Supplementary Material (ESI) for Journal of Materials Chemistry This journal is © The Royal Society of Chemistry 2001 data_global _journal_coden_Cambridge 1145 _publ_requested_journal 'Journal of Materials Chemistry' loop_ _publ_author_name 'Awaludiin, Amir' 'Bickley, Jamie F.' 'Critchlow, Gary W.' 'Davies, Hywel O.' 'Jones, Anthony C.' 'Leedham, Timothy J.' 'Pemble, M.' 'Steiner, Alexander' 'Williams, Paul A.' _publ_contact_author_name 'Prof Anthony C Jones' _publ_contact_author_address ; Prof Anthony C Jones Department of Chemistry University of Liverpool Liverpool L69 7ZD UNITED KINGDOM ; data_tony27 _database_code_CSD 158131 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H48 N4 O8 Ti2' _chemical_formula_weight 568.52 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0020 0.0020 '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' 0.0080 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0040 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ti' 'Ti' 0.2480 0.4460 '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 8.2993(17) _cell_length_b 9.3651(19) _cell_length_c 9.7070(19) _cell_angle_alpha 104.70(2) _cell_angle_beta 104.99(2) _cell_angle_gamma 96.58(2) _cell_volume 691.7(2) _cell_formula_units_Z 1 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.365 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 304 _exptl_absorpt_coefficient_mu 0.624 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 213(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 'Stoe IPDS' _diffrn_measurement_method 'Image plate' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3807 _diffrn_reflns_av_R_equivalents 0.0478 _diffrn_reflns_av_sigmaI/netI 0.0652 _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 -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.29 _diffrn_reflns_theta_max 24.16 _reflns_number_total 2063 _reflns_number_gt 1548 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'IPDS (STOE, 1997)' _computing_cell_refinement ? _computing_data_reduction 'X-RED (STOE, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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 w=1/[\s^2^(Fo^2^)+(0.0429P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2063 _refine_ls_number_parameters 154 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0516 _refine_ls_R_factor_gt 0.0355 _refine_ls_wR_factor_ref 0.0833 _refine_ls_wR_factor_gt 0.0799 _refine_ls_goodness_of_fit_ref 0.913 _refine_ls_restrained_S_all 0.913 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.7040(4) 