# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_global #TrackingRef '- 2012-dalton-cif-merge.cif' _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_email ykim@chungbuk.ac.kr _publ_contact_author_name 'Youngjo Kim' loop_ _publ_author_name 'So Han Kim' 'Da Jung Kim' 'Min Jeong Go' 'Young Soo Ko' 'Junseong Lee' 'Youngjo Kim' #===END data_kyj28-2 _database_code_depnum_ccdc_archive 'CCDC 877504' #TrackingRef '- 2012-dalton-cif-merge.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H26 Cl2 N2 O2 Ti' _chemical_formula_weight 349.15 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 Pna2(1) 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' _cell_length_a 8.5909(12) _cell_length_b 26.375(3) _cell_length_c 7.2737(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1648.1(4) _cell_formula_units_Z 4 _cell_measurement_temperature 130(2) _cell_measurement_reflns_used 1537 _cell_measurement_theta_min 2.50 _cell_measurement_theta_max 23.84 _exptl_crystal_description block _exptl_crystal_colour white _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.407 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 736 _exptl_absorpt_coefficient_mu 0.843 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.91 _exptl_absorpt_correction_T_max 0.96 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 130(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 7584 _diffrn_reflns_av_R_equivalents 0.1357 _diffrn_reflns_av_sigmaI/netI 0.1369 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -31 _diffrn_reflns_limit_k_max 31 _diffrn_reflns_limit_l_min -5 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 2.49 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2027 _reflns_number_gt 1233 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics Diamond _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0305P)^2^+7.7642P] 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 SHELXL _refine_ls_extinction_coef 0.0029(8) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.01(11) _refine_ls_number_reflns 2027 _refine_ls_number_parameters 179 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1333 _refine_ls_R_factor_gt 0.0649 _refine_ls_wR_factor_ref 0.1474 _refine_ls_wR_factor_gt 0.1188 _refine_ls_goodness_of_fit_ref 1.015 _refine_ls_restrained_S_all 1.015 _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 0.7582(2) 0.61292(7) 0.1543(3) 0.0216(4) Uani 1 1 d . . . Cl1 Cl 0.7219(3) 0.52979(9) 0.0299(4) 0.0314(7) Uani 