# 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:\as24js25 _database_code_depnum_ccdc_archive 'CCDC 902939' #TrackingRef 'web_deposit_cif_file_0_MichaelGardiner_1348547463.4.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C29 H37 N O2' _chemical_formula_weight 431.60 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/c _symmetry_space_group_name_Hall '-C 2yc' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 26.9936(15) _cell_length_b 10.4290(19) _cell_length_c 18.5420(17) _cell_angle_alpha 90.00 _cell_angle_beta 107.509(4) _cell_angle_gamma 90.00 _cell_volume 4978.0(11) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 32032 _cell_measurement_theta_min 1.58 _cell_measurement_theta_max 28.72 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.152 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1872 _exptl_absorpt_coefficient_mu 0.071 _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 41288 _diffrn_reflns_av_R_equivalents 0.0323 _diffrn_reflns_av_sigmaI/netI 0.0173 _diffrn_reflns_limit_h_min -35 _diffrn_reflns_limit_h_max 34 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 1.58 _diffrn_reflns_theta_max 28.72 _reflns_number_total 6157 _reflns_number_gt 5469 _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^)+(0.0665P)^2^+4.0125P] 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 6157 _refine_ls_number_parameters 293 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0535 _refine_ls_R_factor_gt 0.0486 _refine_ls_wR_factor_ref 0.1321 _refine_ls_wR_factor_gt 0.1281 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.041 _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 O1 O 0.05191(3) 0.71823(9) 0.09830(4) 0.0279(2) Uani 1 1 d . . . O2 O 0.16460(3) 0.70956(9) 0.18995(5) 0.02692(19) Uani 1 1 d . . . N1 N 0.12200(3) 0.64728(10) 0.01872(5) 0.0219(2) Uani 1 1 d . . . C1 C 0.01513(4) 0.71190(12) 0.02856(6) 0.0226(2) Uani 1 1 d . . . C2 C 0.02593(4) 0.64293(12) -0.02935(6) 0.0224(2) Uani 1 1 d . . . C3 C -0.01032(4) 0.63917(12) -0.10098(6) 0.0233(2) Uani 1 1 d . . . H3 H -0.0023 0.5928 -0.1402 0.028 Uiso 1 1 calc R . . C4 C -0.05780(4) 0.70153(12) -0.11655(6) 0.0230(2) Uani 1 1 d . . . C5 C -0.06792(4) 0.76731(12) -0.05668(6) 0.0235(2) Uani 1 1 d . . . H5 H -0.1004 0.8098 -0.0662 0.028 Uiso 1 1 calc R . . C6 C -0.03304(4) 0.77413(12) 0.01643(6) 0.0228(2) Uani 1 1 d . . . C7 C -0.04630(4) 0.84627(13) 0.08045(7) 0.0270(2) Uani 1 1 d . . . C8 C -0.00895(5) 0.95968(14) 0.10733(8) 0.0349(3) Uani 1 1 d . . . H8A H 0.0269 0.9281 0.1242 0.052 Uiso 1 1 calc R . . H8B H -0.0169 1.0030 0.1494 0.052 Uiso 1 1 calc R . . H8C H -0.0130 1.0203 0.0655 0.052 Uiso 1 1 calc R . . C9 C -0.04282(5) 0.75448(15) 0.14690(7) 0.0344(3) Uani 1 1 d . . . H9A H -0.0078 0.7180 0.1648 0.052 Uiso 1 1 calc R . . H9B H -0.0682 0.6853 0.1300 0.052 Uiso 1 1 calc R . . H9C H -0.0502 0.8018 0.1881 0.052 Uiso 1 1 calc R . . C10 C -0.10177(5) 0.90048(15) 0.05469(8) 0.0344(3) Uani 1 1 d . . . H10A H -0.1088 0.9456 0.0969 0.052 Uiso 1 1 calc R . . H10B H -0.1266 0.8301 0.0380 0.052 Uiso 1 1 calc R . . H10C H -0.1053 0.9603 0.0127 0.052 Uiso 1 1 calc R . . C11 C -0.09690(4) 0.70307(13) -0.19618(6) 0.0260(2) Uani 1 1 d . . . C12 C -0.15136(5) 0.66655(19) -0.19336(8) 0.0439(4) Uani 1 1 d . . . H12A H -0.1504 0.5805 -0.1717 0.066 Uiso 1 1 calc R . . H12B H -0.1757 0.6674 -0.2447 0.066 Uiso 1 1 calc R . . H12C H -0.1628 0.7284 -0.1619 0.066 Uiso 1 1 calc R . . C13 C -0.09753(6) 0.83636(15) -0.22958(8) 0.0417(3) Uani 1 1 d . . . H13A H -0.1224 0.8384 -0.2805 0.063 Uiso 1 1 calc R . . H13B H -0.0628 0.8575 -0.2323 0.063 Uiso 1 1 calc R . . H13C H -0.1079 0.8991 -0.1975 0.063 Uiso 1 1 calc R . . C14 C -0.08181(5) 0.60646(16) -0.24871(7) 0.0378(3) Uani 1 1 d . . . H14A H -0.0811 0.5198 -0.2280 0.057 Uiso 1 1 calc R . . H14B H -0.0474 0.6280 -0.2525 0.057 Uiso 1 1 calc R . . H14C H -0.1073 0.6101 -0.2990 0.057 Uiso 1 1 calc R . . C15 C 0.07553(4) 0.56749(12) -0.01434(6) 0.0235(2) Uani 1 1 d . . . H15A H 0.0751 0.4962 0.0207 0.028 Uiso 1 1 calc R . . H15B H 0.0775 0.5298 -0.0624 0.028 Uiso 1 1 calc R . . C16 C 0.12438(4) 0.75267(13) -0.03291(7) 0.0275(2) Uani 1 1 d . . . H16A H 0.0912 0.7988 -0.0477 0.041 Uiso 1 1 calc R . . H16B H 0.1311 0.7176 -0.0781 0.041 Uiso 1 1 calc R . . H16C H 0.1524 0.8118 -0.0073 0.041 Uiso 1 1 calc R . . C17 C 0.16949(4) 0.57578(12) 0.04245(6) 0.0231(2) Uani 1 1 d . . . C18 C 0.21557(4) 0.63590(13) 0.08679(6) 0.0249(2) Uani 1 1 d . . . C19 C 0.26192(4) 0.56624(14) 0.10419(6) 0.0306(3) Uani 1 1 d . . . H19 H 0.2933 0.6071 0.1319 0.037 Uiso 1 1 calc R . . C20 C 0.26361(5) 0.43974(15) 0.08246(7) 0.0332(3) Uani 1 1 d . . . H20 H 0.2957 0.3950 0.0947 0.040 Uiso 1 1 calc R . . C21 C 0.21797(5) 0.37939(14) 0.04270(7) 0.0318(3) Uani 1 1 d . . . H21 H 0.2183 0.2915 0.0295 0.038 Uiso 1 1 calc R . . C22 C 0.17155(4) 0.44750(13) 0.02207(7) 0.0279(3) Uani 1 1 d . . . H22 H 0.1406 0.4058 -0.0065 0.033 Uiso 1 1 calc R . . C23 C 0.21834(4) 0.76880(13) 0.11653(6) 0.0254(2) Uani 1 1 d . . . C24 C 0.19365(4) 0.80358(12) 0.17051(6) 0.0244(2) Uani 1 1 d . . . C25 C 0.20054(5) 0.92533(13) 0.20247(7) 0.0302(3) Uani 1 1 d . . . H25 H 0.1840 0.9476 0.2393 0.036 Uiso 1 1 calc R . . C26 C 0.23154(5) 1.01483(15) 0.18068(8) 0.0366(3) Uani 1 1 d . . . H26 H 0.2361 1.0979 0.2027 0.044 Uiso 1 1 calc R . . C27 C 0.25568(5) 0.98294(16) 0.12704(7) 0.0384(3) Uani 1 1 d . . . H27 H 0.2765 1.0442 0.1115 0.046 Uiso 1 1 calc R . . C28 C 0.24922(5) 0.86085(15) 0.09619(7) 0.0328(3) Uani 1 1 d . . . H28 H 0.2664 0.8391 0.0600 0.039 Uiso 1 1 calc R . . C29 C 0.14398(6) 0.73764(15) 0.25058(7) 0.0357(3) Uani 1 1 d . . . H29A H 0.1723 0.7616 0.2956 0.054 Uiso 1 1 calc R . . H29B H 0.1261 0.6618 0.2617 0.054 Uiso 1 1 calc R . . H29C H 0.1193 0.8089 0.2361 0.054 Uiso 1 1 calc R . . H1 H 0.0825(9) 0.699(2) 0.0915(12) 0.064 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 O1 0.0155(4) 0.0494(6) 0.0166(4) -0.0043(3) 0.0018(3) 0.0024(3) O2 0.0241(4) 0.0380(5) 0.0218(4) -0.0035(3) 0.0117(3) -0.0053(3) N1 0.0130(4) 0.0343(5) 0.0174(4) -0.0004(4) 0.0030(3) 0.0018(3) C1 0.0146(5) 0.0357(6) 0.0162(5) -0.0010(4) 0.0029(4) -0.0007(4) C2 0.0142(4) 0.0343(6) 0.0186(5) -0.0008(4) 