0.5274(3) 0.4549(3) 0.0300(7) Uani 1 d . . . H1A H 0.6791 0.5368 0.5498 0.036 Uiso 1 calc R . . H1B H 0.8224 0.5763 0.4763 0.036 Uiso 1 calc R . . C2 C 0.6769(4) 0.3638(3) 0.3686(3) 0.0304(7) Uani 1 d . . . H2A H 0.7719 0.3197 0.4119 0.036 Uiso 1 calc R . . H2B H 0.5720 0.3087 0.3738 0.036 Uiso 1 calc R . . C3 C 0.8348(4) 0.4036(4) 0.1998(4) 0.0346(8) Uani 1 d . . . H3A H 0.8263 0.3953 0.0964 0.042 Uiso 1 calc R . . H3B H 0.9126 0.3420 0.2355 0.042 Uiso 1 calc R . . H3C H 0.8769 0.5078 0.2598 0.042 Uiso 1 calc R . . C4 C 0.6049(4) 0.1931(3) 0.1212(4) 0.0374(8) Uani 1 d . . . H4A H 0.5971 0.1844 0.0178 0.045 Uiso 1 calc R . . H4B H 0.4938 0.1571 0.1280 0.045 Uiso 1 calc R . . H4C H 0.6842 0.1332 0.1581 0.045 Uiso 1 calc R . . C5 C 0.2746(4) 0.7403(3) 0.2750(3) 0.0277(7) Uani 1 d . . . H5A H 0.3469 0.7543 0.3766 0.033 Uiso 1 calc R . . H5B H 0.1671 0.6738 0.2590 0.033 Uiso 1 calc R . . C6 C 0.2412(4) 0.8903(3) 0.2561(3) 0.0270(7) Uani 1 d . . . H6A H 0.3499 0.9579 0.2784 0.032 Uiso 1 calc R . . H6B H 0.1772 0.8761 0.1519 0.032 Uiso 1 calc R . . C7 C 0.2523(5) 1.0200(3) 0.5078(4) 0.0446(9) Uani 1 d . . . H7A H 0.1857 1.0654 0.5694 0.054 Uiso 1 calc R . . H7B H 0.3468 1.0954 0.5146 0.054 Uiso 1 calc R . . H7C H 0.2953 0.9391 0.5421 0.054 Uiso 1 calc R . . C8 C 0.0784(5) 1.0813(3) 0.3046(4) 0.0461(9) Uani 1 d . . . H8A H 0.0153 1.1268 0.3698 0.055 Uiso 1 calc R . . H8B H 0.0034 1.0417 0.2031 0.055 Uiso 1 calc R . . H8C H 0.1714 1.1566 0.3085 0.055 Uiso 1 calc R . . C9 C 0.1745(4) 0.2998(4) 0.0327(4) 0.0371(8) Uani 1 d . . . H9A H 0.0899 0.3637 0.0177 0.044 Uiso 1 calc R . . H9B H 0.1178 0.2040 0.0370 0.044 Uiso 1 calc R . . C10 C 0.2510(4) 0.2723(3) -0.0951(3) 0.0279(7) Uani 1 d . . . H10A H 0.3003 0.1814 -0.1037 0.033 Uiso 1 calc R . . H10B H 0.1649 0.2612 -0.1898 0.033 Uiso 1 calc R . . O1 O 0.5927(2) 0.59590(19) 0.3658(2) 0.0260(5) Uani 1 d . . . O2 O 0.3561(3) 0.6747(2) 0.1707(2) 0.0310(5) Uani 1 d . . . O3 O 0.3063(2) 0.3714(2) 0.1677(2) 0.0296(5) Uani 1 d . . . O4 O 0.3797(2) 0.40298(18) -0.0572(2) 0.0211(4) Uani 1 d . . . N1 N 0.6651(3) 0.3516(2) 0.2115(3) 0.0243(6) Uani 1 d . . . N2 N 0.1457(3) 0.9600(2) 0.3532(3) 0.0305(6) Uani 1 d . . . Ti1 Ti 0.47410(6) 0.52137(5) 0.16656(6) 0.02046(16) Uani 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0311(16) 0.0438(17) 0.017(2) 0.0105(14) 0.0062(14) 0.0121(14) C2 0.0326(17) 0.0408(16) 0.027(2) 0.0184(15) 0.0127(15) 0.0169(14) C3 0.0261(16) 0.0526(19) 0.036(2) 0.0195(16) 0.0152(15) 0.0203(15) C4 0.047(2) 