C2 C11 N1 -176.6(3) . . . . ? C1 C2 C11 N1 2.9(5) . . . . ? C11 N1 C12 C13 -94.1(3) . . . . ? Ti1 N1 C12 C13 87.9(3) . . . . ? N1 C12 C13 C14 179.4(3) . . . . ? C12 C13 C14 C15 -115.3(4) . . . . ? C12 C13 C14 C19 66.1(4) . . . . ? C19 C14 C15 C16 0.6(5) . . . . ? C13 C14 C15 C16 -178.0(3) . . . . ? C14 C15 C16 C17 1.1(5) . . . . ? C15 C16 C17 C18 -1.6(5) . . . . ? C16 C17 C18 C19 0.5(5) . . . . ? C17 C18 C19 C14 1.2(5) . . . . ? C15 C14 C19 C18 -1.7(5) . . . . ? C13 C14 C19 C18 176.9(3) . . . . ? Ti1 O2 C20 C21 -8.2(5) . . . . ? Ti1 O2 C20 C25 172.1(2) . . . . ? O2 C20 C21 C22 -175.0(3) . . . . ? C25 C20 C21 C22 4.7(5) . . . . ? O2 C20 C21 C30 9.5(5) . . . . ? C25 C20 C21 C30 -170.8(3) . . . . ? C20 C21 C22 C23 -0.6(5) . . . . ? C30 C21 C22 C23 175.1(3) . . . . ? C21 C22 C23 C24 -2.5(5) . . . . ? C22 C23 C24 C25 1.6(5) . . . . ? C23 C24 C25 C20 2.4(5) . . . . ? C23 C24 C25 C26 -173.7(3) . . . . ? O2 C20 C25 C24 174.2(3) . . . . ? C21 C20 C25 C24 -5.5(4) . . . . ? O2 C20 C25 C26 -9.7(4) . . . . ? C21 C20 C25 C26 170.6(3) . . . . ? C24 C25 C26 C29 -0.2(4) . . . . ? C20 C25 C26 C29 -176.0(3) . . . . ? C24 C25 C26 C28 -121.0(3) . . . . ? C20 C25 C26 C28 63.2(4) . . . . ? C24 C25 C26 C27 117.8(3) . . . . ? C20 C25 C26 C27 -58.0(4) . . . . ? C31 N2 C30 C21 173.8(4) . . . . ? Ti1 N2 C30 C21 -6.7(6) . . . . ? C22 C21 C30 N2 -178.2(4) . . . . ? C20 C21 C30 N2 -2.6(6) . . . . ? C30 N2 C31 C32 -2.6(6) . . . . ? Ti1 N2 C31 C32 177.8(3) . . . . ? N2 C31 C32 C33 -178.8(4) . . . . ? C31 C32 C33 C34 -66.0(5) . . . . ? C31 C32 C33 C38 109.4(4) . . . . ? C38 C33 C34 C35 0.9(6) . . . . ? C32 C33 C34 C35 176.4(3) . . . . ? C33 C34 C35 C36 -0.5(5) . . . . ? C34 C35 C36 C37 0.1(6) . . . . ? C35 C36 C37 C38 -0.2(6) . . . . ? C34 C33 C38 C37 -1.0(6) . . . . ? C32 C33 C38 C37 -176.5(4) . . . . ? C36 C37 C38 C33 0.6(6) . . . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 24.09 _diffrn_measured_fraction_theta_full 0.983 _refine_diff_density_max 1.194 _refine_diff_density_min -0.819 _refine_diff_density_rms 0.077 data_d:\as16js01 _database_code_depnum_ccdc_archive 'CCDC 902043' #TrackingRef 'web_deposit_cif_file_6_MichaelGardiner_1348050215.compound S1.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H26 Cl2 O4 Ti' _chemical_formula_weight 473.23 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' 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 monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 9.9030(9) _cell_length_b 22.683(2) _cell_length_c 10.1360(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.781(2) _cell_angle_gamma 90.00 _cell_volume 