0.0046(4) 0.0001(4) C3 0.0167(5) 0.0357(6) 0.0173(5) -0.0020(4) 0.0049(4) -0.0007(4) C4 0.0156(5) 0.0339(6) 0.0180(5) 0.0010(4) 0.0029(4) -0.0014(4) C5 0.0142(5) 0.0331(6) 0.0223(5) 0.0000(4) 0.0040(4) 0.0006(4) C6 0.0155(5) 0.0333(6) 0.0201(5) -0.0024(4) 0.0059(4) -0.0011(4) C7 0.0178(5) 0.0392(7) 0.0256(5) -0.0077(5) 0.0087(4) -0.0017(4) C8 0.0242(6) 0.0446(8) 0.0376(7) -0.0150(6) 0.0120(5) -0.0066(5) C9 0.0301(6) 0.0525(8) 0.0245(6) -0.0057(5) 0.0139(5) -0.0020(6) C10 0.0198(5) 0.0451(8) 0.0397(7) -0.0140(6) 0.0110(5) 0.0000(5) C11 0.0168(5) 0.0401(7) 0.0186(5) 0.0010(4) 0.0014(4) -0.0011(4) C12 0.0212(6) 0.0823(12) 0.0253(6) -0.0037(7) 0.0025(5) -0.0087(6) C13 0.0371(7) 0.0460(8) 0.0309(7) 0.0070(6) -0.0065(5) -0.0013(6) C14 0.0335(7) 0.0519(9) 0.0223(6) -0.0057(5) -0.0001(5) 0.0008(6) C15 0.0146(5) 0.0348(6) 0.0208(5) -0.0024(4) 0.0046(4) 0.0009(4) C16 0.0178(5) 0.0384(7) 0.0241(5) 0.0036(5) 0.0030(4) 0.0005(4) C17 0.0152(5) 0.0391(6) 0.0155(4) 0.0009(4) 0.0052(4) 0.0037(4) C18 0.0167(5) 0.0441(7) 0.0140(4) 0.0013(4) 0.0046(4) 0.0026(4) C19 0.0158(5) 0.0560(8) 0.0187(5) 0.0025(5) 0.0034(4) 0.0049(5) C20 0.0204(5) 0.0566(8) 0.0230(5) 0.0051(5) 0.0073(4) 0.0138(5) C21 0.0262(6) 0.0446(8) 0.0264(6) 0.0012(5) 0.0107(5) 0.0113(5) C22 0.0198(5) 0.0408(7) 0.0234(5) -0.0020(5) 0.0072(4) 0.0048(5) C23 0.0151(5) 0.0427(7) 0.0160(5) 0.0010(4) 0.0012(4) -0.0019(4) C24 0.0166(5) 0.0363(6) 0.0186(5) 0.0012(4) 0.0027(4) -0.0021(4) C25 0.0254(6) 0.0389(7) 0.0248(5) -0.0011(5) 0.0051(4) -0.0017(5) C26 0.0353(7) 0.0392(7) 0.0306(6) 0.0011(5) 0.0028(5) -0.0079(5) C27 0.0331(7) 0.0522(9) 0.0267(6) 0.0064(6) 0.0039(5) -0.0150(6) C28 0.0217(5) 0.0573(9) 0.0184(5) 0.0019(5) 0.0042(4) -0.0091(5) C29 0.0374(7) 0.0501(8) 0.0256(6) -0.0087(5) 0.0185(5) -0.0108(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. Hydrogen bonds with H..A < r(A) + 2.000 Angstroms and 110 deg. D-H d(D-H) d(H..A) _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 28454 _diffrn_reflns_av_R_equivalents 0.0250 _diffrn_reflns_av_sigmaI/netI 0.0227 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.27 _diffrn_reflns_theta_max 26.54 _reflns_number_total 7664 _reflns_number_gt 7257 _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 DCM molecule, modelled as a two site, completmentary arrangement requiring SADI to give acceptable C-Cl distances. The largest residuals were in the region of C33 and likely arise from further minor disorder components that were not able to be modelled. ; _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^)+(0.1145P)^2^+13.3402P] 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 7664 _refine_ls_number_parameters 444 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0819 _refine_ls_R_factor_gt 0.0796 _refine_ls_wR_factor_ref 0.2232 _refine_ls_wR_factor_gt 0.2214 _refine_ls_goodness_of_fit_ref 1.062 _refine_ls_restrained_S_all 1.065 _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 0.05991(11) 0.35113(5) 0.36098(5) 0.0183(2) Uani 1 1 d . . . Ti2 Ti 0.32543(11) 0.11951(5) -0.15426(6) 0.0197(2) Uani 1 1 d . . . Cl1 Cl 0.25160(17) 0.48286(8) 0.39666(8) 0.0286(3) Uani 1 1 d . . . Cl2 Cl -0.17596(16) 0.40742(7) 0.34226(8) 0.0240(3) Uani 1 1 d . . . Cl3 Cl -0.12042(18) 0.21514(7) 0.34277(8) 0.0298(3) Uani 1 1 d . . . Cl4 Cl 0.26245(18) 0.10218(8) -0.02440(8) 0.0281(3) Uani 1 1 d . . . Cl5 Cl 0.61639(16) 0.14206(8) -0.09825(9) 0.0292(3) Uani 1 1 d . . . Cl6 Cl 0.3649(2) 0.11031(10) -0.28877(9) 0.0397(4) Uani 1 1 d . . . Cl7 Cl -0.2027(4) 0.13224(16) 0.55128(15) 0.0748(7) Uani 1 1 d D . . Cl8 Cl -0.4813(4) 0.07333(18) 0.40405(19) 0.0835(7) Uani 1 1 d D . . O1 O 0.0978(5) 0.3442(2) 0.2594(2) 0.0219(7) Uani 1 1 d . . . O2 O 0.0935(5) 0.3388(2) 0.4913(2) 0.0258(8) Uani 1 1 d . . . O3 O 0.2949(5) 0.2239(2) -0.1633(3) 0.0268(8) Uani 1 1 d . . . O4 O 0.2615(5) -0.0144(2) -0.1647(2) 0.0211(7) Uani 1 1 d . . . N1 N 0.2842(6) 0.2994(2) 0.4003(2) 0.0205(8) Uani 1 1 d . . . N2 N 0.0486(5) 0.0816(2) -0.2028(2) 0.0185(8) Uani 1 1 d . . . C1 C 0.1945(6) 0.3164(3) 0.2154(3) 0.0169(9) Uani 1 1 d . . . C2 C 0.3386(6) 0.2886(3) 0.2611(3) 0.0188(9) Uani 1 1 d . . . C3 C 0.4459(6) 0.2608(3) 0.2185(3) 0.0212(10) Uani 1 1 d . . . H3 H 0.5453 0.2439 0.2484 0.025 Uiso 1 1 calc R . . C4 C 0.4059(6) 0.2581(3) 0.1328(3) 0.0220(10) Uani 1 1 d . . . H4 H 0.4773 0.2386 0.1032 0.026 Uiso 1 1 calc R . . C5 C 0.2601(6) 0.2838(3) 0.0888(3) 0.0203(9) Uani 1 1 d . . . H5 H 0.2335 0.2797 0.0296 0.024 Uiso 1 1 calc R . . C6 C 0.1535(6) 0.3149(3) 0.1278(3) 0.0174(9) Uani 1 1 d . . . C7 C -0.0018(6) 0.3463(3) 0.0792(3) 0.0173(9) Uani 1 1 d . . . C8 C -0.1704(7) 0.2940(3) 0.0967(3) 0.0260(11) Uani 1 1 d . . . H8A H -0.2679 0.3148 0.0654 0.039 Uiso 1 1 calc R . . H8B H -0.1647 0.2990 0.1565 0.039 Uiso 1 1 calc R . . H8C H -0.1862 0.2347 0.0795 0.039 Uiso 1 1 calc R . . C9 C 0.0210(7) 0.4398(3) 0.1037(3) 0.0236(10) Uani 1 1 d . . . H9A H -0.0787 0.4592 0.0725 0.035 Uiso 1 1 calc R . . H9B H 0.1267 0.4733 0.0906 0.035 Uiso 1 1 calc R . . H9C H 0.0296 0.4465 0.1636 0.035 Uiso 1 1 calc R . . C10 C -0.0179(7) 0.3390(3) -0.0154(3) 0.0245(10) Uani 1 1 d . . . H10A H -0.1177 0.3593 -0.0448 0.037 Uiso 1 1 calc R . . H10B H -0.0336 0.2799 -0.0332 0.037 Uiso 1 1 calc R . . H10C H 0.0874 0.3731 -0.0284 0.037 Uiso 1 1 calc R . . C11 C 0.3755(7) 0.2831(3) 0.3508(3) 0.0222(10) Uani 1 1 d . . . H11 H 0.4773 0.2656 0.3760 0.027 Uiso 1 1 calc R . . C12 C 0.3354(8) 0.2809(3) 0.4898(3) 0.0288(11) Uani 1 1 d . . . C13 C 0.5305(9) 0.2991(4) 0.5244(4) 0.0385(14) Uani 1 1 d . . . H13A H 0.5782 0.2618 0.4950 0.058 Uiso 1 1 calc R . . H13B H 0.5557 0.2893 0.5840 0.058 Uiso 1 1 calc R . . H13C H 0.5830 0.3580 0.5163 0.058 Uiso 1 1 calc R . . C14 C 0.2477(10) 0.1887(4) 0.4989(4) 0.0407(15) Uani 1 1 d . . . H14A H 0.2933 0.1517 0.4681 0.061 Uiso 1 1 calc R . . H14B H 0.1227 0.1791 0.4763 0.061 Uiso 1 1 calc R . . H14C H 0.2710 0.1765 0.5579 0.061 Uiso 1 1 calc R . . C15 C 0.2661(8) 0.3403(4) 0.5371(3) 0.0290(11) Uani 1 1 d . . . H15A H 0.2653 0.3214 0.5939 0.035 Uiso 1 1 calc R . . H15B H 0.3403 0.3983 0.5418 0.035 Uiso 1 1 calc R . . C16 C 0.0047(9) 0.3779(4) 0.5408(4) 0.0399(14) Uani 1 1 d . . . H16A H 0.0121 0.3521 