0.0323(16) 0.034(2) 0.0077(14) 0.0117(16) 0.0175(15) C5 0.0315(16) 0.0318(15) 0.023(2) 0.0048(13) 0.0152(14) 0.0112(13) C6 0.0280(15) 0.0306(15) 0.024(2) 0.0041(13) 0.0120(14) 0.0089(13) C7 0.058(2) 0.0358(17) 0.040(3) 0.0008(15) 0.0218(19) 0.0141(16) C8 0.048(2) 0.0352(17) 0.058(3) 0.0108(17) 0.0180(19) 0.0201(16) C9 0.0313(17) 0.0504(18) 0.028(2) 0.0111(15) 0.0114(15) -0.0051(15) C10 0.0268(16) 0.0285(15) 0.025(2) 0.0056(13) 0.0077(14) -0.0039(12) O1 0.0308(11) 0.0294(10) 0.0182(13) 0.0060(9) 0.0081(9) 0.0079(9) O2 0.0403(12) 0.0400(11) 0.0200(14) 0.0070(9) 0.0165(10) 0.0229(10) O3 0.0277(11) 0.0430(11) 0.0182(13) 0.0090(9) 0.0106(9) -0.0009(9) O4 0.0208(10) 0.0243(9) 0.0177(12) 0.0036(8) 0.0085(8) 0.0016(8) N1 0.0257(13) 0.0301(12) 0.0222(16) 0.0093(10) 0.0119(11) 0.0108(10) N2 0.0301(14) 0.0277(12) 0.0348(19) 0.0036(11) 0.0147(13) 0.0113(11) Ti1 0.0217(3) 0.0259(3) 0.0165(3) 0.0054(2) 0.0096(2) 0.0080(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 C1 O1 1.420(3) . ? C1 C2 1.507(4) . ? C2 N1 1.476(4) . ? C3 N1 1.479(3) . ? C4 N1 1.471(4) . ? C5 O2 1.411(3) . ? C5 C6 1.510(4) . ? C6 N2 1.462(3) . ? C7 N2 1.456(4) . ? C8 N2 1.451(4) . ? C9 O3 1.417(4) . ? C9 C10 1.514(4) . ? C10 O4 1.429(3) . ? O1 Ti1 1.836(2) . ? O2 Ti1 1.8263(18) . ? O3 Ti1 1.8653(19) . ? O4 Ti1 1.9880(17) 2_665 ? O4 Ti1 2.064(2) . ? N1 Ti1 2.409(2) . ? Ti1 O4 1.9880(17) 2_665 ? 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 C1 C2 107.6(3) . . ? N1 C2 C1 109.1(2) . . ? O2 C5 C6 109.2(2) . . ? N2 C6 C5 112.3(2) . . ? O3 C9 C10 108.7(2) . . ? O4 C10 C9 104.5(2) . . ? C1 O1 Ti1 128.19(18) . . ? C5 O2 Ti1 129.90(17) . . ? C9 O3 Ti1 117.81(16) . . ? C10 O4 Ti1 133.53(16) . 2_665 ? C10 O4 Ti1 116.04(15) . . ? Ti1 O4 Ti1 109.14(8) 2_665 . ? C4 N1 C2 109.2(2) . . ? C4 N1 C3 108.5(2) . . ? C2 N1 C3 109.8(2) . . ? C4 N1 Ti1 116.68(18) . . ? C2 N1 Ti1 99.73(16) . . ? C3 N1 Ti1 112.52(16) . . ? C8 N2 C7 108.9(2) . . ? C8 N2 C6 110.1(2) . . ? C7 N2 C6 111.3(2) . . ? O2 Ti1 O1 93.42(9) . . ? O2 Ti1 O3 99.34(9) . . ? O1 Ti1 O3 101.43(9) . . ? O2 Ti1 O4 93.74(8) . 2_665 ? O1 Ti1 O4 106.52(9) . 2_665 ? O3 Ti1 O4 148.28(9) . 2_665 ? O2 Ti1 O4 99.88(9) . . ? O1 Ti1 O4 166.56(8) . . ? O3 Ti1 O4 78.46(8) . . ? O4 Ti1 O4 70.86(8) 2_665 . ? O2 Ti1 N1 168.15(9) . . ? O1 Ti1 N1 74.98(8) . . ? O3 Ti1 N1 85.61(8) . . ? O4 Ti1 N1 87.38(7) 2_665 . ? O4 Ti1 N1 91.64(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 C1 C2 N1 43.3(3) . . . . ? O2 C5 C6 N2 175.8(2) . . . . ? O3 C9 C10 O4 -38.1(3) . . . . ? C2 C1 O1 Ti1 -14.0(3) . . . . ? C6 C5 O2 Ti1 163.2(2) . . . . ? C10 C9 O3 Ti1 40.9(3) . . . . ? C9 C10 O4 Ti1 -171.40(19) . . . 