# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Klaus Merz' _publ_contact_author_address ; Lehrstuhl fur Anorganische Chemie Ruhr-Universitat Bochum Universitatsstr. 150 Bochum D-44801 GERMANY ; _publ_contact_author_email KLAUS.MERZ@RUB.DE _publ_section_title ; Active Peroxo Titanium Complexes: Syntheses, Characterization and their Potential in the Photo oxidation Process of 2-Propanol ; loop_ _publ_author_name 'Klaus Merz' 'Markus Rohe' # Attachment '070925t.cif' data_070925t _database_code_depnum_ccdc_archive 'CCDC 664367' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H16 N4 O48 Ti4 Zn' _chemical_formula_weight 1385.38 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' Zn Zn 0.2839 1.4301 '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 10.108(4) _cell_length_b 10.851(5) _cell_length_c 12.690(5) _cell_angle_alpha 65.087(8) _cell_angle_beta 87.377(10) _cell_angle_gamma 79.355(9) _cell_volume 1239.8(9) _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 prism _exptl_crystal_colour orange _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.856 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 690 _exptl_absorpt_coefficient_mu 1.228 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.6394 _exptl_absorpt_correction_T_max 0.8870 _exptl_absorpt_process_details ? _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 'Bruker axs CCD 1000' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5674 _diffrn_reflns_av_R_equivalents 0.0456 _diffrn_reflns_av_sigmaI/netI 0.0776 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.10 _diffrn_reflns_theta_max 24.95 _reflns_number_total 4077 _reflns_number_gt 3264 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1996)' _computing_cell_refinement 'SAINT (Siemens, 1996)' _computing_data_reduction 'SAINT (Siemens, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Siemens, 1996)' _computing_publication_material 'SHELXTL (Siemens, 1996)' _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^)+(0.1242P)^2^+3.3908P] 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 0.018(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4077 _refine_ls_number_parameters 368 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0787 _refine_ls_R_factor_gt 0.0639 _refine_ls_wR_factor_ref 0.1953 _refine_ls_wR_factor_gt 0.1753 _refine_ls_goodness_of_fit_ref 1.038 _refine_ls_restrained_S_all 1.038 _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 Zn1 Zn 1.0000 1.0000 0.5000 0.0229(3) Uani 1 2 d S . . Ti1 Ti 0.44759(9) 1.52528(9) -0.26832(8) 0.0109(3) Uani 1 1 d . . . Ti2 Ti 0.73319(9) 1.43662(9) -0.12918(8) 0.0104(3) Uani 1 1 d . . . O1 O 0.5831(5) 1.1188(4) -0.1498(3) 0.0276(10) Uani 1 1 d . . . C1 C 0.5576(6) 1.1603(6) -0.2538(5) 0.0198(13) Uani 1 1 d . . . O2 O 0.4592(4) 1.1172(4) -0.2856(3) 0.0215(9) Uani 1 1 d . . . C2 C 0.6355(6) 1.2552(6) -0.3474(5) 0.0160(12) Uani 1 1 d . . . H2A H 0.5727 1.3238 -0.4099 0.019 Uiso 1 1 calc R . . H2B H 0.6978 1.2012 -0.3803 0.019 Uiso 1 1 calc R . . O3 O 0.6310(4) 1.4042(4) -0.2465(3) 0.0113(8) Uani 1 1 d . . . C3 C 0.7146(5) 1.3294(5) -0.3015(4) 0.0126(11) Uani 1 1 d . . . C4 C 0.8203(5) 1.2231(5) -0.2089(5) 0.0143(11) Uani 1 1 d . . . O5 O 0.8330(4) 1.2446(4) -0.1184(3) 0.0162(8) Uani 1 1 d . . . C5 C 0.7843(6) 1.4325(5) -0.4004(4) 0.0146(11) Uani 1 1 d . . . H5A H 0.8547 1.3800 -0.4288 0.018 Uiso 1 1 calc R . . H5B H 0.7179 1.4874 -0.4645 0.018 Uiso 1 1 calc R . . O6 O 0.8411(4) 1.5237(4) -0.2667(3) 0.0157(8) Uani 1 1 d . . . C6 C 0.8475(5) 1.5310(5) -0.3713(5) 0.0146(11) Uani 1 1 d . . . O7 O 0.9040(5) 1.6164(4) -0.4478(3) 0.0252(10) Uani 1 1 d . . . C7 C 0.5668(6) 1.7783(5) -0.4158(4) 0.0155(12) Uani 1 1 d . . . O8 O 0.8768(4) 1.3947(4) -0.0244(3) 0.0155(8) Uani 1 1 d . . . C8 C 0.5903(6) 1.8119(5) -0.3150(4) 0.0150(11) Uani 1 1 d . . . H8A H 0.5538 1.9100 -0.3371 0.018 Uiso 1 1 calc R . . H8B H 0.6876 1.7978 -0.3009 0.018 Uiso 1 1 calc R . . O9 O 0.7936(4) 1.5318(4) -0.0510(3) 0.0177(8) Uani 1 1 d . . . C9 C 0.5275(6) 1.7264(5) -0.2009(4) 0.0132(11) Uani 1 1 d . . . O10 O 0.5074(4) 1.6801(4) -0.4036(3) 0.0167(8) Uani 1 1 d . . . C10 C 0.3729(6) 1.7633(5) -0.2199(4) 0.0147(12) Uani 1 1 d . . . O11 O 0.6085(4) 1.8514(4) -0.5121(3) 0.0243(10) Uani 1 1 d . . . C11 C 0.5724(5) 1.7582(5) -0.1018(4) 0.0130(11) Uani 1 1 d . . . H11A H 0.6710 1.7373 -0.0939 0.016 Uiso 1 1 calc R . . H11B H 0.5432 1.8569 -0.1216 0.016 Uiso 1 1 calc R . . O12 O 0.3182(4) 