2276.6(4) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 28713 _cell_measurement_theta_min 2.20 _cell_measurement_theta_max 26.57 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.05 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.381 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 984 _exptl_absorpt_coefficient_mu 0.635 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Low data completion ratio is due to the limitations of the instrument available at the Australian Synchrotron operating under rotation data collection with a fixed detector and affects some high angle data. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron BM' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-BM1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q210' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 30459 _diffrn_reflns_av_R_equivalents 0.0559 _diffrn_reflns_av_sigmaI/netI 0.0339 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.20 _diffrn_reflns_theta_max 26.54 _reflns_number_total 4589 _reflns_number_gt 4390 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 1998)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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^)+(0.0488P)^2^+1.4821P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4589 _refine_ls_number_parameters 268 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0352 _refine_ls_R_factor_gt 0.0340 _refine_ls_wR_factor_ref 0.0913 _refine_ls_wR_factor_gt 0.0904 _refine_ls_goodness_of_fit_ref 1.042 _refine_ls_restrained_S_all 1.042 _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 0.91400(3) 0.184420(12) 0.67649(3) 0.01479(10) Uani 1 1 d . . . Cl1 Cl 1.04462(4) 0.128642(17) 0.81655(4) 0.02114(11) Uani 1 1 d . . . Cl2 Cl 0.95500(4) 0.272501(16) 0.78992(4) 0.01976(11) Uani 1 1 d . . . O1 O 0.75278(10) 0.16892(5) 0.75342(10) 0.0162(2) Uani 1 1 d . . . O2 O 0.79736(11) 0.23886(5) 0.55192(11) 0.0209(2) Uani 1 1 d . . . O3 O 0.89164(11) 0.12781(5) 0.54478(11) 0.0188(2) Uani 1 1 d . . . O4 O 1.07363(11) 0.21061(5) 0.55942(11) 0.0202(2) Uani 1 1 d . . . C1 C 0.62309(15) 0.18479(6) 0.74830(15) 0.0149(3) Uani 1 1 d . . . C2 C 0.58151(16) 0.22602(7) 0.65173(15) 0.0178(3) Uani 1 1 d . . . C3 C 0.44611(16) 0.24457(8) 0.64543(16) 0.0220(3) Uani 1 1 d . . . H3 H 0.4177 0.2725 0.5810 0.026 Uiso 1 1 calc R . . C4 C 0.35571(16) 0.22205(8) 0.73266(17) 0.0239(3) Uani 1 1 d . . . H4 H 0.2643 0.2347 0.7300 0.029 Uiso 1 1 calc R . . C5 C 0.39807(16) 0.18020(7) 0.82617(16) 0.0206(3) Uani 1 1 d . . . H5 H 0.3327 0.1644 0.8841 0.025 Uiso 1 1 calc R . . C6 C 0.53076(15) 0.16056(6) 0.83858(14) 0.0153(3) Uani 1 1 d . . . C7 C 