0.5947 0.060 Uiso 1 1 calc R . . H16B H -0.1170 0.3694 0.5114 0.060 Uiso 1 1 calc R . . H16C H 0.0589 0.4384 0.5498 0.060 Uiso 1 1 calc R . . C17 C 0.1763(7) 0.2688(3) -0.1925(3) 0.0201(9) Uani 1 1 d . . . C18 C 0.0042(6) 0.2238(3) -0.2210(3) 0.0196(9) Uani 1 1 d . . . C19 C -0.1236(7) 0.2681(3) -0.2510(3) 0.0214(10) Uani 1 1 d . . . H19 H -0.2416 0.2386 -0.2690 0.026 Uiso 1 1 calc R . . C20 C -0.0760(7) 0.3546(3) -0.2541(3) 0.0210(10) Uani 1 1 d . . . H20 H -0.1607 0.3849 -0.2759 0.025 Uiso 1 1 calc R . . C21 C 0.0978(6) 0.3976(3) -0.2251(3) 0.0194(9) Uani 1 1 d . . . H21 H 0.1277 0.4572 -0.2275 0.023 Uiso 1 1 calc R . . C22 C 0.2287(6) 0.3575(3) -0.1929(3) 0.0175(9) Uani 1 1 d . . . C23 C 0.4174(6) 0.4062(3) -0.1605(3) 0.0187(9) Uani 1 1 d . . . C24 C 0.4366(7) 0.5016(3) -0.1654(4) 0.0262(11) Uani 1 1 d . . . H24A H 0.5583 0.5311 -0.1444 0.039 Uiso 1 1 calc R . . H24B H 0.3669 0.5200 -0.1315 0.039 Uiso 1 1 calc R . . H24C H 0.3969 0.5147 -0.2235 0.039 Uiso 1 1 calc R . . C25 C 0.5312(7) 0.3795(3) -0.2128(4) 0.0280(11) Uani 1 1 d . . . H25A H 0.6516 0.4110 -0.1916 0.042 Uiso 1 1 calc R . . H25B H 0.4909 0.3916 -0.2712 0.042 Uiso 1 1 calc R . . H25C H 0.5237 0.3190 -0.2089 0.042 Uiso 1 1 calc R . . C26 C 0.4834(7) 0.3889(3) -0.0686(3) 0.0250(10) Uani 1 1 d . . . H26A H 0.6041 0.4204 -0.0486 0.038 Uiso 1 1 calc R . . H26B H 0.4756 0.3284 -0.0637 0.038 Uiso 1 1 calc R . . H26C H 0.4126 0.4069 -0.0351 0.038 Uiso 1 1 calc R . . C27 C -0.0501(6) 0.1327(3) -0.2224(3) 0.0201(9) Uani 1 1 d . . . H27 H -0.1708 0.1082 -0.2396 0.024 Uiso 1 1 calc R . . C28 C -0.0356(7) -0.0111(3) -0.2145(3) 0.0222(10) Uani 1 1 d . . . C29 C -0.0609(8) -0.0383(3) -0.3059(3) 0.0317(12) Uani 1 1 d . . . H29A H -0.1409 -0.0093 -0.3411 0.048 Uiso 1 1 calc R . . H29B H -0.1087 -0.0994 -0.3143 0.048 Uiso 1 1 calc R . . H29C H 0.0507 -0.0236 -0.3211 0.048 Uiso 1 1 calc R . . C30 C -0.2062(7) -0.0337(3) -0.1874(4) 0.0308(12) Uani 1 1 d . . . H30A H -0.2892 -0.0062 -0.2224 0.046 Uiso 1 1 calc R . . H30B H -0.1861 -0.0145 -0.1290 0.046 Uiso 1 1 calc R . . H30C H -0.2526 -0.0950 -0.1936 0.046 Uiso 1 1 calc R . . C31 C 0.0888(7) -0.0552(3) -0.1588(3) 0.0226(10) Uani 1 1 d . . . H31A H 0.0792 -0.0511 -0.1004 0.027 Uiso 1 1 calc R . . H31B H 0.0610 -0.1156 -0.1772 0.027 Uiso 1 1 calc R . . C32 C 0.3828(7) -0.0636(3) -0.1289(4) 0.0320(12) Uani 1 1 d . . . H32A H 0.3760 -0.0746 -0.0714 0.048 Uiso 1 1 calc R . . H32B H 0.5003 -0.0323 -0.1295 0.048 Uiso 1 1 calc R . . H32C H 0.3545 -0.1172 -0.1616 0.048 Uiso 1 1 calc R . . C33 C -0.382(3) 0.0559(14) 0.5080(10) 0.078(9) Uiso 0.38(2) 1 d PD A 1 H33A H -0.4667 0.0522 0.5426 0.093 Uiso 0.38(2) 1 calc PR A 1 H33B H -0.3500 0.0011 0.5085 0.093 Uiso 0.38(2) 1 calc PR A 1 C34 C -0.2805(12) 0.0627(6) 0.4611(5) 0.038(3) Uiso 0.62(2) 1 d PD A 2 H34A H -0.1966 0.0746 0.4255 0.045 Uiso 0.62(2) 1 calc PR A 2 H34B H -0.2908 0.0039 0.4777 0.045 Uiso 0.62(2) 1 calc PR A 2 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 0.0220(5) 0.0180(4) 0.0157(4) 0.0018(3) 0.0030(4) 0.0080(3) Ti2 0.0185(5) 0.0123(4) 0.0259(5) 0.0050(3) 0.0007(4) 0.0036(3) Cl1 0.0288(7) 0.0203(6) 0.0345(7) 0.0011(5) 0.0053(6) 0.0037(5) Cl2 0.0250(6) 0.0235(6) 0.0267(6) 0.0021(4) 0.0071(5) 0.0110(4) Cl3 0.0324(7) 0.0180(6) 0.0324(6) 0.0028(5) -0.0036(6) 0.0044(5) Cl4 0.0326(7) 0.0272(6) 0.0237(6) -0.0015(5) 0.0030(5) 0.0094(5) Cl5 0.0197(6) 0.0232(6) 0.0414(7) 0.0046(5) 0.0003(6) 0.0060(4) Cl6 0.0423(9) 0.0455(8) 0.0283(7) 0.0152(6) 0.0101(6) 0.0029(6) Cl7 0.0911(19) 0.0673(14) 0.0654(13) 0.0116(10) 0.0125(13) 0.0241(12) Cl8 0.0749(17) 0.0781(16) 0.0936(19) -0.0006(13) 0.0184(15) 0.0129(13) O1 0.0211(18) 0.0286(18) 0.0191(16) 0.0022(13) 0.0034(15) 0.0132(14) O2 0.030(2) 0.0293(19) 0.0178(16) 0.0020(13) 0.0044(16) 0.0078(15) O3 0.0175(18) 0.0128(16) 0.044(2) 0.0061(14) -0.0043(17) 0.0026(13) O4 0.0222(19) 0.0134(15) 0.0271(17) 0.0039(12) 0.0036(15) 0.0055(12) N1 0.023(2) 0.0204(19) 0.0158(18) 0.0013(14) -0.0034(17) 0.0086(16) N2 0.021(2) 0.0118(18) 0.0194(18) 0.0028(14) 0.0002(17) 0.0017(14) C1 0.018(2) 0.014(2) 0.020(2) 0.0022(16) 0.0047(19) 0.0050(16) C2 0.016(2) 0.015(2) 0.025(2) 0.0005(17) 0.002(2) 0.0041(16) C3 0.016(2) 0.014(2) 0.033(3) 0.0018(18) 0.005(2) 0.0037(16) C4 0.020(2) 0.016(2) 0.034(3) 0.0010(18) 0.014(2) 0.0034(17) C5 0.022(3) 0.014(2) 0.025(2) 0.0020(17) 0.010(2) 0.0019(17) C6 0.016(2) 0.013(2) 0.021(2) 0.0033(16) 0.0042(19) 0.0008(16) C7 0.016(2) 0.018(2) 0.017(2) 0.0041(16) 0.0042(19) 0.0028(17) C8 0.017(3) 0.032(3) 0.025(2) 0.008(2) 0.004(2) 0.0002(19) C9 0.027(3) 0.020(2) 0.025(2) 0.0049(18) 0.004(2) 0.0111(19) C10 0.025(3) 0.029(3) 0.018(2) 0.0035(18) 0.004(2) 0.005(2) C11 0.018(3) 0.017(2) 0.028(2) 0.0013(18) -0.003(2) 0.0059(17) C12 0.034(3) 0.030(3) 0.020(2) 0.0032(19) -0.003(2) 0.011(2) C13 0.037(4) 0.046(3) 0.029(3) -0.002(2) -0.008(3) 0.018(3) C14 0.057(4) 0.030(3) 0.027(3) 0.012(2) -0.004(3) 0.009(3) C15 0.033(3) 0.034(3) 0.017(2) 0.000(2) 0.000(2) 0.010(2) C16 0.047(4) 0.057(4) 0.022(3) -0.002(2) 0.015(3) 0.018(3) C17 0.021(3) 0.014(2) 0.024(2) 0.0051(17) 0.004(2) 0.0055(17) C18 0.020(2) 0.015(2) 0.024(2) 0.0043(17) 0.006(2) 0.0048(17) C19 0.020(2) 0.020(2) 0.026(2) 0.0042(18) 0.006(2) 0.0064(18) C20 0.023(3) 0.020(2) 0.023(2) 0.0057(18) 0.008(2) 0.0103(18) C21 0.025(3) 0.013(2) 0.024(2) 0.0041(16) 0.010(2) 0.0058(17) C22 0.020(2) 0.013(2) 0.019(2) 0.0028(16) 0.0054(19) 0.0024(16) C23 0.018(2) 0.015(2) 0.022(2) 0.0036(17) 0.005(2) 0.0033(17) C24 0.021(3) 0.017(2) 0.036(3) 0.0055(19) 0.002(2) -0.0003(18) C25 0.023(3) 0.026(3) 0.035(3) -0.002(2) 0.011(2) 0.0020(19) C26 0.021(3) 0.026(2) 0.023(2) 0.0056(19) 0.001(2) 0.0000(19) C27 0.015(2) 0.020(2) 0.022(2) 0.0025(17) -0.001(2) 0.0011(17) C28 0.024(3) 0.011(2) 0.029(2) 0.0019(17) 0.002(2) 0.0020(17) C29 0.035(3) 0.027(3) 0.027(3) -0.003(2) -0.004(2) 0.007(2) C30 0.025(3) 0.016(2) 0.047(3) 0.004(2) 0.007(3) 0.0003(19) C31 0.021(3) 0.014(2) 0.030(2) 0.0048(18) 0.003(2) 0.0020(17) C32 0.025(3) 0.020(2) 0.052(3) 0.013(2) 0.007(3) 0.010(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 1.785(3) . ? Ti1 O2 2.122(4) . ? Ti1 N1 2.167(4) . ? Ti1 Cl2 2.2895(15) . ? Ti1 Cl1 2.3291(15) . ? Ti1 Cl3 2.3363(15) . ? Ti2 O3 1.783(3) . ? Ti2 O4 2.124(3) . ? Ti2 N2 2.160(4) . ? Ti2 Cl5 2.2892(16) . ? Ti2 Cl4 2.3234(15) . ? Ti2 Cl6 2.3293(17) . ? Cl7 C33 1.695(15) . ? Cl7 C34 1.772(9) . ? Cl8 C34 1.744(9) . ? Cl8 C33 1.776(15) . ? O1 C1 1.342(6) . ? O2 C15 1.436(7) . ? O2 C16 1.451(7) . ? O3 C17 1.355(6) . ? O4 C31 1.441(6) . ? O4 C32 1.445(6) . ? N1 C11 1.295(7) . ? N1 C12 1.493(6) . ? N2 C27 1.286(6) . ? N2 C28 1.501(6) . ? C1 C6 1.407(6) . ? C1 C2 1.417(7) . ? C2 C3 1.398(7) . ? C2 C11 1.450(7) . ? C3 C4 1.376(7) . ? C3 H3 0.9500 . ? C4 C5 1.403(7) . ? C4 H4 0.9500 . ? C5 C6 1.382(7) . ? C5 H5 0.9500 . ? C6 C7 1.537(7) . ? C7 C8 1.534(6) . ? C7 C9 1.537(6) . ? C7 C10 1.541(6) . ? 