1.6749(4) -0.2363(3) 0.0172(9) Uani 1 1 d . . . C12 C 0.5144(5) 1.6749(5) 0.0125(4) 0.0112(11) Uani 1 1 d . . . O13 O 0.3091(4) 1.8762(4) -0.2257(3) 0.0178(9) Uani 1 1 d . . . O14 O 0.3902(4) 1.6695(4) 0.0091(3) 0.0128(8) Uani 1 1 d . . . O15 O 0.5902(4) 1.6175(4) 0.1029(3) 0.0129(8) Uani 1 1 d . . . O16 O 0.3962(4) 1.4309(4) -0.3491(3) 0.0191(9) Uani 1 1 d . . . O17 O 0.2877(4) 1.5310(4) -0.3356(3) 0.0181(9) Uani 1 1 d . . . O18 O 0.8907(4) 1.1259(4) -0.2248(3) 0.0208(9) Uani 1 1 d . . . O19 O 0.5674(4) 1.5857(3) -0.1768(3) 0.0105(8) Uani 1 1 d . . . N1 N 0.2942(6) 2.0117(6) -0.0814(5) 0.0359(14) Uani 1 1 d . . . N2 N 0.8660(6) 0.7318(6) 0.2962(5) 0.0331(14) Uani 1 1 d . . . OW1 O 0.8357(5) 0.9747(5) 0.4258(4) 0.0335(12) Uani 1 1 d . . . OW2 O 1.0998(4) 1.0435(4) 0.3439(3) 0.0238(9) Uani 1 1 d . . . OW3 O 0.9233(4) 1.2126(4) 0.4492(4) 0.0272(10) Uani 1 1 d . . . OW4 O 0.8793(5) 0.5852(6) 0.1514(4) 0.0425(13) Uani 1 1 d . . . OW5 O 0.0723(5) 2.1212(5) 0.0140(4) 0.0325(11) Uani 1 1 d . . . OW6 O 1.0109(6) 1.3036(5) 0.1865(4) 0.0394(12) Uani 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 Zn1 0.0261(6) 0.0186(5) 0.0216(6) -0.0065(4) -0.0046(4) -0.0021(4) Ti1 0.0125(6) 0.0096(5) 0.0089(5) -0.0024(4) -0.0028(4) -0.0009(4) Ti2 0.0117(5) 0.0105(5) 0.0087(5) -0.0043(4) -0.0023(4) -0.0001(4) O1 0.048(3) 0.024(2) 0.013(2) -0.0054(17) -0.0031(19) -0.014(2) C1 0.033(4) 0.011(3) 0.016(3) -0.008(2) -0.002(2) 0.000(2) O2 0.029(2) 0.020(2) 0.019(2) -0.0063(16) 0.0010(17) -0.0155(18) C2 0.021(3) 0.016(3) 0.013(3) -0.008(2) -0.002(2) -0.002(2) O3 0.0137(19) 0.0110(18) 0.0106(18) -0.0067(14) -0.0031(14) 0.0008(14) C3 0.018(3) 0.011(2) 0.010(3) -0.007(2) -0.001(2) 0.001(2) C4 0.014(3) 0.012(3) 0.014(3) -0.003(2) -0.003(2) 0.001(2) O5 0.019(2) 0.0145(19) 0.0153(19) -0.0088(15) -0.0055(15) 0.0033(15) C5 0.021(3) 0.014(3) 0.009(3) -0.005(2) 0.001(2) -0.002(2) O6 0.018(2) 0.0172(19) 0.0133(19) -0.0066(15) -0.0011(15) -0.0046(16) C6 0.013(3) 0.013(3) 0.018(3) -0.006(2) -0.002(2) -0.003(2) O7 0.038(3) 0.026(2) 0.016(2) -0.0097(18) 0.0078(18) -0.016(2) C7 0.021(3) 0.012(3) 0.010(3) -0.002(2) 0.000(2) 0.001(2) O8 0.012(2) 0.0155(19) 0.019(2) -0.0098(16) -0.0069(15) 0.0053(15) C8 0.018(3) 0.013(3) 0.012(3) -0.002(2) -0.001(2) -0.005(2) O9 0.017(2) 0.0141(19) 0.022(2) -0.0108(16) -0.0065(16) 0.0061(15) C9 0.020(3) 0.009(2) 0.009(2) -0.002(2) 0.002(2) -0.002(2) O10 0.023(2) 0.0149(19) 0.0111(19) -0.0036(15) -0.0013(15) -0.0052(16) C10 0.020(3) 0.012(3) 0.006(2) 0.000(2) -0.005(2) 0.003(2) O11 0.037(3) 0.029(2) 0.010(2) -0.0057(17) 0.0051(17) -0.020(2) C11 0.014(3) 0.012(3) 0.013(3) -0.005(2) -0.001(2) -0.001(2) O12 0.019(2) 0.0132(19) 0.020(2) -0.0089(16) -0.0031(16) 0.0017(15) C12 0.018(3) 0.006(2) 0.010(3) -0.005(2) 0.002(2) -0.001(2) O13 0.020(2) 0.0132(19) 0.017(2) -0.0051(15) -0.0058(16) 0.0030(16) O14 0.012(2) 0.0131(18) 0.0127(18) -0.0050(15) 0.0013(14) -0.0017(14) O15 0.015(2) 0.0135(18) 0.0097(18) -0.0048(15) -0.0004(15) -0.0007(15) O16 0.017(2) 0.018(2) 0.023(2) -0.0118(17) -0.0080(16) 0.0041(16) O17 0.013(2) 0.020(2) 0.021(2) -0.0091(17) -0.0067(16) 0.0003(16) O18 0.025(2) 0.016(2) 0.019(2) -0.0094(16) -0.0066(17) 0.0089(17) O19 0.0118(19) 0.0077(17) 0.0104(18) -0.0033(14) -0.0021(14) 0.0012(14) N1 0.039(3) 0.038(3) 0.035(3) -0.021(3) 0.002(3) -0.004(3) N2 0.049(4) 0.031(3) 0.022(3) -0.016(2) -0.004(3) 0.001(3) OW1 0.033(3) 0.041(3) 0.019(2) 0.001(2) -0.0137(19) -0.019(2) OW2 0.028(2) 0.021(2) 0.020(2) -0.0081(17) 0.0031(18) -0.0043(18) OW3 0.034(3) 0.011(2) 0.032(2) -0.0054(17) 0.001(2) 0.0001(18) OW4 0.038(3) 0.047(3) 0.038(3) -0.013(2) 0.000(2) -0.008(2) OW5 0.030(3) 0.030(2) 0.033(3) -0.011(2) -0.005(2) 0.002(2) OW6 0.062(4) 0.026(2) 0.026(3) -0.006(2) -0.015(2) -0.006(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zn1 OW1 2.061(4) 2_776 ? Zn1 OW1 2.061(4) . ? Zn1 OW2 2.091(4) 2_776 ? Zn1 OW2 2.091(4) . ? Zn1 OW3 2.115(4) 2_776 ? Zn1 OW3 2.115(4) . ? Ti1 O17 1.841(4) . ? Ti1 O16 1.871(4) . ? Ti1 O10 1.997(4) . ? Ti1 O3 2.020(4) . ? Ti1 O12 2.057(4) . ? Ti1 O19 2.076(4) . ? Ti1 O15 2.087(4) 2_685 ? Ti1 Ti2 3.2227(17) . ? Ti2 O8 1.873(4) . ? Ti2 O9 1.891(4) . ? Ti2 O6 1.986(4) . ? Ti2 O19 2.014(4) . ? Ti2 O14 2.020(4) 2_685 ? Ti2 O3 2.030(4) . ? Ti2 O5 2.091(4) . ? O1 C1 1.225(7) . ? C1 O2 1.318(7) . ? C1 C2 1.509(8) . ? C2 C3 1.517(7) . ? O3 C3 1.425(6) . ? C3 C5 1.532(7) . ? C3 C4 1.540(7) . ? C4 O18 1.244(7) . ? C4 O5 1.281(7) . ? C5 C6 1.515(7) . ? O6 C6 1.296(7) . ? C6 O7 1.230(7) . ? C7 O11 1.248(7) . ? C7 O10 1.268(7) . ? C7 C8 1.510(8) . ? O8 O9 1.475(5) . ? C8 C9 1.537(7) . ? C9 O19 1.407(6) . ? C9 C11 1.543(7) . ? C9 C10 1.544(8) . ? C10 O13 1.249(7) . ? C10 O12 1.282(7) . ? C11 C12 1.510(7) . ? C12 O15 1.262(6) . ? C12 O14 1.271(7) . ? O14 Ti2 2.020(4) 2_685 ? O15 Ti1 2.087(4) 2_685 ? O16 O17 1.453(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag OW1 Zn1 OW1 180.000(1) 2_776 . ? OW1 Zn1 OW2 89.83(18) 2_776 2_776 ? OW1 Zn1 OW2 90.17(18) . 