1 1 d . . . Cl2 Cl 1.0065(3) 0.61325(10) 0.0245(4) 0.0322(7) Uani 1 1 d . . . O1 O 0.8006(7) 0.6634(3) 0.3156(9) 0.0202(18) Uani 1 1 d . . . O2 O 0.6510(7) 0.6511(2) -0.0069(9) 0.0194(17) Uani 1 1 d . . . N1 N 0.7808(9) 0.5729(3) 0.4402(11) 0.024(2) Uani 1 1 d . . . N2 N 0.5079(10) 0.6088(3) 0.2560(11) 0.023(2) Uani 1 1 d . . . C1 C 0.8795(11) 0.6617(4) 0.4908(13) 0.023(3) Uani 1 1 d . . . C2 C 0.8335(13) 0.6116(4) 0.5826(13) 0.032(3) Uani 1 1 d . . . H2A H 0.9218 0.5982 0.6500 0.038 Uiso 1 1 calc R . . H2B H 0.7499 0.6176 0.6695 0.038 Uiso 1 1 calc R . . C3 C 0.8906(13) 0.5285(4) 0.4402(16) 0.038(3) Uani 1 1 d . . . H3A H 0.8958 0.5143 0.5616 0.058 Uiso 1 1 calc R . . H3B H 0.9923 0.5396 0.4033 0.058 Uiso 1 1 calc R . . H3C H 0.8537 0.5032 0.3558 0.058 Uiso 1 1 calc R . . C4 C 0.6222(11) 0.5547(4) 0.4901(15) 0.026(3) Uani 1 1 d . . . H4A H 0.6200 0.5451 0.6187 0.032 Uiso 1 1 calc R . . H4B H 0.5962 0.5251 0.4172 0.032 Uiso 1 1 calc R . . C5 C 0.5057(12) 0.5956(4) 0.4561(15) 0.029(3) Uani 1 1 d . . . H5A H 0.5311 0.6253 0.5289 0.035 Uiso 1 1 calc R . . H5B H 0.4027 0.5841 0.4913 0.035 Uiso 1 1 calc R . . C6 C 0.4015(11) 0.5724(4) 0.1559(16) 0.029(3) Uani 1 1 d . . . H6A H 0.4201 0.5385 0.1988 0.044 Uiso 1 1 calc R . . H6B H 0.4218 0.5741 0.0263 0.044 Uiso 1 1 calc R . . H6C H 0.2951 0.5815 0.1791 0.044 Uiso 1 1 calc R . . C7 C 0.4553(12) 0.6627(4) 0.2219(15) 0.023(3) Uani 1 1 d . . . H7A H 0.4971 0.6848 0.3164 0.028 Uiso 1 1 calc R . . H7B H 0.3426 0.6645 0.2270 0.028 Uiso 1 1 calc R . . C8 C 0.5129(11) 0.6804(3) 0.0301(18) 0.024(2) Uani 1 1 d . . . C11 C 0.8219(13) 0.7057(4) 0.6056(14) 0.035(3) Uani 1 1 d . . . H11A H 0.8572 0.7369 0.5524 0.053 Uiso 1 1 calc R . . H11B H 0.8617 0.7027 0.7284 0.053 Uiso 1 1 calc R . . H11C H 0.7102 0.7054 0.6087 0.053 Uiso 1 1 calc R . . C12 C 1.0540(11) 0.6657(5) 0.4643(16) 0.036(3) Uani 1 1 d . . . H12A H 1.0909 0.6365 0.3988 0.054 Uiso 1 1 calc R . . H12B H 1.1041 0.6674 0.5821 0.054 Uiso 1 1 calc R . . H12C H 1.0776 0.6957 0.3952 0.054 Uiso 1 1 calc R . . C81 C 0.3929(12) 0.6724(4) -0.1227(16) 0.029(3) Uani 1 1 d . . . H81A H 0.4324 0.6859 -0.2360 0.044 Uiso 1 1 calc R . . H81B H 0.2979 0.6895 -0.0909 0.044 Uiso 1 1 calc R . . H81C H 0.3729 0.6368 -0.1370 0.044 Uiso 1 1 calc R . . C82 C 0.5555(11) 0.7360(4) 0.0451(17) 0.030(3) Uani 1 1 d . . . H82A H 0.6396 0.7400 0.1308 0.045 Uiso 1 1 calc R . . H82B H 0.4668 0.7549 0.0873 0.045 Uiso 1 1 calc R . . H82C H 0.5869 0.7484 -0.0733 0.045 