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 1.524(9) . ? C12 C15 1.530(8) . ? C12 C14 1.532(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 H15A 0.9900 . ? C15 H15B 0.9900 . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C17 C18 1.398(7) . ? C17 C22 1.412(6) . ? C18 C19 1.408(7) . ? C18 C27 1.449(6) . ? C19 C20 1.381(7) . ? C19 H19 0.9500 . ? C20 C21 1.402(7) . ? C20 H20 0.9500 . ? C21 C22 1.389(7) . ? C21 H21 0.9500 . ? C22 C23 1.532(7) . ? C23 C24 1.533(6) . ? C23 C26 1.540(7) . ? C23 C25 1.541(7) . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C25 H25A 0.9800 . ? C25 H25B 0.9800 . ? C25 H25C 0.9800 . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? C27 H27 0.9500 . ? C28 C31 1.523(7) . ? C28 C29 1.528(7) . ? C28 C30 1.529(7) . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C30 H30A 0.9800 . ? C30 H30B 0.9800 . ? C30 H30C 0.9800 . ? C31 H31A 0.9900 . ? C31 H31B 0.9900 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? C33 H33A 0.9900 . ? C33 H33B 0.9900 . ? C34 H34A 0.9900 . ? C34 H34B 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 158.81(16) . . ? O1 Ti1 N1 84.71(16) . . ? O2 Ti1 N1 74.13(15) . . ? O1 Ti1 Cl2 104.69(12) . . ? O2 Ti1 Cl2 96.49(11) . . ? N1 Ti1 Cl2 170.58(12) . . ? O1 Ti1 Cl1 94.02(13) . . ? O2 Ti1 Cl1 85.59(11) . . ? N1 Ti1 Cl1 86.10(12) . . ? Cl2 Ti1 Cl1 92.38(6) . . ? O1 Ti1 Cl3 91.83(12) . . ? O2 Ti1 Cl3 87.39(11) . . ? N1 Ti1 Cl3 90.15(12) . . ? Cl2 Ti1 Cl3 90.30(6) . . ? Cl1 Ti1 Cl3 172.73(6) . . ? O3 Ti2 O4 158.48(16) . . ? O3 Ti2 N2 84.29(16) . . ? O4 Ti2 N2 74.25(14) . . ? O3 Ti2 Cl5 102.87(12) . . ? O4 Ti2 Cl5 98.63(11) . . ? N2 Ti2 Cl5 172.60(11) . . ? O3 Ti2 Cl4 95.22(14) . . ? O4 Ti2 Cl4 84.68(10) . . ? N2 Ti2 Cl4 85.03(11) . . ? Cl5 Ti2 Cl4 92.40(6) . . ? O3 Ti2 Cl6 93.61(14) . . ? O4 Ti2 Cl6 84.96(11) . . ? N2 Ti2 Cl6 90.05(12) . . ? Cl5 Ti2 Cl6 91.32(6) . . ? Cl4 Ti2 Cl6 169.41(6) . . ? C33 Cl7 C34 42.1(10) . . ? C34 Cl8 C33 41.5(9) . . ? C1 O1 Ti1 143.8(3) . . ? C15 O2 C16 110.9(4) . . ? C15 O2 Ti1 115.8(3) . . ? C16 O2 Ti1 122.8(3) . . ? C17 O3 Ti2 143.5(3) . . ? C31 O4 C32 111.2(4) . . ? C31 O4 Ti2 115.6(3) . . ? C32 O4 Ti2 122.8(3) . . ? C11 N1 C12 118.1(4) . . ? C11 N1 Ti1 124.1(3) . . ? C12 N1 Ti1 117.8(3) . . ? C27 N2 C28 117.3(4) . . ? C27 N2 Ti2 124.8(3) . . ? C28 N2 Ti2 117.9(3) . . ? O1 C1 C6 121.0(4) . . ? O1 C1 C2 117.0(4) . . ? C6 C1 C2 121.9(4) . . ? C3 C2 C1 119.4(5) . . ? C3 C2 C11 117.6(5) . . ? C1 C2 C11 122.9(4) . . ? C4 C3 C2 119.2(5) . . ? C4 C3 H3 120.4 . . ? C2 C3 H3 120.4 . . ? C3 C4 C5 120.4(4) . . ? C3 C4 H4 119.8 . . ? C5 C4 H4 119.8 . . ? C6 C5 C4 122.8(5) . . ? C6 C5 H5 118.6 . . ? C4 C5 H5 118.6 . . ? C5 C6 C1 116.2(5) . . ? C5 C6 C7 122.5(4) . . ? C1 C6 C7 121.3(4) . . ? C8 C7 C6 110.5(4) . . ? C8 C7 C9 109.7(4) . . ? C6 C7 C9 110.1(4) . . ? C8 C7 C10 107.9(4) . . ? C6 C7 C10 111.2(4) . . ? C9 C7 C10 107.4(4) . . ? 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 126.9(5) . . ? N1 C11 H11 116.6 . . ? C2 C11 H11 116.6 . . ? N1 C12 C13 113.4(5) . . ? N1 C12 C15 105.4(4) . . ? C13 C12 C15 107.8(5) . . ? N1 C12 C14 108.0(4) . . ? C13 C12 C14 111.5(5) . . ? C15 C12 C14 110.6(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 . . ? O2 C15 C12 107.7(4) . . ? O2 C15 H15A 110.2 . . ? C12 C15 H15A 110.2 . . ? O2 C15 H15B 110.2 . . ? C12 C15 H15B 110.2 . . ? H15A C15 H15B 108.5 . . ? O2 C16 H16A 109.5 . . ? O2 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? O2 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? O3 C17 C18 117.3(4) . . ? O3 C17 C22 119.9(4) . . ? C18 C17 C22 122.7(4) . . ? C17 C18 C19 119.2(4) . . ? C17 C18 C27 123.0(4) . . ? C19 C18 C27 117.7(4) . . ? C20 C19 C18 119.5(5) . . ? C20 C19 H19 120.3 . . ? C18 C19 H19 120.3 . . ? C19 C20 C21 119.7(4) . . ? C19 C20 H20 120.1 . . ? C21 C20 H20 120.1 . . ? C22 C21 C20 123.3(4) . . ? C22 C21 H21 118.3 . . ? C20 C21 H21 118.3 . . ? C21 C22 C17 115.5(4) . . ? C21 C22 C23 122.2(4) . . ? C17 C22 C23 122.3(4) . . ? C22 C23 C24 111.3(4) . . ? C22 C23 C26 110.2(4) . . ? C24 C23 C26 107.6(4) . . ? C22 C23 C25 110.1(4) . . ? C24 C23 C25 108.3(4) . . ? C26 C23 C25 109.4(4) . . ? C23 C24 H24A 109.5 . . ? C23 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C23 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C23 C25 H25A 109.5 . . ? C23 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? C23 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? C23 C26 H26A 109.5 . . ? C23 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C23 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? N2 C27 C18 126.6(4) . . ? N2 C27 H27 116.7 . . ? C18 C27 H27 116.7 . . ? N2 C28 C31 106.5(4) . . ? N2 C28 C29 108.1(4) . . ? C31 C28 C29 110.3(4) . . ? N2 C28 C30 112.7(4) . . ? C31 C28 C30 107.6(4) . . ? C29 C28 C30 111.5(5) . . ? C28 C29 H29A 109.5 . . ? C28 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C28 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C28 C30 H30A 109.5 . . ? C28 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? C28 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? O4 C31 C28 107.9(4) . . ? O4 C31 H31A 110.1 . . ? C28 C31 H31A 110.1 . . ? O4 C31 H31B 110.1 . . ? C28 C31 H31B 110.1 . . ? H31A C31 H31B 108.4 . . ? O4 C32 H32A 109.5 . . ? O4 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? O4 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? Cl7 C33 Cl8 113.7(11) . . ? Cl7 C33 H33A 108.8 . . ? Cl8 C33 H33A 108.8 . . ? Cl7 C33 H33B 108.8 . . ? Cl8 C33 H33B 108.8 . . ? H33A C33 H33B 107.7 . . ? Cl8 C34 Cl7 111.5(6) . . ? Cl8 C34 H34A 109.3 . . ? Cl7 C34 H34A 109.3 . . ? Cl8 C34 H34B 109.3 . . ? Cl7 C34 H34B 109.3 . . ? H34A C34 H34B 108.0 . . ? 