2_776 ? OW1 Zn1 OW2 90.17(18) 2_776 . ? OW1 Zn1 OW2 89.83(18) . . ? OW2 Zn1 OW2 180.000(1) 2_776 . ? OW1 Zn1 OW3 92.18(19) 2_776 2_776 ? OW1 Zn1 OW3 87.82(19) . 2_776 ? OW2 Zn1 OW3 90.86(16) 2_776 2_776 ? OW2 Zn1 OW3 89.14(16) . 2_776 ? OW1 Zn1 OW3 87.82(19) 2_776 . ? OW1 Zn1 OW3 92.18(19) . . ? OW2 Zn1 OW3 89.14(16) 2_776 . ? OW2 Zn1 OW3 90.86(16) . . ? OW3 Zn1 OW3 180.000(1) 2_776 . ? O17 Ti1 O16 46.08(17) . . ? O17 Ti1 O10 96.97(17) . . ? O16 Ti1 O10 98.04(17) . . ? O17 Ti1 O3 132.54(16) . . ? O16 Ti1 O3 86.55(16) . . ? O10 Ti1 O3 91.79(16) . . ? O17 Ti1 O12 77.58(17) . . ? O16 Ti1 O12 123.66(17) . . ? O10 Ti1 O12 86.61(16) . . ? O3 Ti1 O12 149.70(16) . . ? O17 Ti1 O19 153.80(16) . . ? O16 Ti1 O19 160.11(16) . . ? O10 Ti1 O19 82.07(15) . . ? O3 Ti1 O19 73.58(14) . . ? O12 Ti1 O19 76.23(15) . . ? O17 Ti1 O15 95.11(17) . 2_685 ? O16 Ti1 O15 96.09(16) . 2_685 ? O10 Ti1 O15 165.52(16) . 2_685 ? O3 Ti1 O15 85.89(14) . 2_685 ? O12 Ti1 O15 88.21(15) . 2_685 ? O19 Ti1 O15 83.57(14) . 2_685 ? O17 Ti1 Ti2 166.27(13) . . ? O16 Ti1 Ti2 123.21(12) . . ? O10 Ti1 Ti2 93.10(12) . . ? O3 Ti1 Ti2 37.38(10) . . ? O12 Ti1 Ti2 112.43(12) . . ? O19 Ti1 Ti2 37.33(10) . . ? O15 Ti1 Ti2 76.42(11) 2_685 . ? O8 Ti2 O9 46.15(16) . . ? O8 Ti2 O6 92.95(17) . . ? O9 Ti2 O6 92.13(17) . . ? O8 Ti2 O19 131.88(15) . . ? O9 Ti2 O19 86.52(16) . . ? O6 Ti2 O19 97.73(15) . . ? O8 Ti2 O14 95.70(16) . 2_685 ? O9 Ti2 O14 99.63(17) . 2_685 ? O6 Ti2 O14 168.22(16) . 2_685 ? O19 Ti2 O14 82.39(15) . 2_685 ? O8 Ti2 O3 153.43(15) . . ? O9 Ti2 O3 159.26(16) . . ? O6 Ti2 O3 82.00(15) . . ? O19 Ti2 O3 74.68(15) . . ? O14 Ti2 O3 86.70(15) 2_685 . ? O8 Ti2 O5 77.78(15) . . ? O9 Ti2 O5 123.87(16) . . ? O6 Ti2 O5 87.77(16) . . ? O19 Ti2 O5 149.04(16) . . ? O14 Ti2 O5 86.27(15) 2_685 . ? O3 Ti2 O5 75.98(14) . . ? O8 Ti2 Ti1 167.51(12) . . ? O9 Ti2 Ti1 125.16(12) . . ? O6 Ti2 Ti1 96.60(12) . . ? O19 Ti2 Ti1 38.68(10) . . ? O14 Ti2 Ti1 76.07(11) 2_685 . ? O3 Ti2 Ti1 37.16(10) . . ? O5 Ti2 Ti1 110.53(11) . . ? O1 C1 O2 118.4(5) . . ? O1 C1 C2 123.2(5) . . ? O2 C1 C2 118.4(5) . . ? C1 C2 C3 112.2(4) . . ? C3 O3 Ti1 139.8(3) . . ? C3 O3 Ti2 113.2(3) . . ? Ti1 O3 Ti2 105.46(16) . . ? O3 C3 C2 112.2(4) . . ? O3 C3 C5 107.7(4) . . ? C2 C3 C5 110.8(4) . . ? O3 C3 C4 106.6(4) . . ? C2 C3 C4 109.6(4) . . ? C5 C3 C4 109.9(4) . . ? O18 C4 O5 123.3(5) . . ? O18 C4 C3 120.9(5) . . ? O5 C4 C3 115.7(5) . . ? C4 O5 Ti2 115.3(3) . . ? C6 C5 C3 116.5(4) . . ? C6 O6 Ti2 135.4(4) . . ? O7 C6 O6 121.5(5) . . ? O7 C6 C5 119.1(5) . . ? O6 C6 C5 119.4(4) . . ? O11 C7 O10 121.2(5) . . ? O11 C7 C8 117.2(5) . . ? O10 C7 C8 121.6(5) . . ? O9 O8 Ti2 67.6(2) . . ? C7 C8 C9 115.1(5) . . ? O8 O9 Ti2 66.3(2) . . ? O19 C9 C8 108.3(4) . . ? O19 C9 C11 111.5(4) . . ? C8 C9 C11 109.9(4) . . ? O19 C9 C10 107.8(4) . . ? C8 C9 C10 108.0(4) . . ? C11 C9 C10 111.1(4) . . ? C7 O10 Ti1 135.1(4) . . ? O13 C10 O12 123.5(5) . . ? O13 C10 C9 120.9(5) . . ? O12 C10 C9 115.4(4) . . ? C12 C11 C9 111.7(4) . . ? C10 O12 Ti1 116.0(3) . . ? O15 C12 O14 125.1(5) . . ? O15 C12 C11 118.9(5) . . ? O14 C12 C11 116.0(5) . . ? C12 O14 Ti2 132.8(3) . 2_685 ? C12 O15 Ti1 129.0(3) . 2_685 ? O17 O16 Ti1 65.9(2) . . ? O16 O17 Ti1 68.0(2) . . ? C9 O19 Ti2 140.1(3) . . ? C9 O19 Ti1 111.6(3) . . ? Ti2 O19 Ti1 103.99(16) . . ? _diffrn_measured_fraction_theta_max 0.942 _diffrn_reflns_theta_full 24.95 _diffrn_measured_fraction_theta_full 0.942 _refine_diff_density_max 0.892 _refine_diff_density_min -1.270 _refine_diff_density_rms 0.174 # Attachment '070621t.cif' data_070621t _database_code_depnum_ccdc_archive 'CCDC 664368' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H23 Li2 O25 Ti' _chemical_formula_weight 701.14 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' Li Li -0.0003 0.0001 '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 monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 13.731(7) _cell_length_b 14.940(9) _cell_length_c 