2_665 ? C9 C10 O4 Ti1 23.2(3) . . . . ? C1 C2 N1 C4 -168.8(2) . . . . ? C1 C2 N1 C3 72.4(3) . . . . ? C1 C2 N1 Ti1 -45.9(2) . . . . ? C5 C6 N2 C8 -165.0(3) . . . . ? C5 C6 N2 C7 74.1(3) . . . . ? C5 O2 Ti1 O1 -44.9(2) . . . . ? C5 O2 Ti1 O3 57.2(2) . . . . ? C5 O2 Ti1 O4 -151.8(2) . . . 2_665 ? C5 O2 Ti1 O4 137.0(2) . . . . ? C5 O2 Ti1 N1 -56.7(5) . . . . ? C1 O1 Ti1 O2 172.7(2) . . . . ? C1 O1 Ti1 O3 72.5(2) . . . . ? C1 O1 Ti1 O4 -92.3(2) . . . 2_665 ? C1 O1 Ti1 O4 -15.7(5) . . . . ? C1 O1 Ti1 N1 -9.7(2) . . . . ? C9 O3 Ti1 O2 76.7(2) . . . . ? C9 O3 Ti1 O1 172.1(2) . . . . ? C9 O3 Ti1 O4 -36.4(3) . . . 2_665 ? C9 O3 Ti1 O4 -21.6(2) . . . . ? C9 O3 Ti1 N1 -114.2(2) . . . . ? C10 O4 Ti1 O2 -100.63(17) . . . . ? Ti1 O4 Ti1 O2 90.55(9) 2_665 . . . ? C10 O4 Ti1 O1 87.9(4) . . . . ? Ti1 O4 Ti1 O1 -80.9(3) 2_665 . . . ? C10 O4 Ti1 O3 -3.01(17) . . . . ? Ti1 O4 Ti1 O3 -171.83(10) 2_665 . . . ? C10 O4 Ti1 O4 168.8(2) . . . 2_665 ? Ti1 O4 Ti1 O4 0.0 2_665 . . 2_665 ? C10 O4 Ti1 N1 82.16(17) . . . . ? Ti1 O4 Ti1 N1 -86.65(9) 2_665 . . . ? C4 N1 Ti1 O2 160.0(4) . . . . ? C2 N1 Ti1 O2 42.7(4) . . . . ? C3 N1 Ti1 O2 -73.7(4) . . . . ? C4 N1 Ti1 O1 147.8(2) . . . . ? C2 N1 Ti1 O1 30.51(16) . . . . ? C3 N1 Ti1 O1 -85.8(2) . . . . ? C4 N1 Ti1 O3 44.7(2) . . . . ? C2 N1 Ti1 O3 -72.57(17) . . . . ? C3 N1 Ti1 O3 171.1(2) . . . . ? C4 N1 Ti1 O4 -104.3(2) . . . 2_665 ? C2 N1 Ti1 O4 138.38(16) . . . 2_665 ? C3 N1 Ti1 O4 22.0(2) . . . 2_665 ? C4 N1 Ti1 O4 -33.5(2) . . . . ? C2 N1 Ti1 O4 -150.87(16) . . . . ? C3 N1 Ti1 O4 92.8(2) . . . . ? _diffrn_measured_fraction_theta_max 0.929 _diffrn_reflns_theta_full 24.16 _diffrn_measured_fraction_theta_full 0.929 _refine_diff_density_max 0.201 _refine_diff_density_min -0.613 _refine_diff_density_rms 0.058 data_tony33 _database_code_CSD 158132 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H64 N4 O8 Ti2' _chemical_formula_weight 680.76 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0020 0.0020 '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' 0.0040 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0080 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ti' 'Ti' 0.2480 0.4460 '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 9.3358(14) _cell_length_b 10.0168(16) _cell_length_c 11.4403(18) _cell_angle_alpha 110.358(17) _cell_angle_beta 107.365(18) _cell_angle_gamma 99.353(18) _cell_volume 913.9(2) _cell_formula_units_Z 