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 3.8(9) . . . . ? N1 Ti1 O1 C1 6.2(5) . . . . ? Cl2 Ti1 O1 C1 -174.5(5) . . . . ? Cl1 Ti1 O1 C1 91.9(5) . . . . ? Cl3 Ti1 O1 C1 -83.7(5) . . . . ? O1 Ti1 O2 C15 27.8(6) . . . . ? N1 Ti1 O2 C15 25.2(3) . . . . ? Cl2 Ti1 O2 C15 -153.8(3) . . . . ? Cl1 Ti1 O2 C15 -61.9(3) . . . . ? Cl3 Ti1 O2 C15 116.1(3) . . . . ? O1 Ti1 O2 C16 169.5(5) . . . . ? N1 Ti1 O2 C16 166.9(5) . . . . ? Cl2 Ti1 O2 C16 -12.2(4) . . . . ? Cl1 Ti1 O2 C16 79.7(4) . . . . ? Cl3 Ti1 O2 C16 -102.2(4) . . . . ? O4 Ti2 O3 C17 -3.1(9) . . . . ? N2 Ti2 O3 C17 -7.4(6) . . . . ? Cl5 Ti2 O3 C17 174.5(6) . . . . ? Cl4 Ti2 O3 C17 -91.9(6) . . . . ? Cl6 Ti2 O3 C17 82.3(6) . . . . ? O3 Ti2 O4 C31 -31.5(6) . . . . ? N2 Ti2 O4 C31 -27.1(3) . . . . ? Cl5 Ti2 O4 C31 150.9(3) . . . . ? Cl4 Ti2 O4 C31 59.2(3) . . . . ? Cl6 Ti2 O4 C31 -118.6(3) . . . . ? O3 Ti2 O4 C32 -173.4(5) . . . . ? N2 Ti2 O4 C32 -169.0(4) . . . . ? Cl5 Ti2 O4 C32 9.0(4) . . . . ? Cl4 Ti2 O4 C32 -82.7(4) . . . . ? Cl6 Ti2 O4 C32 99.5(4) . . . . ? O1 Ti1 N1 C11 2.5(4) . . . . ? O2 Ti1 N1 C11 -178.4(4) . . . . ? Cl2 Ti1 N1 C11 -172.9(5) . . . . ? Cl1 Ti1 N1 C11 -91.9(4) . . . . ? Cl3 Ti1 N1 C11 94.4(4) . . . . ? O1 Ti1 N1 C12 -176.9(4) . . . . ? O2 Ti1 N1 C12 2.2(3) . . . . ? Cl2 Ti1 N1 C12 7.7(10) . . . . ? Cl1 Ti1 N1 C12 88.7(3) . . . . ? Cl3 Ti1 N1 C12 -85.1(3) . . . . ? O3 Ti2 N2 C27 0.1(4) . . . . ? O4 Ti2 N2 C27 -178.2(4) . . . . ? Cl5 Ti2 N2 C27 165.8(7) . . . . ? Cl4 Ti2 N2 C27 95.9(4) . . . . ? Cl6 Ti2 N2 C27 -93.5(4) . . . . ? O3 Ti2 N2 C28 -179.8(4) . . . . ? O4 Ti2 N2 C28 1.8(3) . . . . ? Cl5 Ti2 N2 C28 -14.1(11) . . . . ? Cl4 Ti2 N2 C28 -84.1(3) . . . . ? Cl6 Ti2 N2 C28 86.6(3) . . . . ? Ti1 O1 C1 C6 169.5(4) . . . . ? Ti1 O1 C1 C2 -10.4(8) . . . . ? O1 C1 C2 C3 -178.6(4) . . . . ? C6 C1 C2 C3 1.5(7) . . . . ? O1 C1 C2 C11 5.0(7) . . . . ? C6 C1 C2 C11 -174.9(4) . . . . ? C1 C2 C3 C4 -2.3(7) . . . . ? C11 C2 C3 C4 174.3(4) . . . . ? C2 C3 C4 C5 0.7(7) . . . . ? C3 C4 C5 C6 1.8(7) . . . . ? C4 C5 C6 C1 -2.5(7) . . . . ? C4 C5 C6 C7 177.5(4) . . . . ? O1 C1 C6 C5 -179.0(4) . . . . ? C2 C1 C6 C5 0.8(6) . . . . ? O1 C1 C6 C7 0.9(6) . . . . ? C2 C1 C6 C7 -179.2(4) . . . . ? C5 C6 C7 C8 119.2(5) . . . . ? C1 C6 C7 C8 -60.8(6) . . . . ? C5 C6 C7 C9 -119.5(5) . . . . ? C1 C6 C7 C9 60.6(5) . . . . ? C5 C6 C7 C10 -0.6(6) . . . . ? C1 C6 C7 C10 179.4(4) . . . . ? C12 N1 C11 C2 173.6(4) . . . . ? Ti1 N1 C11 C2 -5.8(7) . . . . ? C3 C2 C11 N1 -174.4(5) . . . . ? C1 C2 C11 N1 2.1(8) . . . . ? C11 N1 C12 C13 37.2(6) . . . . ? Ti1 N1 C12 C13 -143.4(4) . . . . ? C11 N1 C12 C15 154.9(5) . . . . ? Ti1 N1 C12 C15 -25.6(5) . . . . ? C11 N1 C12 C14 -86.9(6) . . . . ? Ti1 N1 C12 C14 92.5(5) . . . . ? C16 O2 C15 C12 167.0(5) . . . . ? Ti1 O2 C15 C12 -47.0(5) . . . . ? N1 C12 C15 O2 43.9(6) . . . . ? C13 C12 C15 O2 165.4(4) . . . . ? C14 C12 C15 O2 -72.5(5) . . . . ? Ti2 O3 C17 C18 9.0(8) . . . . ? Ti2 O3 C17 C22 -171.4(4) . . . . ? O3 C17 C18 C19 179.3(4) . . . . ? C22 C17 C18 C19 -0.3(7) . . . . ? O3 C17 C18 C27 -1.7(7) . . . . ? C22 C17 C18 C27 178.7(4) . . . . ? C17 C18 C19 C20 1.9(7) . . . . ? C27 C18 C19 C20 -177.2(4) . . . . ? C18 C19 C20 C21 -1.9(7) . . . . ? C19 C20 C21 C22 0.3(7) . . . . ? C20 C21 C22 C17 1.2(7) . . . . ? C20 C21 C22 C23 -179.2(4) . . . . ? O3 C17 C22 C21 179.2(4) . . . . ? C18 C17 C22 C21 -1.2(7) . . . . ? O3 C17 C22 C23 -0.4(7) . . . . ? C18 C17 C22 C23 179.2(4) . . . . ? C21 C22 C23 C24 2.4(6) . . . . ? C17 C22 C23 C24 -178.0(4) . . . . ? C21 C22 C23 C26 121.6(5) . . . . ? C17 C22 C23 C26 -58.8(6) . . . . ? C21 C22 C23 C25 -117.7(5) . . . . ? C17 C22 C23 C25 61.9(6) . . . . ? C28 N2 C27 C18 -176.0(5) . . . . ? Ti2 N2 C27 C18 4.1(7) . . . . ? C17 C18 C27 N2 -3.8(8) . . . . ? C19 C18 C27 N2 175.2(5) . . . . ? C27 N2 C28 C31 -159.2(4) . . . . ? Ti2 N2 C28 C31 20.8(5) . . . . ? C27 N2 C28 C29 82.3(5) . . . . ? Ti2 N2 C28 C29 -97.8(4) . . . . ? C27 N2 C28 C30 -41.4(6) . . . . ? Ti2 N2 C28 C30 138.6(4) . . . . ? C32 O4 C31 C28 -167.2(4) . . . . ? Ti2 O4 C31 C28 46.6(5) . . . . ? N2 C28 C31 O4 -40.8(5) . . . . ? C29 C28 C31 O4 76.3(5) . . . . ? C30 C28 C31 O4 -161.9(4) . . . . ? C34 Cl7 C33 Cl8 -55.1(11) . . . . ? C34 Cl8 C33 Cl7 57.4(12) . . . . ? C33 Cl8 C34 Cl7 -52.5(11) . . . . ? C33 Cl7 C34 Cl8 55.2(12) . . . . ? _diffrn_measured_fraction_theta_max 0.881 _diffrn_reflns_theta_full 26.54 _diffrn_measured_fraction_theta_full 0.881 _refine_diff_density_max 2.094 _refine_diff_density_min -2.144 _refine_diff_density_rms 0.144 data_d:\as27jsp3 _database_code_depnum_ccdc_archive 'CCDC 902941' #TrackingRef 'web_deposit_cif_file_2_MichaelGardiner_1348547463.6.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '(C29 H37 Cl4 N O2 Ti), 1.25(C7 H8), (C H2 Cl2)' _chemical_formula_sum 'C38.75 H49 Cl6 N O2 Ti' _chemical_formula_weight 821.39 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 tetragonal _symmetry_space_group_name_H-M 'I -4' _symmetry_space_group_name_Hall 'I -4' _symmetry_Int_Tables_number 82 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'y, -x, -z' '-x, -y, z' '-y, x, -z' 'x+1/2, y+1/2, z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, -z+1/2' _cell_length_a 22.585(2) _cell_length_b 22.585(2) _cell_length_c 16.1750(18) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8250.7(14) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 49830 _cell_measurement_theta_min 1.55 _cell_measurement_theta_max 28.78 _exptl_crystal_description prism _exptl_crystal_colour colourless _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 1.323 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3428 _exptl_absorpt_coefficient_mu 0.629 _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 0.71073 _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 68917 _diffrn_reflns_av_R_equivalents 0.0568 _diffrn_reflns_av_sigmaI/netI 0.0298 _diffrn_reflns_limit_h_min -30 _diffrn_reflns_limit_h_max 30 _diffrn_reflns_limit_k_min -30 _diffrn_reflns_limit_k_max 29 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 