0.57683(15) 0.11627(7) 0.94434(15) 0.0173(3) Uani 1 1 d . . . C8 C 0.68420(16) 0.14456(7) 1.03578(15) 0.0189(3) Uani 1 1 d . . . H8A H 0.7618 0.1569 0.9835 0.028 Uiso 1 1 calc R . . H8B H 0.7137 0.1158 1.1023 0.028 Uiso 1 1 calc R . . H8C H 0.6454 0.1790 1.0796 0.028 Uiso 1 1 calc R . . C9 C 0.63692(17) 0.06100(7) 0.87948(17) 0.0231(3) Uani 1 1 d . . . H9A H 0.7133 0.0724 0.8245 0.035 Uiso 1 1 calc R . . H9B H 0.5677 0.0418 0.8245 0.035 Uiso 1 1 calc R . . H9C H 0.6681 0.0336 0.9481 0.035 Uiso 1 1 calc R . . C10 C 0.45757(17) 0.09726(8) 1.02977(17) 0.0252(3) Uani 1 1 d . . . H10A H 0.4889 0.0688 1.0962 0.038 Uiso 1 1 calc R . . H10B H 0.3879 0.0789 0.9738 0.038 Uiso 1 1 calc R . . H10C H 0.4198 0.1319 1.0738 0.038 Uiso 1 1 calc R . . C11 C 0.67420(16) 0.24969(7) 0.55801(15) 0.0200(3) Uani 1 1 d . . . H11 H 0.639(2) 0.2776(9) 0.493(2) 0.024 Uiso 1 1 d . . . C12 C 0.94168(15) 0.11232(7) 0.42884(14) 0.0168(3) Uani 1 1 d . . . C13 C 1.05850(16) 0.14124(7) 0.38301(16) 0.0193(3) Uani 1 1 d . . . C14 C 1.11886(17) 0.12335(7) 0.26416(16) 0.0240(3) Uani 1 1 d . . . H14 H 1.1985 0.1421 0.2343 0.029 Uiso 1 1 calc R . . C15 C 1.06120(19) 0.07862(8) 0.19265(17) 0.0283(4) Uani 1 1 d . . . H15 H 1.1010 0.0660 0.1127 0.034 Uiso 1 1 calc R . . C16 C 0.94333(18) 0.05132(8) 0.23749(17) 0.0252(3) Uani 1 1 d . . . H16 H 0.9047 0.0207 0.1852 0.030 Uiso 1 1 calc R . . C17 C 0.87977(15) 0.06659(7) 0.35454(15) 0.0190(3) Uani 1 1 d . . . C18 C 0.75185(16) 0.03581(7) 0.40321(16) 0.0203(3) Uani 1 1 d . . . C19 C 0.78286(18) 0.00398(8) 0.53394(18) 0.0262(4) Uani 1 1 d . . . H19A H 0.7010 -0.0157 0.5649 0.039 Uiso 1 1 calc R . . H19B H 0.8135 0.0327 0.6000 0.039 Uiso 1 1 calc R . . H19C H 0.8538 -0.0254 0.5203 0.039 Uiso 1 1 calc R . . C20 C 0.63774(16) 0.08096(8) 0.42224(18) 0.0247(3) Uani 1 1 d . . . H20A H 0.5569 0.0607 0.4537 0.037 Uiso 1 1 calc R . . H20B H 0.6172 0.1003 0.3379 0.037 Uiso 1 1 calc R . . H20C H 0.6665 0.1106 0.4872 0.037 Uiso 1 1 calc R . . C21 C 0.70139(19) -0.01055(8) 0.30379(19) 0.0296(4) Uani 1 1 d . . . H21A H 0.6201 -0.0296 0.3377 0.044 Uiso 1 1 calc R . . H21B H 0.7718 -0.0403 0.2909 0.044 Uiso 1 1 calc R . . H21C H 0.6801 0.0086 0.2194 0.044 Uiso 1 1 calc R . . C22 C 1.11794(16) 0.18877(7) 0.45521(16) 0.0202(3) Uani 1 1 d . . . H22 H 1.197(2) 0.2059(9) 0.421(2) 0.024 Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.01162(15) 0.01811(16) 0.01464(15) 0.00007(9) 0.00025(10) -0.00104(9) Cl1 0.01632(19) 0.0221(2) 0.0249(2) 0.00205(14) -0.00317(14) 0.00270(13) Cl2 0.02069(19) 0.01865(19) 0.01994(19) -0.00176(13) 0.00066(14) -0.00058(13) O1 0.0121(5) 0.0197(5) 0.0168(5) 0.0025(4) 