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 0.0252(10) 0.0271(9) 0.0126(8) -0.0020(12) -0.0008(10) 0.0021(10) Cl1 0.0381(16) 0.0291(15) 0.0269(15) -0.0110(15) -0.0037(17) 0.0038(12) Cl2 0.0271(15) 0.0496(17) 0.0199(14) -0.005(2) 0.0033(14) 0.0054(13) O1 0.028(4) 0.016(4) 0.017(4) 0.003(3) 0.002(4) -0.005(3) O2 0.022(4) 0.027(4) 0.009(4) 0.001(3) -0.003(3) 0.001(3) N1 0.024(5) 0.033(5) 0.014(5) -0.001(4) 0.001(4) 0.000(4) N2 0.033(5) 0.022(5) 0.014(5) -0.004(4) -0.004(5) -0.002(5) C1 0.027(6) 0.034(7) 0.007(6) 0.000(6) -0.011(5) -0.003(5) C2 0.050(7) 0.042(7) 0.004(5) 0.005(6) 0.001(5) -0.018(6) C3 0.048(8) 0.042(8) 0.025(7) 0.002(6) -0.003(6) 0.019(6) C4 0.036(7) 0.035(7) 0.007(6) 0.008(6) -0.002(5) -0.006(5) C5 0.029(6) 0.039(7) 0.019(6) -0.001(5) -0.001(6) -0.010(5) C6 0.023(6) 0.041(7) 0.024(6) 0.002(7) -0.003(6) -0.006(5) C7 0.025(6) 0.022(6) 0.023(6) 0.000(5) 0.003(5) 0.007(5) C8 0.030(6) 0.024(5) 0.017(5) 0.009(6) 0.014(6) 0.001(5) C11 0.046(8) 0.042(8) 0.018(7) 0.003(6) -0.002(5) -0.004(6) C12 0.021(6) 0.067(9) 0.019(7) 0.009(6) 0.005(5) -0.004(6) C81 0.025(7) 0.035(7) 0.028(7) 0.006(6) 0.001(5) 0.008(5) C82 0.025(6) 0.038(6) 0.026(7) 0.008(7) 0.010(6) 0.000(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O2 1.799(7) . ? Ti1 O1 1.812(7) . ? Ti1 N2 2.277(9) . ? Ti1 Cl2 2.333(3) . ? Ti1 N1 2.340(9) . ? Ti1 Cl1 2.393(3) . ? O1 C1 1.444(11) . ? O2 C8 1.441(11) . ? N1 C4 1.489(12) . ? N1 C3 1.505(12) . ? N1 C2 1.522(12) . ? N2 C5 1.496(13) . ? N2 C6 1.512(12) . ? N2 C7 1.513(13) . ? C1 C11 1.513(13) . ? C1 C12 1.516(13) . ? C1 C2 1.532(14) . ? C4 C5 1.492(14) . ? C7 C8 1.552(15) . ? C8 C82 1.516(12) . ? C8 C81 1.530(16) . ? 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 96.5(3) . . ? O2 Ti1 N2 75.8(3) . . ? O1 Ti1 N2 90.8(3) . . ? O2 Ti1 Cl2 101.7(2) . . ? O1 Ti1 Cl2 94.3(2) . . ? N2 Ti1 Cl2 174.5(3) . . ? O2 Ti1 N1 150.9(3) . . ? O1 Ti1 N1 74.9(3) . . ? N2 Ti1 N1 76.6(3) . . ? Cl2 Ti1 N1 106.6(2) . . ? O2 Ti1 Cl1 101.5(2) . . ? O1 Ti1 Cl1 160.9(2) . . ? N2 Ti1 Cl1 87.5(2) . . ? Cl2 Ti1 Cl1 88.25(11) . . ? N1 Ti1 Cl1 86.2(2) . . ? C1 O1 Ti1 129.9(6) . . ? C8 O2 Ti1 126.9(7) . . ? C4 N1 C3 108.8(8) . . ? C4 N1 C2 108.8(8) . . ? C3 N1 C2 109.6(9) . . ? C4 N1 Ti1 106.6(6) . . ? C3 N1 Ti1 113.8(6) . . ? C2 N1 Ti1 109.1(5) . . ? C5 N2 C6 108.3(8) . . ? C5 N2 C7 112.0(8) . . ? C6 N2 C7 109.7(8) . . ? C5 N2 Ti1 109.8(6) . . ? C6 N2 Ti1 116.4(6) . . ? C7 N2 Ti1 100.6(6) . . ? O1 C1 C11 108.0(8) . . ? O1 C1 C12 