1.55 _diffrn_reflns_theta_max 28.78 _reflns_number_total 10587 _reflns_number_gt 9354 _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. DCM and toluene lattice solvent was present. The DCM and one toluene was refined without problem, while a further toluene molecule resided on a high symmetry site and was disordered. This was refined with exensive use of exyz/eadp, free, part and fractional occupancies. The NH proton was positionally refined. ; _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^)+(0.0598P)^2^+9.1523P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.02(3) _refine_ls_number_reflns 10587 _refine_ls_number_parameters 458 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0528 _refine_ls_R_factor_gt 0.0433 _refine_ls_wR_factor_ref 0.1127 _refine_ls_wR_factor_gt 0.1064 _refine_ls_goodness_of_fit_ref 1.058 _refine_ls_restrained_S_all 1.058 _refine_ls_shift/su_max 0.008 _refine_ls_shift/su_mean 0.002 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 0.871063(19) 0.32293(2) 0.89396(3) 0.02383(9) Uani 1 1 d . . . Cl1 Cl 0.78879(3) 0.29914(3) 0.96569(5) 0.03728(16) Uani 1 1 d . . . Cl2 Cl 0.87381(3) 0.32159(3) 0.75372(4) 0.03306(14) Uani 1 1 d . . . Cl3 Cl 0.89576(3) 0.22091(3) 0.88973(5) 0.03209(14) Uani 1 1 d . . . Cl4 Cl 0.84061(3) 0.42061(3) 0.89068(5) 0.03212(14) Uani 1 1 d . . . Cl5 Cl 0.62273(8) 0.75629(5) 0.80017(10) 0.0871(4) Uani 1 1 d . . . Cl6 Cl 0.63373(6) 0.63000(5) 0.82998(8) 0.0678(3) Uani 1 1 d . . . O1 O 0.93812(8) 0.33796(9) 0.94492(11) 0.0255(4) Uani 1 1 d . . . O2 O 1.01214(9) 0.12130(9) 0.87113(15) 0.0355(5) Uani 1 1 d . . . N1 N 1.03023(9) 0.24330(9) 0.81644(13) 0.0212(4) Uani 1 1 d . . . C1 C 0.99560(10) 0.34314(11) 0.96989(16) 0.0219(5) Uani 1 1 d . . . C2 C 1.04043(11) 0.33121(10) 0.91256(14) 0.0199(4) Uani 1 1 d . . . C3 C 1.09941(11) 0.34092(11) 0.93490(15) 0.0223(5) Uani 1 1 d . . . H3 H 1.1299 0.3333 0.8958 0.027 Uiso 1 1 calc R . . C4 C 1.11439(11) 0.36150(11) 1.01339(16) 0.0228(5) Uani 1 1 d . . . C5 C 1.06868(11) 0.37004(11) 1.06942(16) 0.0240(5) Uani 1 1 d . . . H5 H 1.0788 0.3825 1.1237 0.029 Uiso 1 1 calc R . . C6 C 1.00885(11) 0.36157(11) 1.05147(16) 0.0234(5) Uani 1 1 d . . . C7 C 0.96079(11) 0.37196(11) 1.11715(16) 0.0253(5) Uani 1 1 d . . . C8 C 0.98756(13) 0.38632(15) 1.20218(18) 0.0339(6) Uani 1 1 d . . . H8A H 1.0127 0.4215 1.1977 0.051 Uiso 1 1 calc R . . H8B H 1.0113 0.3527 1.2212 0.051 Uiso 1 1 calc R . . H8C H 0.9556 0.3939 1.2418 0.051 Uiso 1 1 calc R . . C9 C 0.92258(13) 0.42566(14) 1.09193(19) 0.0352(6) Uani 1 1 d . . . H9A H 0.9480 0.4605 1.0850 0.053 Uiso 1 1 calc R . . H9B H 0.8932 0.4335 1.1351 0.053 Uiso 1 1 calc R . . H9C H 0.9023 0.4171 1.0397 0.053 Uiso 1 1 calc R . . C10 C 0.92235(13) 0.31702(14) 1.12864(18) 0.0326(6) Uani 1 1 d . . . H10A H 0.9044 0.3061 1.0756 0.049 Uiso 1 1 calc R . . H10B H 0.8911 0.3255 1.1690 0.049 Uiso 1 1 calc R . . H10C H 0.9469 0.2842 1.1487 0.049 Uiso 1 1 calc R . . C11 C 1.17863(12) 0.37532(13) 1.03871(16) 0.0291(5) Uani 1 1 d . . . C12 C 1.19487(13) 0.33947(15) 1.1159(2) 0.0384(6) Uani 1 1 d . . . H12A H 1.1666 0.3482 1.1602 0.058 Uiso 1 1 calc R . . H12B H 1.2349 0.3502 1.1339 0.058 Uiso 1 1 calc R . . H12C H 1.1935 0.2971 1.1028 0.058 Uiso 1 1 calc R . . C13 C 1.22301(12) 0.36083(16) 0.9707(2) 0.0365(6) Uani 1 1 d . . . H13A H 1.2132 0.3834 0.9208 0.055 Uiso 1 1 calc R . . H13B H 1.2214 0.3184 0.9584 0.055 Uiso 1 1 calc R . . H13C H 1.2630 0.3714 0.9892 0.055 Uiso 1 1 calc R . . C14 C 1.18232(14) 0.44227(15) 1.0587(2) 0.0405(7) Uani 1 1 d . . . H14A H 1.1538 0.4520 1.1023 0.061 Uiso 1 1 calc R . . H14B H 1.1731 0.4652 1.0089 0.061 Uiso 1 1 calc R . . H14C H 1.2224 0.4520 1.0775 0.061 Uiso 1 1 calc R . . C15 C 1.02722(10) 0.31092(10) 0.82579(15) 0.0208(4) Uani 1 1 d . . . H15A H 1.0560 0.3293 0.7874 0.025 Uiso 1 1 calc R . . H15B H 0.9872 0.3247 0.8100 0.025 Uiso 1 1 calc R . . C16 C 1.00458(12) 0.22441(12) 0.73505(16) 0.0266(5) Uani 1 1 d . . . H16A H 0.9644 0.2402 0.7296 0.040 Uiso 1 1 calc R . . H16B H 1.0033 0.1811 0.7324 0.040 Uiso 1 1 calc R . . H16C H 1.0293 0.2396 0.6900 0.040 Uiso 1 1 calc R . . C17 C 1.09102(10) 0.22126(10) 0.82976(17) 0.0226(4) Uani 1 1 d . . . C18 C 1.10615(11) 0.19438(11) 0.90458(17) 0.0251(5) Uani 1 1 d . . . C19 C 1.16571(12) 0.18069(12) 0.91716(19) 0.0294(6) Uani 1 1 d . . . H19 H 1.1777 0.1629 0.9677 0.035 Uiso 1 1 calc R . . C20 C 1.20779(12) 0.19273(12) 0.85680(19) 0.0309(6) Uani 1 1 d . . . H20 H 1.2482 0.1837 0.8667 0.037 Uiso 1 1 calc R . . C21 C 1.19116(12) 0.21777(12) 0.78256(19) 0.0294(5) Uani 1 1 d . . . H21 H 1.2199 0.2248 0.7408 0.035 Uiso 1 1 calc R . . C22 C 1.13245(11) 0.23264(11) 0.76904(16) 0.0244(5) Uani 1 1 d . . . H22 H 1.1208 0.2505 0.7184 0.029 Uiso 1 1 calc R . . C23 C 1.06174(12) 0.17888(12) 0.96936(18) 0.0278(5) Uani 1 1 d . . . C24 C 1.01500(12) 0.14025(13) 0.9511(2) 0.0323(6) Uani 1 1 d . . . C25 C 0.97524(13) 0.12379(15) 1.0127(2) 0.0426(8) Uani 1 1 d . . . H25 H 0.9434 0.0978 1.0001 0.051 Uiso 1 1 calc R . . C26 C 0.98199(15) 0.14514(17) 1.0917(2) 0.0490(9) Uani 1 1 d . . . H26 H 0.9547 0.1337 1.1334 0.059 Uiso 1 1 calc R . . C27 C 1.02803(15) 0.18313(16) 1.1113(2) 0.0454(8) Uani 1 1 d . . . H27 H 1.0324 0.1976 1.1662 0.054 Uiso 1 1 calc R . . C28 C 1.06780(14) 0.19991(14) 1.05000(19) 0.0343(6) Uani 1 1 d . . . H28 H 1.0994 0.2260 1.0632 0.041 Uiso 1 1 calc R . . C29 C 0.96597(14) 0.08080(13) 0.8496(3) 0.0460(9) Uani 1 1 d . . . H29A H 0.9275 0.0984 0.8629 0.069 Uiso 1 1 calc R . . H29B H 0.9710 0.0440 0.8808 0.069 Uiso 1 1 calc R . . H29C H 0.9678 0.0723 0.7902 0.069 Uiso 1 1 calc R . . C30 C 0.6676(2) 0.6917(2) 0.7908(5) 0.0878(19) Uani 1 1 d . . . H30A H 0.6768 0.6850 0.7317 0.105 Uiso 1 1 calc R . . H30B H 0.7054 0.6983 0.8203 0.105 Uiso 1 1 calc R . . C31 C 1.09972(18) 0.09839(17) 0.6307(2) 0.0478(8) Uani 1 1 d . . . C32 C 1.0442(2) 0.0720(2) 0.6213(3) 0.0626(12) Uani 1 1 d . . . H32 H 1.0356 0.0362 0.6498 0.075 Uiso 1 1 calc R . . C33 C 1.0023(2) 0.0965(2) 0.5722(3) 0.0711(15) Uani 1 1 d . . . H33 H 0.9650 0.0773 0.5666 0.085 Uiso 1 1 calc R . . H1 H 1.0077(19) 0.2303(18) 0.847(2) 0.046 Uiso 1 1 d . . . C34 C 1.0126(2) 0.1492(2) 0.5295(3) 0.0673(13) Uani 