0.0002(4) 0.0011(4) O2 0.0180(5) 0.0259(6) 0.0187(5) 0.0052(4) -0.0014(4) -0.0023(4) O3 0.0180(5) 0.0222(6) 0.0164(5) -0.0023(4) 0.0015(4) -0.0035(4) O4 0.0173(5) 0.0228(6) 0.0206(5) -0.0008(4) 0.0034(4) -0.0033(4) C1 0.0121(7) 0.0166(7) 0.0159(7) -0.0027(5) -0.0019(5) -0.0004(5) C2 0.0171(7) 0.0200(7) 0.0162(7) -0.0013(6) -0.0019(6) 0.0007(6) C3 0.0203(8) 0.0263(8) 0.0193(7) -0.0003(6) -0.0069(6) 0.0057(6) C4 0.0137(7) 0.0344(9) 0.0234(8) -0.0032(7) -0.0033(6) 0.0052(6) C5 0.0144(7) 0.0281(8) 0.0194(7) -0.0051(6) 0.0000(6) -0.0021(6) C6 0.0147(7) 0.0168(7) 0.0144(7) -0.0030(5) -0.0009(5) -0.0016(5) C7 0.0169(7) 0.0169(7) 0.0180(7) 0.0002(6) 0.0003(6) -0.0036(6) C8 0.0197(7) 0.0200(7) 0.0169(7) 0.0019(6) -0.0028(6) -0.0039(6) C9 0.0279(8) 0.0167(7) 0.0248(8) -0.0017(6) 0.0002(6) -0.0013(6) C10 0.0234(8) 0.0275(8) 0.0249(8) 0.0036(7) 0.0031(7) -0.0075(6) C11 0.0220(7) 0.0212(7) 0.0167(7) 0.0017(6) -0.0052(6) -0.0009(6) C12 0.0173(7) 0.0189(7) 0.0141(7) 0.0010(6) -0.0012(5) 0.0045(6) C13 0.0198(7) 0.0195(7) 0.0188(7) 0.0023(6) 0.0015(6) 0.0038(6) C14 0.0247(8) 0.0257(8) 0.0219(8) 0.0025(6) 0.0064(6) 0.0052(6) C15 0.0327(9) 0.0333(9) 0.0191(8) -0.0031(7) 0.0053(7) 0.0065(7) C16 0.0279(8) 0.0265(8) 0.0212(8) -0.0054(6) -0.0033(7) 0.0049(7) C17 0.0189(7) 0.0198(7) 0.0181(7) 0.0003(6) -0.0041(6) 0.0044(6) C18 0.0183(7) 0.0198(7) 0.0225(8) -0.0022(6) -0.0043(6) 0.0007(6) C19 0.0239(8) 0.0243(8) 0.0302(9) 0.0044(7) -0.0051(7) -0.0037(6) C20 0.0172(7) 0.0259(8) 0.0311(9) -0.0030(7) -0.0022(6) 0.0031(6) C21 0.0257(8) 0.0293(9) 0.0336(9) -0.0105(7) -0.0063(7) -0.0017(7) C22 0.0180(7) 0.0218(8) 0.0208(8) 0.0046(6) 0.0033(6) 0.0003(6) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.8206(11) . ? Ti1 O3 1.8633(11) . ? Ti1 O4 2.0763(11) . ? Ti1 O2 2.1009(11) . ? Ti1 Cl1 2.2889(5) . ? Ti1 Cl2 2.3379(5) . ? O1 C1 1.3342(18) . ? O2 C11 1.246(2) . ? O3 C12 1.3288(18) . ? O4 C22 1.252(2) . ? C1 C2 1.411(2) . ? C1 C6 1.414(2) . ? C2 C3 1.406(2) . ? C2 C11 1.434(2) . ? C3 C4 1.366(2) . ? C3 H3 0.9500 . ? C4 C5 1.402(2) . ? C4 H4 0.9500 . ? C5 C6 1.391(2) . ? C5 H5 0.9500 . ? C6 C7 1.534(2) . ? C7 C10 1.536(2) . ? C7 C9 1.539(2) . ? C7 C8 1.541(2) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11 0.98(2) . ? C12 C13 1.414(2) . ? C12 C17 1.417(2) . ? C13 C14 1.412(2) . ? C13 C22 1.426(2) . ? C14 C15 1.367(3) . ? C14 H14 0.9500 . ? C15 C16 1.403(3) . ? C15 H15 0.9500 . ? C16 C17 1.394(2) . ? C16 H16 0.9500 . ? C17 C18 1.534(2) . ? C18 C21 1.535(2) . ? C18 C19 1.536(2) . ? C18 C20 1.539(2) . ? C19 H19A 0.9800 . ? C19 H19B 0.9800 . ? C19 H19C 0.9800 . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 0.9800 . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? C22 H22 0.95(2) . ? 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 O3 94.44(5) . . ? O1 Ti1 O4 168.23(5) . . ? O3 Ti1 O4 82.63(5) . . ? O1 Ti1 O2 83.85(5) . . ? O3 Ti1 O2 85.15(5) . . ? O4 Ti1 O2 84.55(4) . . ? O1 Ti1 Cl1 96.84(4) . . ? O3 Ti1 Cl1 97.13(4) . . ? O4 Ti1 Cl1 94.84(3) . . ? O2 Ti1 Cl1 177.55(4) . . ? O1 Ti1 Cl2 95.85(4) . . ? O3 Ti1 Cl2 163.62(4) . . ? O4 Ti1 Cl2 84.72(3) . . ? O2 Ti1 Cl2 83.32(3) . . ? Cl1 Ti1 Cl2 94.271(17) . . ? C1 O1 Ti1 141.31(10) . . ? C11 O2 Ti1 128.05(10) . . ? C12 O3 Ti1 140.69(10) . . ? C22 O4 Ti1 130.35(11) . . ? O1 C1 C2 118.52(13) . . ? O1 C1 C6 120.04(13) . . ? C2 C1 C6 121.43(14) . . ? C3 C2 C1 119.93(14) . . ? C3 C2 C11 118.46(14) . . ? C1 C2 C11 121.61(14) . . ? C4 C3 C2 119.46(15) . . ? C4 C3 H3 120.3 . . ? C2 C3 H3 120.3 . . ? C3 C4 C5 119.88(15) . . ? C3 C4 H4 120.1 . . ? C5 C4 H4 120.1 . . ? C6 C5 C4 123.47(15) . . ? C6 C5 H5 118.3 . . ? C4 C5 H5 118.3 . . ? C5 C6 C1 115.81(14) . . ? C5 C6 C7 122.98(14) . . ? C1 C6 C7 121.21(13) . . ? C6 C7 C10 110.74(13) . . ? C6 C7 C9 110.37(12) . . ? C10 C7 C9 108.48(13) . . ? C6 C7 C8 110.10(12) . . ? C10 C7 C8 107.91(13) . . ? C9 C7 C8 109.18(13) . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 H10A 109.5 . . ? C7 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? O2 C11 C2 126.48(14) . . ? O2 C11 H11 116.0(12) . . ? C2 C11 H11 117.6(12) . . ? O3 C12 C13 118.98(14) . . ? O3 C12 C17 120.00(14) . . ? C13 C12 C17 121.01(14) . . ? C14 C13 C12 120.32(15) . . ? C14 C13 C22 118.61(15) . . ? C12 C13 C22 121.07(14) . . ? C15 C14 C13 119.15(16) . . ? C15 C14 H14 120.4 . . ? C13 C14 H14 120.4 . . ? C14 C15 C16 119.95(15) . . ? C14 C15 H15 120.0 . . ? C16 C15 H15 120.0 . . ? C17 C16 C15 123.59(16) . . ? C17 C16 H16 118.2 . . ? C15 C16 H16 118.2 . . ? C16 C17 C12 115.93(15) . . ? C16 C17 C18 123.02(14) . . ? C12 C17 C18 121.04(14) . . ? C17 C18 C21 111.32(14) . . ? C17 C18 C19 109.58(13) . . ? C21 C18 C19 107.67(14) . . ? C17 C18 C20 110.40(13) . . ? C21 C18 C20 107.76(13) . . ? C19 C18 C20 110.06(14) . . ? C18 C19 H19A 109.5 . . ? C18 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C18 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? C18 C20 H20A 109.5 . . ? C18 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C18 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C18 C21 H21A 109.5 . . ? C18 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C18 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? O4 C22 C13 125.84(15) . . ? O4 C22 H22 116.8(12) . . ? C13 C22 H22 