1 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'block' _exptl_crystal_colour colourless _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.237 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 368 _exptl_absorpt_coefficient_mu 0.484 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 213(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 'Stoe IPDS' _diffrn_measurement_method 'Image plate' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5798 _diffrn_reflns_av_R_equivalents 0.0286 _diffrn_reflns_av_sigmaI/netI 0.0362 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.06 _diffrn_reflns_theta_max 24.25 _reflns_number_total 2692 _reflns_number_gt 2219 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'IPDS (STOE, 1997)' _computing_cell_refinement ? _computing_data_reduction 'X-RED (STOE, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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 w=1/[\s^2^(Fo^2^)+(0.0549P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2692 _refine_ls_number_parameters 190 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0377 _refine_ls_R_factor_gt 0.0299 _refine_ls_wR_factor_ref 0.0823 _refine_ls_wR_factor_gt 0.0794 _refine_ls_goodness_of_fit_ref 1.014 _refine_ls_restrained_S_all 1.014 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.3654(3) 0.1933(2) 0.6181(2) 0.0303(5) Uani 1 d . . . C2 C 0.2886(3) 0.0327(3) 0.5118(3) 0.0471(6) Uani 1 d . . . H2A H 0.2243 -0.0226 0.5423 0.057 Uiso 1 calc R . . H2B H 0.3695 -0.0132 0.4977 0.057 Uiso 1 calc R . . H2C H 0.2231 0.0318 0.4276 0.057 Uiso 1 calc R . . C3 C 0.4722(3) 0.1965(3) 0.7495(3) 0.0471(6) Uani 1 d . . . H3A H 0.4104 0.1426 0.7826 0.056 Uiso 1 calc R . . H3B H 0.5223 0.2991 0.8160 0.056 Uiso 1 calc R . . H3C H 0.5521 0.1500 0.7336 0.056 Uiso 1 calc R . . C4 C 0.2471(3) 0.2834(2) 0.6392(2) 0.0319(5) Uani 1 d . . . C5 C 0.1724(3) 0.2590(3) 0.7345(3) 0.0492(7) Uani 1 d . . . H5A H 0.1081 0.1561 0.6951 0.059 Uiso 1 calc R . . H5B H 0.1072 0.3244 0.7489 0.059 Uiso 1 calc R . . H5C H 0.2542 0.2810 0.8202 0.059 Uiso 1 calc R . . C6 C 0.1187(3) 0.2534(3) 0.5059(3) 0.0440(6) Uani 1 d . . . H6A H 0.0531 0.1506 0.4643 0.053 Uiso 1 calc R . . H6B H 0.1665 0.2708 0.4459 0.053 Uiso 1 calc R . . H6C H 0.0548 0.3196 0.5225 0.053 Uiso 1 calc R . . C7 C 0.8310(3) 0.5172(3) 0.8276(2) 0.0390(6) Uani 1 d . . . H7A H 0.8215 0.4154 0.7684 0.047 Uiso 1 calc R . . H7B H 0.8542 0.5234 0.9191 0.047 Uiso 1 calc R . . C8 C 0.9644(3) 0.6254(3) 0.8283(2) 0.0407(6) Uani 