110.5(8) . . ? C11 C1 C12 109.9(9) . . ? O1 C1 C2 106.9(8) . . ? C11 C1 C2 109.7(9) . . ? C12 C1 C2 111.8(9) . . ? N1 C2 C1 111.0(8) . . ? N1 C4 C5 109.9(8) . . ? C4 C5 N2 108.7(9) . . ? N2 C7 C8 109.6(8) . . ? O2 C8 C82 109.5(7) . . ? O2 C8 C81 110.2(9) . . ? C82 C8 C81 110.4(9) . . ? O2 C8 C7 105.6(8) . . ? C82 C8 C7 107.6(10) . . ? C81 C8 C7 113.3(8) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.626 _refine_diff_density_min -0.624 _refine_diff_density_rms 0.124 data_kyj24-p-1 _database_code_depnum_ccdc_archive 'CCDC 888924' #TrackingRef '- 2012-dalton-cif-merge.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H40 N2 O4 Ti' _chemical_formula_weight 396.42 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.1651(4) _cell_length_b 9.2522(3) _cell_length_c 15.1186(6) _cell_angle_alpha 105.316(2) _cell_angle_beta 97.911(2) _cell_angle_gamma 109.093(2) _cell_volume 1132.61(8) _cell_formula_units_Z 2 _cell_measurement_temperature 130(2) _cell_measurement_reflns_used 9990 _cell_measurement_theta_min 1.44 _cell_measurement_theta_max 34.47 _exptl_crystal_description block _exptl_crystal_colour white _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.162 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 432 _exptl_absorpt_coefficient_mu 0.399 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.90 _exptl_absorpt_correction_T_max 0.95 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 130(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 32384 _diffrn_reflns_av_R_equivalents 0.0270 _diffrn_reflns_av_sigmaI/netI 0.0286 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.44 _diffrn_reflns_theta_max 34.47 _reflns_number_total 8432 _reflns_number_gt 7204 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics Diamond _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0469P)^2^+0.1791P] 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 8432 _refine_ls_number_parameters 236 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0383 _refine_ls_R_factor_gt 0.0305 _refine_ls_wR_factor_ref 0.0897 _refine_ls_wR_factor_gt 0.0853 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 1.026 _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 0.743288(17) 0.467841(18) 0.257090(10) 0.01798(5) Uani 1 1 d . . . O1 O 0.83505(7) 0.57505(8) 0.17467(4) 0.02053(12) Uani 1 1 d . . . O2 O 0.70163(8) 0.32737(8) 0.33024(5) 0.02339(13) Uani 1 1 d . . . O3 O 0.76526(8) 0.64382(8) 0.35635(5) 0.02355(13) Uani 1 1 d . . . O4 O 