117.4(12) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O3 Ti1 O1 C1 -89.34(16) . . . . ? O4 Ti1 O1 C1 -14.3(3) . . . . ? O2 Ti1 O1 C1 -4.71(15) . . . . ? Cl1 Ti1 O1 C1 172.92(15) . . . . ? Cl2 Ti1 O1 C1 77.89(15) . . . . ? O1 Ti1 O2 C11 3.53(14) . . . . ? O3 Ti1 O2 C11 98.54(14) . . . . ? O4 Ti1 O2 C11 -178.43(14) . . . . ? Cl1 Ti1 O2 C11 -102.8(8) . . . . ? Cl2 Ti1 O2 C11 -93.12(13) . . . . ? O1 Ti1 O3 C12 164.12(16) . . . . ? O4 Ti1 O3 C12 -4.41(15) . . . . ? O2 Ti1 O3 C12 80.70(16) . . . . ? Cl1 Ti1 O3 C12 -98.40(15) . . . . ? Cl2 Ti1 O3 C12 35.3(3) . . . . ? O1 Ti1 O4 C22 -79.2(3) . . . . ? O3 Ti1 O4 C22 -2.94(14) . . . . ? O2 Ti1 O4 C22 -88.74(14) . . . . ? Cl1 Ti1 O4 C22 93.64(14) . . . . ? Cl2 Ti1 O4 C22 -172.50(14) . . . . ? Ti1 O1 C1 C2 3.0(2) . . . . ? Ti1 O1 C1 C6 -176.81(11) . . . . ? O1 C1 C2 C3 -178.72(14) . . . . ? C6 C1 C2 C3 1.1(2) . . . . ? O1 C1 C2 C11 1.6(2) . . . . ? C6 C1 C2 C11 -178.54(14) . . . . ? C1 C2 C3 C4 -0.5(2) . . . . ? C11 C2 C3 C4 179.19(15) . . . . ? C2 C3 C4 C5 -0.9(3) . . . . ? C3 C4 C5 C6 1.7(3) . . . . ? C4 C5 C6 C1 -1.1(2) . . . . ? C4 C5 C6 C7 177.90(14) . . . . ? O1 C1 C6 C5 179.47(13) . . . . ? C2 C1 C6 C5 -0.3(2) . . . . ? O1 C1 C6 C7 0.5(2) . . . . ? C2 C1 C6 C7 -179.33(13) . . . . ? C5 C6 C7 C10 0.7(2) . . . . ? C1 C6 C7 C10 179.57(13) . . . . ? C5 C6 C7 C9 120.80(16) . . . . ? C1 C6 C7 C9 -60.29(17) . . . . ? C5 C6 C7 C8 -118.59(16) . . . . ? C1 C6 C7 C8 60.32(18) . . . . ? Ti1 O2 C11 C2 -1.4(2) . . . . ? C3 C2 C11 O2 178.38(16) . . . . ? C1 C2 C11 O2 -2.0(3) . . . . ? Ti1 O3 C12 C13 7.9(2) . . . . ? Ti1 O3 C12 C17 -173.47(11) . . . . ? O3 C12 C13 C14 176.12(14) . . . . ? C17 C12 C13 C14 -2.5(2) . . . . ? O3 C12 C13 C22 -3.8(2) . . . . ? C17 C12 C13 C22 177.60(14) . . . . ? C12 C13 C14 C15 1.4(2) . . . . ? C22 C13 C14 C15 -178.67(15) . . . . ? C13 C14 C15 C16 0.2(3) . . . . ? C14 C15 C16 C17 -0.9(3) . . . . ? C15 C16 C17 C12 -0.1(2) . . . . ? C15 C16 C17 C18 -179.21(15) . . . . ? O3 C12 C17 C16 -176.80(14) . . . . ? C13 C12 C17 C16 1.8(2) . . . . ? O3 C12 C17 C18 2.3(2) . . . . ? C13 C12 C17 C18 -179.10(13) . . . . ? C16 C17 C18 C21 -2.9(2) . . . . ? C12 C17 C18 C21 178.06(14) . . . . ? C16 C17 C18 C19 116.08(17) . . . . ? C12 C17 C18 C19 -62.95(18) . . . . ? C16 C17 C18 C20 -122.54(16) . . . . ? C12 C17 C18 C20 58.43(18) . . . . ? Ti1 O4 C22 C13 6.0(2) . . . . ? C14 C13 C22 O4 177.61(15) . . . . ? C12 C13 C22 O4 -2.5(3) . . . . ? _diffrn_measured_fraction_theta_max 0.967 _diffrn_reflns_theta_full 26.54 _diffrn_measured_fraction_theta_full 0.967 _refine_diff_density_max 0.327 _refine_diff_density_min -0.582 _refine_diff_density_rms 0.068