1 1 d . . . H34 H 0.9829 0.1662 0.4955 0.081 Uiso 1 1 calc R . . C35 C 1.0683(2) 0.17616(18) 0.5382(3) 0.0567(10) Uani 1 1 d . . . H35 H 1.0769 0.2121 0.5103 0.068 Uiso 1 1 calc R . . C36 C 1.11015(16) 0.14976(16) 0.5879(2) 0.0432(8) Uani 1 1 d . . . H36 H 1.1479 0.1679 0.5928 0.052 Uiso 1 1 calc R . . C37 C 1.1458(2) 0.0719(2) 0.6843(3) 0.0668(11) Uani 1 1 d . . . H37A H 1.1501 0.0958 0.7345 0.100 Uiso 1 1 calc R . . H37B H 1.1836 0.0709 0.6545 0.100 Uiso 1 1 calc R . . H37C H 1.1342 0.0315 0.6994 0.100 Uiso 1 1 calc R . . C38A C 1.0000 0.5000 0.8824(7) 0.097(3) Uani 0.50 2 d SP A 1 H38A H 1.0026 0.4592 0.9026 0.145 Uiso 0.25 1 calc PR A 1 H38B H 0.9634 0.5182 0.9026 0.145 Uiso 0.25 1 calc PR A 1 H38C H 1.0341 0.5226 0.9026 0.145 Uiso 0.25 1 calc PR A 1 C38B C 1.0000 0.5000 0.8824(7) 0.097(3) Uani 0.50 2 d SP B 2 H38D H 1.0000 0.5000 0.9411 0.116 Uiso 0.50 2 calc SPR B 2 C39 C 1.0000 0.5000 0.7988(7) 0.043(2) Uani 0.50 2 d SP . . C40 C 0.9730(3) 0.4549(3) 0.7540(6) 0.054(2) Uani 0.50 1 d P A . H40 H 0.9538 0.4237 0.7830 0.064 Uiso 0.50 1 calc PR . . C41 C 0.9732(4) 0.4542(5) 0.6725(7) 0.076(3) Uani 0.50 1 d P . . H41 H 0.9545 0.4215 0.6463 0.092 Uiso 0.50 1 calc PR A . 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 0.01913(19) 0.0291(2) 0.02327(19) 0.00017(18) -0.00226(17) 0.00345(16) Cl1 0.0235(3) 0.0371(4) 0.0512(4) 0.0066(3) 0.0080(3) 0.0033(3) Cl2 0.0334(3) 0.0420(4) 0.0238(3) 0.0000(3) -0.0039(3) 0.0126(3) Cl3 0.0311(3) 0.0285(3) 0.0367(3) 0.0045(3) 0.0058(3) 0.0061(2) Cl4 0.0343(3) 0.0279(3) 0.0342(3) 0.0005(3) -0.0075(3) 0.0048(2) Cl5 0.1135(11) 0.0487(6) 0.0991(10) 0.0091(6) -0.0063(8) 0.0054(6) Cl6 0.0814(7) 0.0461(5) 0.0758(7) -0.0014(5) 0.0174(6) -0.0062(5) O1 0.0201(8) 0.0329(9) 0.0233(8) -0.0035(7) -0.0022(7) 0.0039(7) O2 0.0269(9) 0.0257(9) 0.0538(14) 0.0068(9) -0.0035(9) -0.0072(7) N1 0.0212(9) 0.0213(9) 0.0212(10) 0.0006(8) 0.0006(8) -0.0007(7) C1 0.0180(10) 0.0246(11) 0.0232(11) 0.0018(9) -0.0026(9) 0.0011(9) C2 0.0211(10) 0.0182(10) 0.0204(11) 0.0022(8) -0.0006(8) 0.0024(8) C3 0.0200(11) 0.0231(11) 0.0239(12) 0.0020(9) 0.0033(9) 0.0001(9) C4 0.0203(11) 0.0231(11) 0.0250(12) 0.0003(9) -0.0003(9) 0.0018(9) C5 0.0233(11) 0.0266(12) 0.0220(12) -0.0020(9) -0.0024(9) 0.0009(9) C6 0.0212(11) 0.0264(12) 0.0227(11) 0.0006(9) -0.0005(9) 0.0024(9) C7 0.0225(11) 0.0306(12) 0.0227(12) -0.0043(10) 0.0009(9) 0.0036(9) C8 0.0265(12) 0.0505(17) 0.0248(13) -0.0082(12) 0.0021(10) 0.0042(12) C9 0.0322(14) 0.0402(15) 0.0334(15) -0.0087(12) 0.0007(11) 0.0115(12) C10 0.0298(13) 0.0396(15) 0.0285(14) -0.0035(11) 0.0065(10) -0.0038(11) C11 0.0208(12) 0.0377(15) 0.0289(12) -0.0018(11) -0.0015(10) -0.0021(11) C12 0.0281(13) 0.0513(17) 0.0357(15) 0.0059(14) -0.0017(12) -0.0005(12) C13 0.0200(12) 0.0539(19) 0.0357(15) -0.0032(13) -0.0008(11) -0.0028(12) C14 0.0306(14) 0.0395(16) 0.0515(19) -0.0081(14) -0.0022(13) -0.0081(12) C15 0.0207(10) 0.0206(10) 0.0210(10) -0.0002(9) -0.0005(9) 0.0030(8) C16 0.0249(12) 0.0287(12) 0.0261(13) -0.0034(10) -0.0006(10) -0.0020(10) C17 0.0207(10) 0.0181(10) 0.0291(12) 0.0005(9) 0.0007(10) -0.0015(8) C18 0.0224(11) 0.0210(10) 0.0320(14) 0.0048(9) -0.0012(10) -0.0002(9) C19 0.0237(12) 0.0242(12) 0.0402(15) 0.0048(10) -0.0030(10) 0.0007(9) C20 0.0202(12) 0.0276(13) 0.0449(16) 0.0005(11) -0.0004(11) 0.0033(10) C21 0.0225(12) 0.0274(12) 0.0381(15) -0.0012(11) 0.0056(10) 0.0002(10) C22 0.0232(11) 0.0227(11) 0.0274(13) -0.0007(9) 0.0025(9) 0.0009(9) C23 0.0242(12) 0.0238(12) 0.0355(14) 0.0101(10) 0.0008(10) 0.0050(9) C24 0.0245(12) 0.0268(13) 0.0456(16) 0.0134(12) -0.0004(11) 0.0043(10) C25 0.0229(13) 0.0408(16) 0.064(2) 0.0276(16) 0.0053(13) 0.0059(11) C26 0.0346(16) 0.060(2) 0.052(2) 0.0343(18) 0.0162(14) 0.0157(15) C27 0.0472(18) 0.0526(19) 0.0363(15) 0.0147(15) 0.0084(15) 0.0225(15) C28 0.0339(14) 0.0341(14) 0.0350(15) 0.0108(12) 0.0011(12) 0.0086(11) C29 0.0302(15) 0.0250(13) 0.083(3) 0.0032(15) -0.0069(15) -0.0092(11) C30 0.049(3) 0.065(3) 0.150(6) 0.028(3) 0.008(3) -0.004(2) C31 0.057(2) 0.0452(18) 0.0416(18) -0.0127(14) 0.0122(15) -0.0051(16) C32 0.067(3) 0.058(2) 0.063(3) -0.019(2) 0.022(2) -0.028(2) C33 0.048(2) 0.077(3) 0.088(3) -0.045(3) 0.011(2) -0.018(2) C34 0.059(2) 0.077(3) 0.066(3) -0.033(2) -0.016(2) 0.014(2) C35 0.074(3) 0.046(2) 0.050(2) -0.0099(17) 0.004(2) 0.0045(19) C36 0.0425(17) 0.0467(18) 0.0402(17) -0.0126(14) 0.0087(13) -0.0117(14) C37 0.078(3) 0.062(3) 0.060(3) 0.001(2) -0.001(2) -0.004(2) C38A 0.133(8) 0.055(4) 0.103(6) 0.000 0.000 -0.029(5) C38B 0.133(8) 0.055(4) 0.103(6) 0.000 0.000 -0.029(5) C39 0.048(5) 0.029(4) 0.053(6) 0.000 0.000 -0.003(4) C40 0.036(3) 0.028(3) 0.097(7) -0.007(4) -0.001(4) -0.001(2) C41 0.036(4) 0.111(8) 0.083(7) -0.052(6) -0.020(4) 0.029(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Hydrogen bonds with H..A < r(A) + 2.000 Angstroms and 110 deg. D-H d(D-H) d(H..A) _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 7522 _diffrn_reflns_av_R_equivalents 0.0204 _diffrn_reflns_av_unetI/netI 0.0176 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.89 _diffrn_reflns_theta_max 24.00 _reflns_number_total 1945 _reflns_number_gt 1869 _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^)+(0.0229P)^2^+0.6376P] 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 1945 _refine_ls_number_parameters 163 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0290 _refine_ls_R_factor_gt 0.0281 _refine_ls_wR_factor_ref 0.0677 _refine_ls_wR_factor_gt 0.0673 _refine_ls_goodness_of_fit_ref 1.105 _refine_ls_restrained_S_all 1.105 _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 0.5000 0.01324(15) Uani 1 2 d S . . Cl1 Cl 0.23438(6) 0.17932(5) 0.46123(5) 0.01826(15) Uani 1 1 d . . . Cl2 Cl 0.34137(6) 0.07097(5) 0.74874(5) 0.01738(15) Uani 1 1 d . . . O1 O 0.40181(17) -0.15183(14) 0.51500(14) 0.0158(3) Uani 1 1 d . . . O2 O 0.54879(18) -0.30295(15) 0.02968(15) 0.0211(3) Uani 1 1 d . . . N1 N 0.2773(2) -0.20608(18) 0.32112(17) 0.0146(3) Uani 1 1 d . . . H1 H 0.325(3) -0.154(3) 0.343(2) 0.021 Uiso 1 1 d . . . C1 C 0.3591(2) -0.2637(2) 0.5857(2) 0.0140(4) Uani 1 1 d . . . C2 C 0.2780(2) -0.3409(2) 0.5329(2) 0.0143(4) Uani 1 1 d . . . C3 C 0.2317(3) -0.4590(2) 0.6078(2) 