14.911(9) _cell_angle_alpha 90.00 _cell_angle_beta 115.474(14) _cell_angle_gamma 90.00 _cell_volume 2762(3) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour colorless _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.686 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1436 _exptl_absorpt_coefficient_mu 0.420 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9592 _exptl_absorpt_correction_T_max 0.9793 _exptl_absorpt_process_details ? _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 'Bruker axs CCD 1000' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15219 _diffrn_reflns_av_R_equivalents 0.0867 _diffrn_reflns_av_sigmaI/netI 0.0915 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.64 _diffrn_reflns_theta_max 25.10 _reflns_number_total 4836 _reflns_number_gt 3126 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1996)' _computing_cell_refinement 'SAINT (Siemens, 1996)' _computing_data_reduction 'SAINT (Siemens, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Siemens, 1996)' _computing_publication_material 'SHELXTL (Siemens, 1996)' _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^)+(0.0755P)^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 SHELXL _refine_ls_extinction_coef 0.0219(13) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4836 _refine_ls_number_parameters 460 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0897 _refine_ls_R_factor_gt 0.0521 _refine_ls_wR_factor_ref 0.1395 _refine_ls_wR_factor_gt 0.1206 _refine_ls_goodness_of_fit_ref 0.956 _refine_ls_restrained_S_all 0.956 _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 0.19505(5) 0.23528(4) 0.17269(5) 0.0166(2) Uani 1 1 d . . . Li1 Li 0.0992(5) 0.3014(4) 0.3345(5) 0.0298(16) Uani 1 1 d . . . Li2 Li 0.4954(5) 0.2016(5) 0.5877(5) 0.0321(17) Uani 1 1 d . . . O1 O -0.1918(2) 0.17473(18) 0.2480(2) 0.0333(7) Uani 1 1 d . . . C1 C -0.1146(3) 0.2093(2) 0.2416(3) 0.0187(8) Uani 1 1 d . . . O2 O -0.0556(2) 0.26976(17) 0.3053(2) 0.0246(6) Uani 1 1 d . . . C2 C -0.0824(3) 0.1831(2) 0.1607(3) 0.0211(9) Uani 1 1 d . . . H2A H -0.1464 0.1598 0.1046 0.025 Uiso 1 1 calc R . . H2B H -0.0301 0.1340 0.1854 0.025 Uiso 1 1 calc R . . O3 O 0.07256(19) 0.20686(16) 0.04054(19) 0.0213(6) Uani 1 1 d . . . C3 C -0.0332(3) 0.2573(2) 0.1218(3) 0.0178(8) Uani 1 1 d . . . O4 O -0.1062(2) 0.21103(17) -0.05051(19) 0.0220(6) Uani 1 1 d . . . C4 C -0.0249(3) 0.2228(2) 0.0279(3) 0.0191(8) Uani 1 1 d . . . O5 O -0.0237(3) 0.39779(18) -0.0053(3) 0.0477(9) Uani 1 1 d . . . C5 C -0.0578(3) 0.4128(2) 0.0552(3) 0.0243(9) Uani 1 1 d . . . O6 O -0.0589(3) 0.49269(19) 0.0898(3) 0.0448(9) Uani 1 1 d . . . H6 H -0.025(4) 0.525(3) 0.063(4) 0.063(17) Uiso 1 1 d . . . C6 C -0.1027(3) 0.3418(2) 0.0970(3) 0.0211(9) Uani 1 1 d . . . H6A H -0.1762 0.3271 0.0487 0.025 Uiso 1 1 calc R . . H6B H -0.1062 0.3642 0.1573 0.025 Uiso 1 1 calc R . . O7 O 0.07363(19) 0.27692(15) 0.19217(19) 0.0186(6) Uani 1 1 d . . . C7 C 0.5029(3) 0.3372(3) 0.2995(3) 0.0247(9) Uani 1 1 d . . . O8 O 0.5647(3) 0.2892(2) 0.3767(2) 0.0390(8) Uani 1 1 d . . . H8 H 0.599(6) 0.248(4) 0.363(6) 0.11(3) Uiso 1 1 d . . . C8 C 0.4387(3) 0.4072(3) 0.3211(3) 0.0245(9) Uani 1 1 d . . . H8A H 0.4598 0.4664 0.3071 0.029 Uiso 1 1 calc R . . H8B H 0.4546 0.4051 0.3917 0.029 Uiso 1 1 calc R . . O9 O 0.4981(2) 0.3241(2) 0.2174(2) 0.0356(7) Uani 1 1 d . . . C9 C 0.3175(3) 0.3938(2) 0.2586(3) 0.0183(8) Uani 1 1 d . . . O10 O 0.3086(2) 0.47001(17) 0.1132(2) 0.0277(7) Uani 1 1 d . . . C10 C 0.2470(3) 0.4644(2) 0.2792(3) 0.0231(9) Uani 1 1 d . . . H10A H 0.2726 0.5245 0.2737 0.028 Uiso 1 1 calc R . . H10B H 0.1722 0.4589 0.2290 0.028 Uiso 1 1 calc R . . O11 O 0.2282(2) 0.33694(16) 0.09564(19) 0.0214(6) Uani 1 1 d . . . C11 C 0.2507(3) 0.4530(2) 0.3802(3) 0.0198(8) Uani 1 1 d . . . O12 O 0.3255(2) 0.50169(18) 0.4493(2) 0.0324(7) Uani 1 1 d . . . C12 C 0.2856(3) 0.4018(2) 0.1478(3) 0.0214(9) Uani 1 1 d . . . O13 O 0.1909(2) 0.40246(17) 0.3969(2) 0.0251(6) Uani 1 1 d . . . C13 C 0.1210(3) -0.0191(2) 0.1238(3) 0.0234(9) Uani 1 1 d . . . O14 O 0.28907(19) 0.30598(15) 0.27523(19) 0.0189(6) Uani 1 1 d . . . C14 C 0.2203(3) -0.0275(2) 0.2197(3) 0.0246(9) Uani 1 1 d . . . H14A H 0.2651 -0.0767 0.2152 0.030 Uiso 1 1 calc R . . H14B H 0.2001 -0.0408 0.2738 0.030 Uiso 1 1 calc R . . O15 O 0.1276(2) 0.00092(18) 0.0471(2) 0.0330(7) Uani 1 1 d . . . C15 C 0.2842(3) 0.0602(2) 0.2416(3) 0.0196(8) Uani 1 1 d . . . O16 O 0.0297(2) -0.03347(19) 0.1292(2) 