1 d . . . H8A H 1.0594 0.5942 0.8512 0.049 Uiso 1 calc R . . H8B H 0.9388 0.6210 0.7372 0.049 Uiso 1 calc R . . C9 C 1.1041(3) 0.8787(3) 0.8981(3) 0.0512(7) Uani 1 d . . . H9A H 1.1254 0.9807 0.9615 0.061 Uiso 1 calc R . . H9B H 1.0560 0.8692 0.8066 0.061 Uiso 1 calc R . . H9C H 1.2017 0.8533 0.9097 0.061 Uiso 1 calc R . . C10 C 1.0655(4) 0.7999(3) 1.0622(2) 0.0589(7) Uani 1 d . . . H10A H 1.0856 0.9033 1.1216 0.071 Uiso 1 calc R . . H10B H 1.1634 0.7746 1.0783 0.071 Uiso 1 calc R . . H10C H 0.9928 0.7361 1.0799 0.071 Uiso 1 calc R . . C11 C 0.3002(2) 0.6459(2) 0.5265(2) 0.0275(5) Uani 1 d . . . H11A H 0.1877 0.5954 0.4732 0.033 Uiso 1 calc R . . H11B H 0.3323 0.7266 0.5013 0.033 Uiso 1 calc R . . C12 C 0.3295(3) 0.7106(2) 0.6762(2) 0.0303(5) Uani 1 d . . . H12A H 0.3200 0.8120 0.7052 0.036 Uiso 1 calc R . . H12B H 0.2508 0.6495 0.6922 0.036 Uiso 1 calc R . . C13 C 0.5074(3) 0.7477(3) 0.8959(2) 0.0427(6) Uani 1 d . . . H13A H 0.6123 0.7495 0.9460 0.051 Uiso 1 calc R . . H13B H 0.4304 0.6715 0.8977 0.051 Uiso 1 calc R . . H13C H 0.4924 0.8442 0.9368 0.051 Uiso 1 calc R . . C14 C 0.6098(3) 0.8260(2) 0.7531(2) 0.0350(5) Uani 1 d . . . H14A H 0.7127 0.8258 0.8054 0.042 Uiso 1 calc R . . H14B H 0.5970 0.9240 0.7922 0.042 Uiso 1 calc R . . H14C H 0.6000 0.8022 0.6608 0.042 Uiso 1 calc R . . N1 N 0.9976(2) 0.7784(2) 0.92268(18) 0.0371(4) Uani 1 d . . . N2 N 0.4875(2) 0.71395(18) 0.75450(16) 0.0287(4) Uani 1 d . . . O1 O 0.45949(16) 0.27333(14) 0.57191(13) 0.0256(3) Uani 1 d . . . O2 O 0.34084(17) 0.43397(15) 0.69728(14) 0.0297(3) Uani 1 d . . . O3 O 0.68836(17) 0.54780(16) 0.78272(14) 0.0337(4) Uani 1 d . . . O4 O 0.38728(15) 0.54216(14) 0.49801(13) 0.0223(3) Uani 1 d . . . Ti1 Ti 0.50306(4) 0.48029(4) 0.63971(3) 0.02143(13) Uani 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0296(12) 0.0265(11) 0.0430(12) 0.0203(10) 0.0191(10) 0.0064(11) C2 0.0501(17) 0.0268(12) 0.0716(17) 0.0203(12) 0.0365(14) 0.0054(13) C3 0.0508(17) 0.0520(16) 0.0603(16) 0.0420(14) 0.0260(13) 0.0196(14) C4 0.0295(13) 0.0282(12) 0.0426(12) 0.0180(10) 0.0184(10) 0.0046(11) C5 0.0539(17) 0.0436(15) 0.0718(17) 0.0313(14) 0.0449(15) 0.0141(14) C6 0.0253(13) 0.0456(15) 0.0606(15) 0.0261(12) 0.0144(11) 0.0052(12) C7 0.0339(14) 0.0351(13) 0.0409(13) 0.0152(10) 0.0055(10) 0.0112(12) C8 0.0290(13) 0.0393(14) 0.0441(13) 0.0083(11) 0.0121(10) 0.0101(12) C9 0.0470(16) 0.0476(16) 0.0446(14) 0.0118(12) 0.0154(12) -0.0014(14) C10 0.0621(19) 0.0578(18) 0.0418(14) 0.0174(13) 0.0126(13) 0.0022(16) C11 0.0246(11) 0.0275(11) 