0.54151(8) 0.39519(9) 0.18192(5) 0.02554(13) Uani 1 1 d . . . N1 N 1.01435(9) 0.52999(10) 0.30118(5) 0.02237(14) Uani 1 1 d . . . N2 N 0.76917(10) 0.23276(10) 0.17147(6) 0.02535(15) Uani 1 1 d . . . C1 C 0.98586(10) 0.70192(11) 0.20226(6) 0.02017(15) Uani 1 1 d . . . C11 C 0.96442(13) 0.86376(12) 0.22987(8) 0.0299(2) Uani 1 1 d . . . H11A H 0.9029 0.8728 0.1746 0.045 Uiso 1 1 calc R . . H11B H 1.0691 0.9529 0.2525 0.045 Uiso 1 1 calc R . . H11C H 0.9075 0.8693 0.2802 0.045 Uiso 1 1 calc R . . C12 C 1.06474(12) 0.69125(13) 0.11891(7) 0.02721(18) Uani 1 1 d . . . H12A H 1.0776 0.5873 0.0996 0.041 Uiso 1 1 calc R . . H12B H 1.1694 0.7800 0.1382 0.041 Uiso 1 1 calc R . . H12C H 0.9976 0.6997 0.0657 0.041 Uiso 1 1 calc R . . C2 C 1.08606(11) 0.69159(11) 0.29114(7) 0.02348(16) Uani 1 1 d . . . H2A H 1.1964 0.7112 0.2848 0.028 Uiso 1 1 calc R . . H2B H 1.0904 0.7764 0.3485 0.028 Uiso 1 1 calc R . . C3 C 1.07175(13) 0.53886(15) 0.39959(8) 0.0335(2) Uani 1 1 d . . . H3A H 1.0262 0.4312 0.4055 0.050 Uiso 1 1 calc R . . H3B H 1.0389 0.6147 0.4428 0.050 Uiso 1 1 calc R . . H3C H 1.1882 0.5766 0.4156 0.050 Uiso 1 1 calc R . . C4 C 1.05342(12) 0.40806(13) 0.23395(8) 0.0294(2) Uani 1 1 d . . . H4A H 1.1592 0.4112 0.2617 0.035 Uiso 1 1 calc R . . H4B H 1.0583 0.4341 0.1747 0.035 Uiso 1 1 calc R . . C5 C 0.92898(13) 0.24011(13) 0.21205(9) 0.0320(2) Uani 1 1 d . . . H5A H 0.9560 0.1602 0.1665 0.038 Uiso 1 1 calc R . . H5B H 0.9282 0.2118 0.2708 0.038 Uiso 1 1 calc R . . C6 C 0.74506(16) 0.20762(14) 0.06910(7) 0.0363(2) Uani 1 1 d . . . H6A H 0.8269 0.2966 0.0588 0.055 Uiso 1 1 calc R . . H6B H 0.6395 0.2049 0.0439 0.055 Uiso 1 1 calc R . . H6C H 0.7528 0.1047 0.0367 0.055 Uiso 1 1 calc R . . C7 C 0.64288(13) 0.10216(12) 0.18840(7) 0.0300(2) Uani 1 1 d . . . H7A H 0.6695 0.0045 0.1770 0.036 Uiso 1 1 calc R . . H7B H 0.5403 0.0736 0.1436 0.036 Uiso 1 1 calc R . . C8 C 0.62563(12) 0.15717(12) 0.29211(7) 0.02690(18) Uani 1 1 d . . . C81 C 0.69677(16) 0.07991(14) 0.35546(9) 0.0382(2) Uani 1 1 d . . . H81A H 0.8116 0.1140 0.3604 0.057 Uiso 1 1 calc R . . H81B H 0.6459 -0.0384 0.3279 0.057 Uiso 1 1 calc R . . H81C H 0.6783 0.1147 0.4186 0.057 Uiso 1 1 calc R . . C82 C 0.44806(14) 0.10881(16) 0.28904(9) 0.0411(3) Uani 1 1 d . . . H82A H 0.4344 0.1379 0.3537 0.062 Uiso 1 1 calc R . . H82B H 0.3929 -0.0084 0.2576 0.062 Uiso 1 1 calc R . . H82C H 0.4032 0.1659 0.2539 0.062 Uiso 1 1 calc R . . C31 C 0.71383(11) 0.65794(12) 0.44152(6) 0.02488(17) Uani 1 1 d . . . H31 H 0.7255 0.5708 0.4659 0.030 Uiso 1 1 calc R . . C32 C 0.81880(15) 0.82107(16) 0.51419(8) 0.0422(3) Uani 1 1 d . . . H32A H 0.9307 0.8342 0.5211 0.063 Uiso 1 1 calc R . . H32B H 0.7915 0.8272 0.5752 0.063 Uiso 1 1 calc R . . H32C H 0.8021 0.9074 0.4933 0.063 Uiso 1 1 calc R . . C33 C 0.53981(13) 0.63598(16) 0.42208(8) 0.0354(2) Uani 1 1 d . . . H33A H 0.5271 0.7217 0.3990 0.053 Uiso 1 1 calc R . . H33B H 0.5037 0.6419 0.4805 0.053 Uiso 1 1 calc R . . H33C H 0.4761 0.5301 0.3741 0.053 Uiso 1 1 calc R . . C41 C 0.47771(11) 0.44188(13) 0.10827(7) 0.02716(18) Uani 1 1 d . . . H41 H 0.5540 0.4578 0.0671 0.033 Uiso 1 1 calc R . . C42 C 0.45877(15) 0.60100(15) 0.14975(9) 0.0381(2) Uani 1 1 d . . . H42A H 0.3861 0.5880 0.1915 0.057 Uiso 1 1 calc R . . H42B H 0.4151 0.6329 0.0985 0.057 Uiso 1 1 calc R . . H42C H 0.5628 0.6849 0.1861 0.057 Uiso 1 1 calc R . . C43 C 0.32140(15) 0.30807(17) 0.04898(9) 0.0461(3) Uani 1 1 d . . . H43A H 0.3388 0.2078 0.0232 0.069 Uiso 1 1 calc R . . H43B H 0.2789 0.3388 -0.0031 0.069 Uiso 1 1 calc R . . H43C H 0.2452 0.2909 0.0884 0.069 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 0.01757(7) 0.01885(7) 0.01825(7) 0.00672(5) 0.00498(5) 0.00716(5) O1 0.0188(3) 0.0217(3) 0.0204(3) 0.0085(2) 0.0038(2) 0.0061(2) O2 0.0267(3) 0.0208(3) 0.0226(3) 0.0084(2) 0.0076(2) 0.0073(2) O3 0.0263(3) 0.0233(3) 0.0215(3) 0.0063(2) 0.0094(2) 0.0095(3) O4 0.0200(3) 0.0297(3) 0.0257(3) 0.0114(3) 0.0026(2) 0.0073(3) N1 0.0208(3) 0.0278(4) 0.0231(3) 0.0129(3) 0.0062(3) 0.0111(3) N2 0.0312(4) 0.0222(4) 0.0258(4) 0.0091(3) 0.0118(3) 0.0111(3) C1 0.0197(4) 0.0204(4) 0.0205(4) 0.0079(3) 0.0051(3) 0.0069(3) C11 0.0345(5) 0.0213(4) 0.0338(5) 0.0086(4) 0.0056(4) 0.0122(4) C12 0.0255(4) 0.0328(5) 0.0249(4) 0.0127(4) 0.0096(3) 0.0091(4) C2 0.0199(4) 0.0254(4) 0.0236(4) 0.0096(3) 0.0031(3) 0.0063(3) C3 0.0271(5) 0.0494(6) 0.0293(5) 0.0229(5) 0.0036(4) 0.0146(4) C4 0.0284(5) 0.0318(5) 0.0402(5) 0.0184(4) 0.0165(4) 0.0184(4) C5 0.0361(5) 0.0289(5) 0.0450(6) 0.0191(4) 0.0194(4) 0.0205(4) C6 0.0552(7) 0.0295(5) 0.0258(5) 0.0067(4) 0.0177(5) 0.0168(5) C7 0.0371(5) 0.0205(4) 0.0295(5) 0.0073(4) 0.0111(4) 0.0070(4) C8 0.0298(5) 0.0215(4) 0.0274(4) 0.0093(3) 0.0090(4) 0.0055(3) C81 0.0537(7) 0.0288(5) 0.0380(6) 0.0189(5) 0.0140(5) 0.0156(5) C82 0.0303(5) 0.0400(6) 0.0424(6) 0.0103(5) 0.0131(5) 0.0011(5) C31 0.0256(4) 0.0296(4) 0.0203(4) 0.0078(3) 0.0077(3) 0.0112(4) C32 0.0356(6) 0.0451(7) 0.0287(5) -0.0055(5) 0.0059(4) 0.0087(5) C33 