0.0183(4) Uani 1 1 d . . . H3 H 0.1760 -0.5103 0.5735 0.022 Uiso 1 1 calc R . . C4 C 0.2655(3) -0.5011(2) 0.7294(2) 0.0201(4) Uani 1 1 d . . . H4 H 0.2346 -0.5813 0.7786 0.024 Uiso 1 1 calc R . . C5 C 0.3461(3) -0.4243(2) 0.7797(2) 0.0191(4) Uani 1 1 d . . . H5 H 0.3695 -0.4530 0.8640 0.023 Uiso 1 1 calc R . . C6 C 0.3926(3) -0.3076(2) 0.7097(2) 0.0175(4) Uani 1 1 d . . . H6 H 0.4474 -0.2571 0.7459 0.021 Uiso 1 1 calc R . . C7 C 0.2407(2) -0.3064(2) 0.4058(2) 0.0145(4) Uani 1 1 d . . . H7 H 0.1830 -0.3633 0.3814 0.017 Uiso 1 1 calc R . . C8 C 0.2281(3) -0.1629(2) 0.1937(2) 0.0163(4) Uani 1 1 d . . . C9 C 0.1653(3) -0.2774(2) 0.1526(2) 0.0193(4) Uani 1 1 d . . . H9A H 0.0538 -0.2798 0.2328 0.029 Uiso 1 1 calc R . . H9B H 0.2675 -0.3792 0.1298 0.029 Uiso 1 1 calc R . . H9C H 0.1341 -0.2468 0.0686 0.029 Uiso 1 1 calc R . . C10 C 0.0706(3) -0.0026(2) 0.2346(2) 0.0206(4) Uani 1 1 d . . . H10A H 0.1151 0.0683 0.2607 0.031 Uiso 1 1 calc R . . H10B H -0.0394 -0.0053 0.3163 0.031 Uiso 1 1 calc R . . H10C H 0.0354 0.0318 0.1529 0.031 Uiso 1 1 calc R . . C11 C 0.4022(3) -0.1553(2) 0.0721(2) 0.0172(4) Uani 1 1 d . . . H11A H 0.3700 -0.1140 -0.0105 0.021 Uiso 1 1 calc R . . H11B H 0.4452 -0.0858 0.1044 0.021 Uiso 1 1 calc R . . C12 C 0.7212(3) -0.2980(2) -0.0709(2) 0.0251(5) Uani 1 1 d . . . H12A H 0.8191 -0.4018 -0.0977 0.038 Uiso 1 1 calc R . . H12B H 0.7600 -0.2347 -0.0277 0.038 Uiso 1 1 calc R . . H12C H 0.7030 -0.2539 -0.1566 0.038 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 0.0175(3) 0.0133(3) 0.0135(3) 0.00318(17) -0.00815(19) -0.00879(19) Cl1 0.0193(2) 0.0181(2) 0.0194(3) 0.00473(18) -0.01017(19) -0.00732(19) Cl2 0.0216(3) 0.0193(3) 0.0137(3) 0.00215(17) -0.00749(18) -0.01001(19) O1 0.0206(7) 0.0154(7) 0.0156(7) 0.0044(5) -0.0084(5) -0.0104(5) O2 0.0195(7) 0.0177(7) 0.0205(8) 0.0038(5) -0.0025(6) -0.0072(6) N1 0.0168(8) 0.0162(8) 0.0139(9) 0.0013(6) -0.0070(6) -0.0085(7) C1 0.0146(9) 0.0111(9) 0.0127(10) 0.0017(7) -0.0028(7) -0.0042(7) C2 0.0127(9) 0.0124(9) 0.0140(10) -0.0010(7) -0.0022(7) -0.0036(7) C3 0.0186(9) 0.0140(9) 0.0205(11) 0.0007(8) -0.0040(8) -0.0081(8) C4 0.0215(10) 0.0142(9) 0.0174(11) 0.0049(7) -0.0016(8) -0.0064(8) C5 0.0231(10) 0.0158(9) 0.0106(10) 0.0017(7) -0.0037(8) -0.0025(8) C6 0.0199(10) 0.0153(9) 0.0147(11) -0.0014(7) -0.0061(8) -0.0045(8) C7 0.0129(9) 0.0132(9) 0.0161(11) -0.0015(7) -0.0038(7) -0.0051(7) C8 0.0195(10) 0.0163(9) 0.0163(11) 0.0028(7) -0.0099(8) -0.0076(8) C9 0.0226(10) 0.0203(10) 0.0192(11) 0.0009(8) -0.0105(8) -0.0102(8) C10 0.0225(10) 0.0174(10) 0.0236(12) 0.0028(8) -0.0119(8) -0.0066(8) C11 0.0220(10) 0.0161(9) 0.0151(11) 0.0048(7) -0.0091(8) -0.0078(8) C12 0.0249(11) 0.0266(11) 0.0211(11) 0.0022(8) -0.0023(9) -0.0139(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 1.8936(12) 2_656 ? Ti1 O1 1.8936(12) . ? Ti1 Cl2 2.3563(5) . ? Ti1 Cl2 2.3563(5) 2_656 ? Ti1 Cl1 2.3768(5) . ? Ti1 Cl1 2.3768(5) 2_656 ? O1 C1 1.331(2) . ? O2 C11 1.416(2) . ? O2 C12 1.425(2) . ? N1 C7 1.288(2) . ? N1 C8 1.491(3) . ? N1 H1 0.84(2) . ? C1 C6 1.397(3) . ? C1 C2 1.419(3) . ? C2 C3 1.411(3) . ? C2 C7 1.431(3) . ? C3 C4 1.371(3) . ? C3 H3 0.9500 . ? C4 C5 1.398(3) . ? C4 H4 0.9500 . ? C5 C6 1.381(3) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C9 1.523(3) . ? C8 C11 1.526(3) . ? C8 C10 1.531(3) . ? 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 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Ti1 O1 180.0 2_656 . ? O1 Ti1 Cl2 88.70(4) 2_656 . ? O1 Ti1 Cl2 91.30(4) . . ? O1 Ti1 Cl2 91.30(4) 2_656 2_656 ? O1 Ti1 Cl2 88.70(4) . 2_656 ? Cl2 Ti1 Cl2 180.000(1) . 2_656 ? O1 Ti1 Cl1 90.52(4) 2_656 . ? O1 Ti1 Cl1 89.48(4) . . ? Cl2 Ti1 Cl1 90.487(17) . . ? Cl2 Ti1 Cl1 89.513(18) 2_656 . ? O1 Ti1 Cl1 89.48(4) 2_656 2_656 ? O1 Ti1 Cl1 90.52(4) . 2_656 ? Cl2 Ti1 Cl1 89.513(17) . 2_656 ? Cl2 Ti1 Cl1 90.487(18) 2_656 2_656 ? Cl1 Ti1 Cl1 180.000(1) . 2_656 ? C1 O1 Ti1 148.68(13) . . ? C11 O2 C12 111.76(14) . . ? C7 N1 C8 126.93(16) . . ? C7 N1 H1 117.2(16) . . ? C8 N1 H1 115.6(16) . . ? O1 C1 C6 122.02(17) . . ? O1 C1 C2 118.87(17) . . ? C6 C1 C2 119.12(17) . . ? C3 C2 C1 119.09(18) . . ? C3 C2 C7 117.35(17) . . ? C1 C2 C7 123.55(17) . . ? C4 C3 C2 121.19(18) . . ? C4 C3 H3 119.4 . . ? C2 C3 H3 119.4 . . ? C3 C4 C5 119.03(18) . . ? C3 C4 H4 120.5 . . ? C5 C4 H4 120.5 . . ? C6 C5 C4 121.5(2) . . ? C6 C5 H5 119.3 . . ? C4 C5 H5 119.3 . . ? C5 C6 C1 120.12(18) . . ? C5 C6 H6 119.9 . . ? C1 C6 H6 119.9 . . ? N1 C7 C2 126.68(17) . . ? N1 C7 H7 116.7 . . ? C2 C7 H7 116.7 . . ? N1 C8 C9 110.96(15) . . ? N1 C8 C11 107.37(15) . . ? C9 C8 C11 111.48(16) . . ? N1 C8 C10 106.50(15) . . ? C9 C8 C10 111.39(15) . . ? C11 C8 C10 108.93(15) . . ? 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 . . ? O2 C11 C8 110.12(15) . . ? O2 C11 H11A 109.6 . . ? C8 C11 H11A 109.6 . . ? O2 C11 H11B 109.6 . . ? C8 C11 H11B 109.6 . . ? H11A C11 H11B 108.2 . . ? O2 C12 H12A 109.5 . . ? O2 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? O2 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? 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 137(100) 2_656 . . . ? Cl2 Ti1 O1 C1 -41.8(2) . . . . ? Cl2 Ti1 O1 C1 138.2(2) 2_656 . . . ? Cl1 Ti1 O1 C1 -132.3(2) . . . . ? Cl1 Ti1 O1 C1 47.7(2) 2_656 . . . ? Ti1 O1 C1 C6 -0.6(3) . . . . ? Ti1 O1 C1 C2 179.75(15) . . . . ? O1 C1 C2 C3 -179.70(16) . . . . ? C6 C1 C2 C3 0.6(3) . . . . ? O1 C1 C2 C7 0.7(3) . . . . ? C6 C1 C2 C7 -179.03(17) . . . . ? C1 C2 C3 C4 -0.7(3) . . . . ? C7 C2 C3 C4 178.95(17) . . . . ? C2 C3 C4 C5 0.5(3) . . . . ? C3 C4 C5 C6 -0.1(3) . . . . ? C4 C5 C6 C1 0.0(3) . . . . ? O1 C1 C6 C5 -179.98(16) . . . . ? C2 C1 C6 C5 -0.3(3) . . . . ? C8 N1 C7 C2 -175.92(17) . . . . ? C3 C2 C7 N1 -178.04(17) . . . . ? C1 C2 C7 N1 1.6(3) . . . . ? C7 N1 C8 C9 -12.8(2) . . . . ? C7 N1 C8 C11 -134.85(18) . . . . ? C7 N1 C8 C10 108.6(2) . . . . ? C12 O2 C11 C8 -172.62(16) . . . . ? N1 C8 C11 O2 66.52(19) . . . . ? C9 C8 C11 O2 -55.2(2) . . . . ? C10 C8 C11 O2 -178.52(15) . . . . ? _diffrn_measured_fraction_theta_max 0.894 _diffrn_reflns_theta_full 24.00 _diffrn_measured_fraction_theta_full 0.894 _refine_diff_density_max 0.234 _refine_diff_density_min -0.282 _refine_diff_density_rms 0.045