0.0349(11) 0.0134(9) 0.0139(9) 0.0136(10) C12 0.0333(13) 0.0243(11) 0.0378(11) 0.0114(9) 0.0197(10) 0.0122(10) C13 0.0586(17) 0.0383(13) 0.0292(11) 0.0086(10) 0.0191(11) 0.0180(13) C14 0.0372(14) 0.0206(11) 0.0363(12) 0.0064(9) 0.0099(10) 0.0019(11) N1 0.0298(11) 0.0376(11) 0.0351(10) 0.0102(8) 0.0100(8) 0.0048(10) N2 0.0336(11) 0.0243(9) 0.0275(9) 0.0091(7) 0.0130(8) 0.0079(9) O1 0.0252(8) 0.0208(7) 0.0356(8) 0.0143(6) 0.0158(6) 0.0056(7) O2 0.0342(9) 0.0255(8) 0.0381(8) 0.0157(6) 0.0220(7) 0.0097(7) O3 0.0264(8) 0.0354(9) 0.0321(8) 0.0132(7) 0.0047(6) 0.0052(7) O4 0.0217(7) 0.0190(7) 0.0288(7) 0.0100(6) 0.0125(6) 0.0076(6) Ti1 0.0208(2) 0.0188(2) 0.0257(2) 0.01028(15) 0.00985(15) 0.00449(16) _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 C1 O1 1.427(2) . ? C1 C3 1.522(3) . ? C1 C2 1.524(3) . ? C1 C4 1.558(3) . ? C4 O2 1.417(3) . ? C4 C5 1.522(3) . ? C4 C6 1.526(3) . ? C7 O3 1.402(3) . ? C7 C8 1.508(4) . ? C8 N1 1.451(3) . ? C9 N1 1.455(3) . ? C10 N1 1.452(3) . ? C11 O4 1.430(2) . ? C11 C12 1.523(3) . ? C12 N2 1.468(3) . ? C13 N2 1.478(3) . ? C14 N2 1.473(3) . ? N2 Ti1 2.3041(17) . ? O1 Ti1 1.8665(14) . ? O2 Ti1 1.8768(14) . ? O3 Ti1 1.8131(15) . ? O4 Ti1 2.0128(13) . ? O4 Ti1 2.0909(13) 2_666 ? Ti1 O4 2.0909(13) 2_666 ? 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 C1 C3 108.14(18) . . ? O1 C1 C2 108.89(17) . . ? C3 C1 C2 110.00(19) . . ? O1 C1 C4 102.95(15) . . ? C3 C1 C4 112.31(18) . . ? C2 C1 C4 114.12(19) . . ? O2 C4 C5 109.27(18) . . ? O2 C4 C6 108.15(17) . . ? C5 C4 C6 109.6(2) . . ? O2 C4 C1 103.57(16) . . ? C5 C4 C1 113.89(18) . . ? C6 C4 C1 112.07(18) . . ? O3 C7 C8 111.40(18) . . ? N1 C8 C7 113.63(19) . . ? O4 C11 C12 110.02(15) . . ? N2 C12 C11 109.68(15) . . ? C8 N1 C10 112.2(2) . . ? C8 N1 C9 110.08(19) . . ? C10 N1 C9 109.3(2) . . ? C12 N2 C14 111.26(16) . . ? C12 N2 C13 110.64(17) . . ? C14 N2 C13 109.07(17) . . ? C12 N2 Ti1 103.77(12) . . ? C14 N2 Ti1 108.66(12) . . ? C13 N2 Ti1 113.38(12) . . ? C1 O1 Ti1 118.88(11) . . ? C4 O2 Ti1 118.31(12) . . ? C7 O3 Ti1 142.44(14) . . ? C11 O4 Ti1 121.10(11) . . ? C11 O4 Ti1 123.94(11) . 2_666 ? Ti1 O4 Ti1 108.93(6) . 2_666 ? O3 Ti1 O1 103.43(7) . . ? O3 Ti1 O2 107.98(7) . . ? O1 Ti1 O2 80.05(6) . . ? O3 Ti1 O4 139.26(6) . . ? O1 Ti1 O4 111.22(6) . . ? O2 Ti1 O4 98.69(6) . . ? O3 Ti1 O4 92.96(6) . 2_666 ? O1 Ti1 O4 83.37(6) . 2_666 ? O2 Ti1 O4 155.75(6) . 2_666 ? O4 Ti1 O4 71.07(6) . 2_666 ? O3 Ti1 N2 81.88(7) . . ? O1 Ti1 N2 158.50(6) . . ? O2 Ti1 N2 78.51(6) . . ? O4 Ti1 N2 73.79(6) . . ? O4 Ti1 N2 117.47(6) 2_666 . ? 