0.0264(5) 0.0466(6) 0.0342(5) 0.0115(5) 0.0123(4) 0.0145(4) C41 0.0230(4) 0.0353(5) 0.0236(4) 0.0105(4) 0.0028(3) 0.0121(4) C42 0.0398(6) 0.0444(6) 0.0409(6) 0.0184(5) 0.0111(5) 0.0255(5) C43 0.0329(6) 0.0506(7) 0.0390(6) 0.0074(6) -0.0086(5) 0.0089(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O3 1.8317(7) . ? Ti1 O4 1.8352(7) . ? Ti1 O2 1.8996(7) . ? Ti1 O1 1.9078(6) . ? Ti1 N1 2.3138(8) . ? Ti1 N2 2.3232(8) . ? O1 C1 1.4084(11) . ? O2 C8 1.4105(11) . ? O3 C31 1.4198(11) . ? O4 C41 1.4172(11) . ? N1 C3 1.4796(12) . ? N1 C4 1.4808(12) . ? N1 C2 1.4815(12) . ? N2 C5 1.4805(13) . ? N2 C6 1.4766(13) . ? N2 C7 1.4817(13) . ? C1 C11 1.5297(13) . ? C1 C12 1.5336(13) . ? C1 C2 1.5633(12) . ? C4 C5 1.5132(15) . ? C7 C8 1.5626(14) . ? C8 C82 1.5306(16) . ? C8 C81 1.5324(15) . ? C31 C32 1.5145(15) . ? C31 C33 1.5162(14) . ? C41 C43 1.5128(16) . ? C41 C42 1.5167(15) . ? 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 O3 Ti1 O4 106.85(3) . . ? O3 Ti1 O2 92.58(3) . . ? O4 Ti1 O2 98.57(3) . . ? O3 Ti1 O1 99.81(3) . . ? O4 Ti1 O1 92.13(3) . . ? O2 Ti1 O1 160.58(3) . . ? O3 Ti1 N1 89.60(3) . . ? O4 Ti1 N1 160.18(3) . . ? O2 Ti1 N1 91.47(3) . . ? O1 Ti1 N1 73.84(3) . . ? O3 Ti1 N2 160.59(3) . . ? O4 Ti1 N2 89.25(3) . . ? O2 Ti1 N2 73.94(3) . . ? O1 Ti1 N2 90.13(3) . . ? N1 Ti1 N2 77.11(3) . . ? C1 O1 Ti1 123.97(5) . . ? C8 O2 Ti1 124.57(6) . . ? C31 O3 Ti1 132.25(6) . . ? C41 O4 Ti1 132.18(6) . . ? C3 N1 C4 110.47(8) . . ? C3 N1 C2 109.73(8) . . ? C4 N1 C2 110.66(7) . . ? C3 N1 Ti1 113.82(6) . . ? C4 N1 Ti1 108.38(6) . . ? C2 N1 Ti1 103.57(5) . . ? C5 N2 C6 110.80(8) . . ? C5 N2 C7 110.78(8) . . ? C6 N2 C7 110.10(8) . . ? C5 N2 Ti1 107.93(6) . . ? C6 N2 Ti1 113.36(6) . . ? C7 N2 Ti1 103.64(6) . . ? O1 C1 C11 108.85(7) . . ? O1 C1 C12 109.60(7) . . ? C11 C1 C12 108.46(8) . . ? O1 C1 C2 108.37(7) . . ? C11 C1 C2 108.43(8) . . ? C12 C1 C2 113.06(7) . . ? N1 C2 C1 110.44(7) . . ? N1 C4 C5 110.46(8) . . ? N2 C5 C4 110.61(8) . . ? N2 C7 C8 110.77(8) . . ? O2 C8 C82 109.03(9) . . ? O2 C8 C81 109.61(8) . . ? C82 C8 C81 108.59(9) . . ? O2 C8 C7 108.33(8) . . ? C82 C8 C7 108.18(9) . . ? C81 C8 C7 113.03(9) . . ? O3 C31 C32 108.99(9) . . ? O3 C31 C33 109.72(8) . . ? C32 C31 C33 111.90(9) . . ? O4 C41 C43 109.43(9) . . ? O4 C41 C42 109.87(8) . . ? C43 C41 C42 112.03(9) . . ? _diffrn_measured_fraction_theta_max 0.881 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.401 _refine_diff_density_min -0.404 _refine_diff_density_rms 0.045