0.0332(7) Uani 1 1 d . . . H16 H -0.028(4) -0.029(3) 0.063(4) 0.071(18) Uiso 1 1 d . . . C16 C 0.3913(3) 0.0578(3) 0.3355(3) 0.0258(9) Uani 1 1 d . . . H16A H 0.4300 0.0034 0.3330 0.031 Uiso 1 1 calc R . . H16B H 0.4348 0.1089 0.3330 0.031 Uiso 1 1 calc R . . O17 O 0.3030(2) 0.01901(19) 0.4377(2) 0.0316(7) Uani 1 1 d . . . C17 C 0.3862(3) 0.0597(2) 0.4336(3) 0.0244(9) Uani 1 1 d . . . O18 O 0.4555(2) 0.09631(18) 0.5056(2) 0.0326(7) Uani 1 1 d . . . C18 C 0.3145(3) 0.0840(2) 0.1575(3) 0.0219(9) Uani 1 1 d . . . O19 O 0.3662(2) 0.03081(17) 0.1317(2) 0.0278(7) Uani 1 1 d . . . O20 O 0.28692(19) 0.16344(16) 0.12262(19) 0.0200(6) Uani 1 1 d . . . O21 O 0.21725(19) 0.13088(15) 0.24705(19) 0.0178(6) Uani 1 1 d . . . O22 O 0.1606(3) 0.1928(2) 0.3946(3) 0.0441(10) Uani 1 1 d . . . H22A H 0.177(3) 0.160(3) 0.367(3) 0.020(13) Uiso 1 1 d . . . H22B H 0.186(6) 0.174(4) 0.449(5) 0.10(3) Uiso 1 1 d . . . O23 O 0.3889(3) 0.2828(2) 0.5056(3) 0.0374(8) Uani 1 1 d . . . H23B H 0.342(4) 0.307(3) 0.534(4) 0.066(17) Uiso 1 1 d . . . H23A H 0.342(5) 0.277(4) 0.445(5) 0.08(2) Uiso 1 1 d . . . O24 O 0.6270(3) 0.2497(3) 0.5870(3) 0.0538(10) Uani 1 1 d . . . H24A H 0.667(5) 0.287(4) 0.634(5) 0.062(19) Uiso 1 1 d . . . H24B H 0.590(7) 0.278(5) 0.518(7) 0.14(3) Uiso 1 1 d . . . O25 O 0.6767(3) 0.1602(2) 0.3511(3) 0.0512(11) Uani 1 1 d . . . H25A H 0.727(5) 0.175(4) 0.346(5) 0.09(3) Uiso 1 1 d . . . H25B H 0.665(7) 0.097(6) 0.355(6) 0.14(3) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.0152(4) 0.0199(4) 0.0162(4) -0.0002(3) 0.0081(3) -0.0006(3) Li1 0.025(4) 0.033(4) 0.027(4) -0.002(3) 0.007(3) -0.003(3) Li2 0.026(4) 0.044(4) 0.029(4) -0.002(3) 0.014(3) -0.006(3) O1 0.0334(17) 0.0415(17) 0.0325(18) -0.0089(14) 0.0213(15) -0.0155(14) C1 0.018(2) 0.0195(19) 0.018(2) 0.0034(16) 0.0075(17) 0.0007(16) O2 0.0251(15) 0.0268(14) 0.0227(16) -0.0063(12) 0.0109(13) -0.0104(12) C2 0.021(2) 0.022(2) 0.021(2) -0.0002(16) 0.0093(18) -0.0012(16) O3 0.0184(14) 0.0251(14) 0.0216(16) -0.0005(11) 0.0098(12) 0.0016(11) C3 0.0141(18) 0.024(2) 0.014(2) 0.0002(16) 0.0049(16) -0.0010(15) O4 0.0164(14) 0.0299(15) 0.0170(15) -0.0016(12) 0.0046(12) -0.0024(11) C4 0.023(2) 0.0141(18) 0.022(2) 0.0022(16) 0.0116(19) -0.0009(16) O5 0.085(3) 0.0263(16) 0.062(2) 0.0006(16) 0.060(2) -0.0011(16) C5 0.026(2) 0.023(2) 0.028(2) 0.0035(18) 0.015(2) 0.0049(17) O6 0.079(3) 0.0244(16) 0.059(2) -0.0064(15) 0.055(2) -0.0074(16) C6 0.020(2) 0.021(2) 0.026(2) 0.0034(17) 0.0128(18) 0.0028(16) O7 0.0160(13) 0.0209(13) 0.0168(14) -0.0009(11) 0.0050(11) -0.0009(10) C7 0.019(2) 0.035(2) 0.021(2) -0.0015(19) 0.0088(18) -0.0082(18) O8 0.0399(19) 0.056(2) 0.0226(18) 0.0079(15) 0.0152(15) 0.0145(16) C8 0.022(2) 0.033(2) 0.020(2) -0.0046(18) 0.0103(18) -0.0068(17) O9 0.0346(17) 0.0493(18) 0.0245(18) 0.0014(14) 0.0143(15) 0.0071(14) C9 0.018(2) 0.0207(19) 0.016(2) -0.0037(16) 0.0069(17) -0.0047(15) O10 0.0371(17) 0.0251(14) 0.0246(17) 0.0000(12) 0.0165(14) -0.0070(12) C10 0.028(2) 0.0205(19) 0.022(2) -0.0027(17) 0.0122(19) -0.0015(17) O11 0.0251(15) 0.0217(14) 0.0165(15) -0.0041(12) 0.0082(12) -0.0049(12) C11 0.024(2) 0.0197(19) 0.018(2) 0.0005(16) 0.0111(18) 0.0022(17) O12 0.0349(17) 0.0401(16) 0.0210(17) -0.0064(13) 0.0109(14) -0.0140(14) C12 0.020(2) 0.023(2) 0.025(2) -0.0008(18) 0.0128(19) -0.0003(17) O13 0.0258(15) 0.0292(15) 0.0220(16) -0.0019(12) 0.0122(13) -0.0032(12) C13 0.026(2) 0.0138(19) 0.029(3) -0.0044(17) 0.0112(19) -0.0035(16) O14 0.0177(14) 0.0204(13) 0.0208(15) 0.0013(11) 0.0103(12) -0.0003(10) C14 0.028(2) 0.022(2) 0.022(2) 0.0026(17) 0.0086(19) 0.0032(17) O15 0.0333(17) 0.0375(17) 0.0235(18) 0.0054(13) 0.0078(14) -0.0062(13) C15 0.0170(19) 0.0222(19) 0.020(2) 0.0006(16) 0.0079(17) 0.0039(15) O16 0.0245(17) 0.0453(18) 0.0270(19) 0.0006(14) 0.0083(15) 0.0000(14) C16 0.022(2) 0.037(2) 0.018(2) 0.0014(18) 0.0073(18) 0.0039(17) O17 0.0269(16) 0.0449(18) 0.0252(17) -0.0006(13) 0.0131(14) -0.0034(13) C17 0.028(2) 0.021(2) 0.023(2) 0.0022(18) 0.009(2) 0.0099(18) O18 0.0329(17) 0.0374(17) 0.0219(17) -0.0043(14) 0.0065(14) 0.0015(14) C18 0.017(2) 0.027(2) 0.019(2) -0.0019(17) 0.0059(17) 0.0006(17) O19 0.0265(16) 0.0372(16) 0.0220(16) 0.0058(13) 0.0125(13) 0.0164(13) O20 0.0195(14) 0.0220(13) 0.0207(15) 0.0020(11) 0.0109(12) 0.0030(11) O21 0.0185(13) 0.0223(13) 0.0172(15) 0.0001(11) 0.0120(12) 0.0014(11) O22 0.072(3) 0.039(2) 0.028(2) 0.0064(17) 0.028(2) 0.0256(18) O23 0.0318(18) 0.049(2) 0.036(2) 0.0033(16) 0.0193(18) 