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 C1 C4 O2 -40.33(19) . . . . ? C3 C1 C4 O2 75.8(2) . . . . ? C2 C1 C4 O2 -158.17(17) . . . . ? O1 C1 C4 C5 -158.9(2) . . . . ? C3 C1 C4 C5 -42.8(3) . . . . ? C2 C1 C4 C5 83.3(3) . . . . ? O1 C1 C4 C6 76.0(2) . . . . ? C3 C1 C4 C6 -167.91(19) . . . . ? C2 C1 C4 C6 -41.8(2) . . . . ? O3 C7 C8 N1 64.3(2) . . . . ? O4 C11 C12 N2 29.6(2) . . . . ? C7 C8 N1 C10 69.5(3) . . . . ? C7 C8 N1 C9 -168.46(19) . . . . ? C11 C12 N2 C14 69.8(2) . . . . ? C11 C12 N2 C13 -168.76(17) . . . . ? C11 C12 N2 Ti1 -46.84(17) . . . . ? C3 C1 O1 Ti1 -84.60(18) . . . . ? C2 C1 O1 Ti1 155.89(14) . . . . ? C4 C1 O1 Ti1 34.43(19) . . . . ? C5 C4 O2 Ti1 157.22(15) . . . . ? C6 C4 O2 Ti1 -83.56(18) . . . . ? C1 C4 O2 Ti1 35.51(18) . . . . ? C8 C7 O3 Ti1 106.4(2) . . . . ? C12 C11 O4 Ti1 7.5(2) . . . . ? C12 C11 O4 Ti1 -142.12(14) . . . 2_666 ? C7 O3 Ti1 O1 35.5(2) . . . . ? C7 O3 Ti1 O2 119.2(2) . . . . ? C7 O3 Ti1 O4 -112.5(2) . . . . ? C7 O3 Ti1 O4 -48.4(2) . . . 2_666 ? C7 O3 Ti1 N2 -165.7(2) . . . . ? C1 O1 Ti1 O3 92.53(14) . . . . ? C1 O1 Ti1 O2 -13.75(13) . . . . ? C1 O1 Ti1 O4 -109.29(13) . . . . ? C1 O1 Ti1 O4 -175.99(14) . . . 2_666 ? C1 O1 Ti1 N2 -9.6(2) . . . . ? C4 O2 Ti1 O3 -115.88(14) . . . . ? C4 O2 Ti1 O1 -14.88(13) . . . . ? C4 O2 Ti1 O4 95.30(13) . . . . ? C4 O2 Ti1 O4 32.7(2) . . . 2_666 ? C4 O2 Ti1 N2 166.69(14) . . . . ? C11 O4 Ti1 O3 -81.98(16) . . . . ? Ti1 O4 Ti1 O3 71.67(10) 2_666 . . . ? C11 O4 Ti1 O1 131.66(14) . . . . ? Ti1 O4 Ti1 O1 -74.69(7) 2_666 . . . ? C11 O4 Ti1 O2 49.02(14) . . . . ? Ti1 O4 Ti1 O2 -157.32(7) 2_666 . . . ? C11 O4 Ti1 O4 -153.66(17) . . . 2_666 ? Ti1 O4 Ti1 O4 0.0 2_666 . . 2_666 ? C11 O4 Ti1 N2 -26.24(14) . . . . ? Ti1 O4 Ti1 N2 127.41(8) 2_666 . . . ? C12 N2 Ti1 O3 -174.09(13) . . . . ? C14 N2 Ti1 O3 67.44(13) . . . . ? C13 N2 Ti1 O3 -54.01(16) . . . . ? C12 N2 Ti1 O1 -68.0(2) . . . . ? C14 N2 Ti1 O1 173.56(15) . . . . ? C13 N2 Ti1 O1 52.1(2) . . . . ? C12 N2 Ti1 O2 -63.77(12) . . . . ? C14 N2 Ti1 O2 177.76(13) . . . . ? C13 N2 Ti1 O2 56.31(15) . . . . ? C12 N2 Ti1 O4 38.92(12) . . . . ? C14 N2 Ti1 O4 -79.55(13) . . . . ? C13 N2 Ti1 O4 159.00(16) . . . . ? C12 N2 Ti1 O4 96.79(13) . . . 2_666 ? C14 N2 Ti1 O4 -21.68(14) . . . 2_666 ? C13 N2 Ti1 O4 -143.13(15) . . . 2_666 ? _diffrn_measured_fraction_theta_max 0.912 _diffrn_reflns_theta_full 24.25 _diffrn_measured_fraction_theta_full 0.912 _refine_diff_density_max 0.287 _refine_diff_density_min -0.215 _refine_diff_density_rms 0.044