0.0123(15) O24 0.033(2) 0.088(3) 0.035(2) -0.002(2) 0.0096(18) -0.0171(19) O25 0.052(2) 0.040(2) 0.083(3) 0.0126(19) 0.049(2) 0.0081(18) _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 O14 1.850(3) . ? Ti1 O21 1.861(3) . ? Ti1 O7 1.915(3) . ? Ti1 O3 2.010(3) . ? Ti1 O20 2.028(3) . ? Ti1 O11 2.070(3) . ? Ti1 Li1 3.356(7) . ? Li1 O22 1.869(8) . ? Li1 O13 1.930(7) . ? Li1 O7 2.030(8) . ? Li1 O2 2.033(7) . ? Li2 O23 1.889(8) . ? Li2 O18 1.923(8) . ? Li2 O24 1.949(8) . ? Li2 O9 1.955(8) 4_566 ? O1 C1 1.220(4) . ? C1 O2 1.308(4) . ? C1 C2 1.505(5) . ? C2 C3 1.536(5) . ? O3 C4 1.291(4) . ? C3 O7 1.419(4) . ? C3 C6 1.528(5) . ? C3 C4 1.541(5) . ? O4 C4 1.234(5) . ? O5 C5 1.203(5) . ? C5 O6 1.303(5) . ? C5 C6 1.493(5) . ? C7 O9 1.213(5) . ? C7 O8 1.311(5) . ? C7 C8 1.489(5) . ? C8 C9 1.532(5) . ? O9 Li2 1.955(8) 4_565 ? C9 O14 1.421(4) . ? C9 C12 1.520(5) . ? C9 C10 1.548(5) . ? O10 C12 1.243(4) . ? C10 C11 1.495(5) . ? O11 C12 1.280(4) . ? C11 O13 1.217(4) . ? C11 O12 1.318(5) . ? C13 O15 1.224(5) . ? C13 O16 1.307(5) . ? C13 C14 1.498(6) . ? C14 C15 1.531(5) . ? C15 O21 1.425(4) . ? C15 C18 1.523(5) . ? C15 C16 1.534(5) . ? C16 C17 1.496(5) . ? O17 C17 1.319(5) . ? C17 O18 1.216(5) . ? C18 O19 1.233(4) . ? C18 O20 1.285(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O14 Ti1 O21 96.25(12) . . ? O14 Ti1 O7 91.88(11) . . ? O21 Ti1 O7 96.44(10) . . ? O14 Ti1 O3 157.37(11) . . ? O21 Ti1 O3 105.10(11) . . ? O7 Ti1 O3 78.54(11) . . ? O14 Ti1 O20 106.44(11) . . ? O21 Ti1 O20 78.89(11) . . ? O7 Ti1 O20 161.43(11) . . ? O3 Ti1 O20 85.30(11) . . ? O14 Ti1 O11 78.33(11) . . ? O21 Ti1 O11 157.93(10) . . ? O7 Ti1 O11 105.05(11) . . ? O3 Ti1 O11 84.38(11) . . ? O20 Ti1 O11 82.16(10) . . ? O14 Ti1 Li1 65.66(14) . . ? O21 Ti1 Li1 80.36(14) . . ? O7 Ti1 Li1 32.77(14) . . ? O3 Ti1 Li1 110.21(14) . . ? O20 Ti1 Li1 156.79(14) . . ? O11 Ti1 Li1 115.55(14) . . ? O22 Li1 O13 112.5(4) . . ? O22 Li1 O7 100.6(3) . . ? O13 Li1 O7 115.4(4) . . ? O22 Li1 O2 96.6(3) . . ? O13 Li1 O2 133.6(4) . . ? O7 Li1 O2 92.3(3) . . ? O22 Li1 Ti1 81.6(3) . . ? O13 Li1 Ti1 101.6(3) . . ? O7 Li1 Ti1 30.71(13) . . ? O2 Li1 Ti1 118.3(3) . . ? O23 Li2 O18 100.6(4) . . ? O23 Li2 O24 102.8(4) . . ? O18 Li2 O24 107.9(4) . . ? O23 Li2 O9 116.6(4) . 4_566 ? O18 Li2 O9 110.4(4) . 4_566 ? O24 Li2 O9 117.0(4) . 4_566 ? O1 C1 O2 121.5(3) . . ? O1 C1 C2 121.2(3) . . ? O2 C1 C2 117.3(3) . . ? C1 O2 Li1 125.4(3) . . ? C1 C2 C3 116.3(3) . . ? C4 O3 Ti1 118.8(2) . . ? O7 C3 C6 110.4(3) . . ? O7 C3 C2 110.6(3) . . ? C6 C3 C2 110.9(3) . . ? O7 C3 C4 106.5(3) . . ? C6 C3 C4 109.9(3) . . ? C2 C3 C4 108.5(3) . . ? O4 C4 O3 124.8(4) . . ? O4 C4 C3 121.2(3) . . ? O3 C4 C3 114.0(3) . . ? O5 C5 O6 122.9(4) . . ? O5 C5 C6 123.0(4) . . ? O6 C5 C6 114.1(4) . . ? C5 C6 C3 111.1(3) . . ? C3 O7 Ti1 120.7(2) . . ? C3 O7 Li1 118.0(3) . . ? Ti1 O7 Li1 116.5(2) . . ? O9 C7 O8 122.1(4) . . ? O9 C7 C8 123.5(4) . . ? O8 C7 C8 114.4(4) . . ? C7 C8 C9 111.5(3) . . ? C7 O9 Li2 177.3(4) . 4_565 ? O14 C9 C12 106.8(3) . . ? O14 C9 C8 108.8(3) . . ? C12 C9 C8 112.4(3) . . ? O14 C9 C10 110.6(3) . . ? C12 C9 C10 104.5(3) . . ? C8 C9 C10 113.5(3) . . ? C11 C10 C9 111.7(3) . . ? C12 O11 Ti1 116.3(2) . . ? O13 C11 O12 123.3(4) . . ? O13 C11 C10 122.9(3) . . ? O12 C11 C10 113.7(3) . . ? O10 C12 O11 124.7(4) . . ? O10 C12 C9 120.6(3) . . ? O11 C12 C9 114.5(3) . . ? C11 O13 Li1 138.1(3) . . ? O15 C13 O16 123.8(4) . . ? O15 C13 C14 120.6(4) . . ? O16 C13 C14 115.6(4) . . ? C9 O14 Ti1 122.0(2) . . ? C13 C14 C15 109.6(3) . . ? O21 C15 C18 106.6(3) . . ? O21 C15 C14 108.8(3) . . ? C18 C15 C14 111.0(3) . . ? O21 C15 C16 110.7(3) . . ? C18 C15 C16 105.2(3) . . ? C14 C15 C16 114.3(3) . . ? C17 C16 C15 117.5(3) . . ? O18 C17 O17 122.2(4) . . ? O18 C17 C16 121.6(4) . . ? O17 C17 C16 116.3(4) . . ? C17 O18 Li2 146.1(3) . . ? O19 C18 O20 125.3(4) . . ? O19 C18 C15 120.3(3) . . ? O20 C18 C15 114.3(3) . . ? C18 O20 Ti1 117.4(2) . . ? C15 O21 Ti1 122.1(2) . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 25.10 _diffrn_measured_fraction_theta_full 0.983 _refine_diff_density_max 0.584 _refine_diff_density_min -0.441 _refine_diff_density_rms 0.096 # Attachment '0708281.cif' data_0708281 _database_code_depnum_ccdc_archive 'CCDC 664369' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H16 Li2 N4 O41 Ti4' _chemical_formula_weight 1221.89 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' Li Li -0.0003 0.0001 '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 13.123(6) _cell_length_b 15.486(7) _cell_length_c 15.608(8) _cell_angle_alpha 84.250(12) _cell_angle_beta 82.297(11) _cell_angle_gamma 66.054(11) _cell_volume 2869(2) _cell_formula_units_Z 2 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.414 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1220 _exptl_absorpt_coefficient_mu 0.637 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9390 _exptl_absorpt_correction_T_max 0.9688 _exptl_absorpt_process_details ? _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 'Bruker axs CCD 1000' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13687 _diffrn_reflns_av_R_equivalents 0.0624 _diffrn_reflns_av_sigmaI/netI 0.1294 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.05 _diffrn_reflns_theta_max 25.00 _reflns_number_total 9616 _reflns_number_gt 5840 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1996)' _computing_cell_refinement 'SAINT (Siemens, 1996)' _computing_data_reduction 'SAINT (Siemens, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Siemens, 1996)' _computing_publication_material 'SHELXTL (Siemens, 1996)' _refine_special_details ; The atoms Li1 und Li2 are restrained so that Uij components approximate to isotropic behavior ; _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^)+(0.1323P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 9616 _refine_ls_number_parameters 676 _refine_ls_number_restraints 12 _refine_ls_R_factor_all 0.1065 _refine_ls_R_factor_gt 0.0770 _refine_ls_wR_factor_ref 0.2187 _refine_ls_wR_factor_gt 0.2023 _refine_ls_goodness_of_fit_ref 0.927 _refine_ls_restrained_S_all 0.927 _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 0.42867(8) 0.63293(7) -0.14990(6) 0.0196(3) Uani 1 1 d . . . Ti2 Ti 0.34332(9) 0.46365(8) -0.12999(6) 0.0211(3) Uani 1 1 d . . . C1 C 0.5029(5) 0.4109(5) -0.2955(4) 0.0280(14) Uani 1 1 d . . . O1 O 0.4104(3) 0.4225(3) -0.2500(3) 0.0302(10) Uani 1 1 d . . . C2 C 0.6031(5) 0.4044(5) -0.2533(4) 0.0250(13) Uani 1 1 d . . . H2A H 0.6248 0.4560 -0.2779 0.030 Uiso 1 1 calc R . . H2B H 0.6658 0.3447 -0.2681 0.030 Uiso 1 1 calc R . . O2 O 0.5137(4) 0.4065(4) -0.3742(3) 0.0525(15) Uani 1 1 d . . . O3 O 0.4843(3) 0.4910(3) -0.1335(2) 0.0178(8) Uani 1 1 d . . . C3 C 0.5850(5) 0.4094(4) -0.1550(4) 0.0208(12) Uani 1 1 d . . . C4 C 0.5640(5) 0.3218(5) -0.1177(4) 0.0259(14) Uani 1 1 d . . . O4 O 0.4635(3) 0.3362(3) -0.0872(3) 0.0264(9) Uani 1 1 d . . . O5 O 0.6421(4) 0.2418(3) -0.1197(3) 0.0321(10) Uani 1 1 d . . . C5 C 0.6650(5) 0.4260(4) -0.0235(4) 0.0207(12) Uani 1 1 d . . . C6 C 0.6847(5) 0.4131(4) -0.1200(3) 0.0200(12) Uani 1 1 d . . . H6A H 0.7010 0.4656 -0.1498 0.024 Uiso 1 1 calc R . . H6B H 0.7503 0.3543 -0.1322 0.024 Uiso 1 1 calc R . . O6 O 0.6251(3) 0.3717(3) 0.0232(2) 0.0220(9) Uani 1 1 d . . . C7 C 0.3914(5) 0.6358(4) -0.3412(4) 0.0300(15) Uani 1 1 d . . . O7 O 0.6876(3) 0.4882(3) 0.0066(2) 0.0236(9) Uani 1 1 d . . . C8 C 0.2705(6) 0.6453(5) -0.3181(4) 0.0318(15) Uani 1 1 d . . . H8A H 0.2667 0.5854 -0.3289 0.038 Uiso 1 1 calc R . . H8B H 0.2230 0.6942 -0.3571 0.038 Uiso 1 1 calc R . . O8 O 0.4504(3) 0.6337(3) -0.2805(3) 0.0291(10) Uani 1 1 d . . . C9 C 0.2211(5) 0.6703(4) -0.2241(4) 0.0223(13) Uani 1 1 d . . . O9 O 0.4284(4) 0.6305(4) -0.4174(3) 0.0454(13) Uani 1 1 d . . . O10 O 0.2962(3) 0.6007(3) -0.1689(2) 0.0217(9) Uani 1 1 d . . . C10 C 0.2196(5) 0.7648(5) -0.2073(4) 0.0277(14) Uani 1 1 d . . . C11 C 0.1038(5) 0.6729(5) -0.2083(4) 0.0305(15) Uani 1 1 d . . . H11A H 0.0581 0.7172 -0.2512 0.037 Uiso 1 1 calc R . . H11B H 0.1069 0.6100 -0.2166 0.037 Uiso 1 1 calc R . . O11 O 0.2953(3) 0.7645(3) -0.1635(3) 0.0262(9) Uani 1 1 d . . . C12 C 0.0486(5) 0.7020(5) -0.1200(4) 0.0317(15) Uani 1 1 d . . . O12 O 0.1509(4) 0.8390(3) -0.2399(3) 0.0366(11) Uani 1 1 d . . . C13 C 1.0161(6) 0.6959(5) 0.2259(4) 0.0324(15) Uani 1 1 d . . . O13 O 0.0831(4) 0.7360(4) -0.0703(3) 0.0533(15) Uani 1 1 d . . . C14 C 0.9829(6) 0.6133(5) 0.2400(4) 0.0299(14) Uani 1 1 d . . . H14A H 1.0163 0.5729 0.1907 0.036 Uiso 1 1 calc R . . H14B H 0.9013 0.6371 0.2407 0.036 Uiso 1 1 calc R . . O14 O -0.0426(4) 0.6863(4) -0.0993(3) 0.0544(15) Uani 1 1 d . . . O15 O 0.4982(3) 0.7159(3) -0.1472(3) 0.0273(10) Uani 1 1 d . . . C15 C 1.0171(5) 0.5522(4) 0.3236(4) 0.0216(13) Uani 1 1 d . . . O16 O 0.5750(3) 0.6173(3) -0.1419(3) 0.0271(10) Uani 1 1 d . . . C16 C 1.1457(5) 0.5101(4) 0.3174(4) 0.0234(13) Uani 1 1 d . . . O17 O 0.2637(4) 0.3865(4) -0.1061(3) 0.0426(12) Uani 1 1 d . . . O18 O 0.1957(4) 0.4805(3) -0.1390(3) 0.0413(12) Uani 1 1 d . . . Ti3 Ti 0.83364(8) 0.69378(7) 0.45972(7) 0.0211(3) Uani 1 1 d . . . Ti4 Ti 1.08932(9) 0.66874(7) 0.41606(7) 0.0215(3) Uani 1 1 d . . . C17 C 0.9740(5) 0.4739(4) 0.3336(4) 0.0220(13) Uani 1 1 d . . . H17A H 0.8931 0.5022 0.3293 0.026 Uiso 1 1 calc R . . H17B H 1.0094 0.4318 0.2855 0.026 Uiso 1 1 calc R . . C18 C 0.9959(5) 0.4160(4) 0.4173(4) 0.0209(13) Uani 1 1 d . . . C19 C 0.9965(5) 0.8605(4) 0.5859(4) 0.0305(15) Uani 1 1 d . . . O19 O 0.9991(5) 0.7427(4) 0.1573(3) 0.0576(16) Uani 1 1 d . . . C20 C 0.9606(6) 0.9000(4) 0.4982(4) 0.0301(15) Uani 1 1 d . . . H20A H 1.0275 0.8872 0.4568 0.036 Uiso 1 1 calc R . . H20B H 0.9203 0.9688 0.5001 0.036 Uiso 1 1 calc R . . O20 O 1.0609(4) 0.7171(3) 0.2847(3) 0.0312(10) Uani 1 1 d . . . C21 C 0.8868(6) 0.8597(4) 0.4664(4) 0.0296(15) Uani 1 1 d . . . O21 O 0.9778(3) 0.6109(3) 0.3950(2) 0.0213(9) Uani 1 1 d . . . C22 C 0.7816(5) 0.8754(5) 0.5281(5) 0.0338(16) Uani 1 1 d . . . O22 O 1.2019(4) 0.4484(3) 0.2658(3) 0.0340(11) Uani 1 1 d . . . C23 C 0.8512(6) 0.9070(5) 0.3763(4) 0.0341(16) Uani 1 1 d . . . H23A H 0.8018 0.9736 0.3840 0.041 Uiso 1 1 calc R . . H23B H 0.9185 0.9054 0.3394 0.041 Uiso 1 1 calc R . . O23 O 1.1894(3) 0.5444(3) 0.3680(3) 0.0264(9) Uani 1 1 d . . . C24 C 0.7927(6) 0.8634(5) 0.3296(4) 0.0367(17) Uani 1 1 d . . . O24 O 1.0981(3) 0.3809(3) 0.4347(2) 0.0237(9) Uani 1 1 d . . . O25 O 0.9163(3) 0.4047(3) 0.4630(3) 0.0241(9) Uani 1 1 d . . . O26 O 1.0801(4) 0.8828(3) 0.6045(3) 0.0445(13) Uani 1 1 d . . . O27 O 0.9561(4) 0.8165(4) 0.6362(3) 0.0443(13) Uani 1 1 d . . . O28 O 0.9436(3) 0.7603(3) 0.4588(3) 0.0238(9) Uani 1 1 d . . . O29 O 0.7481(3) 0.8074(3) 0.5382(3) 0.0297(10) Uani 1 1 d . . . O30 O 0.7296(4) 0.9528(4) 0.5618(4) 0.0514(14) Uani 1 1 d . . . O31 O 0.7838(4) 0.7862(3) 0.3580(3) 0.0306(10) Uani 1 1 d . . . O32 O 0.7562(5) 0.9026(4) 0.2610(4) 0.0664(18) Uani 1 1 d . . . O33 O 0.6934(3) 0.6866(3) 0.4850(3) 0.0312(10) Uani 1 1 d . . . O34 O 0.7714(3) 0.6145(3) 0.4261(3) 0.0305(10) Uani 1 1 d . . . O35 O 1.1760(4) 0.7375(3) 0.3872(3) 0.0361(11) Uani 1 1 d . . . O36 O 1.1893(4) 0.6917(3) 0.4745(3) 0.0334(11) Uani 1 1 d . . . Li1 Li 0.1949(11) 0.9291(9) 0.3494(9) 0.050(3) Uani 1 1 d U . . Li2 Li 0.7605(12) 0.1282(10) 0.0168(9) 0.056(3) Uani 1 1 d U . . N1 N 0.3446(8) 0.7927(6) 0.4585(5) 0.083(3) Uani 1 1 d . . . N2 N 0.2344(6) 0.3578(6) 0.1037(4) 0.061(2) Uani 1 1 d . . . N3 N 0.1408(6) 0.8541(5) 0.2147(5) 0.0537(18) Uani 1 1 d . . . N4 N 0.3978(7) 0.2041(5) 0.0098(6) 0.071(2) Uani 1 1 d . . . OW1 O 0.6405(4) 0.5098(4) 0.5014(3) 0.0496(13) Uani 1 1 d . . . OW2 O 0.8570(5) 0.7311(4) 0.0560(4) 0.0603(15) Uani 1 1 d . . . OW3 O 0.3762(5) 0.2875(5) 0.3266(4) 0.0686(17) Uani 1 1 d . . . OW4 O 0.2193(6) 0.2230(5) 0.2542(5) 0.085(2) Uani 1 1 d . . . OW5 O 0.4174(11) 0.8977(9) 0.1707(12) 0.231(8) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.0225(5) 0.0274(6) 0.0158(5) 0.0017(4) -0.0088(4) -0.0156(5) Ti2 0.0246(6) 0.0281(6) 0.0183(5) -0.0008(4) -0.0069(4) -0.0169(5) C1 0.036(4) 0.039(4) 0.014(3) 0.000(3) -0.013(3) -0.018(3) O1 0.031(2) 0.044(3) 0.025(2) -0.007(2) -0.011(2) -0.021(2) C2 0.025(3) 0.033(4) 0.017(3) -0.003(3) -0.004(2) -0.011(3) O2 0.036(3) 0.093(4) 0.024(3) -0.010(3) -0.010(2) -0.017(3) O3 0.0173(19) 0.028(2) 0.0131(19) 0.0003(16) -0.0059(15) -0.0134(17) C3 0.019(3) 0.026(3) 0.017(3) -0.006(2) -0.002(2) -0.007(3) C4 0.037(4) 0.031(4) 0.016(3) -0.002(3) -0.010(3) -0.017(3) O4 0.023(2) 0.031(3) 0.029(2) 0.0018(19) -0.0028(18) -0.0154(19) O5 0.035(3) 0.027(3) 0.035(3) 0.000(2) -0.010(2) -0.012(2) C5 0.019(3) 0.026(3) 0.020(3) -0.002(2) -0.008(2) -0.010(3) C6 0.024(3) 0.022(3) 0.018(3) 0.000(2) -0.005(2) -0.013(3) O6 0.023(2) 0.032(2) 0.018(2) -0.0054(17) -0.0022(16) -0.0176(19) C7 0.037(4) 0.029(4) 0.020(3) 0.002(3) -0.013(3) -0.007(3) O7 0.028(2) 0.032(2) 0.016(2) -0.0010(17) -0.0071(17) -0.0166(19) C8 0.044(4) 0.039(4) 0.019(3) 0.005(3) -0.019(3) -0.020(3) O8 0.034(2) 0.044(3) 0.017(2) 0.0044(19) -0.0079(18) -0.024(2) C9 0.027(3) 0.025(3) 0.024(3) 0.005(3) -0.020(3) -0.015(3) O9 0.042(3) 0.071(4) 0.016(2) -0.004(2) -0.004(2) -0.015(3) O10 0.024(2) 0.031(2) 0.016(2) 0.0026(17) -0.0091(16) -0.0147(18) C10 0.028(3) 0.035(4) 0.017(3) 0.000(3) -0.006(3) -0.009(3) C11 0.032(3) 0.031(4) 0.034(4) 0.002(3) -0.016(3) -0.015(3) O11 0.029(2) 0.027(2) 0.029(2) -0.0025(18) -0.0158(19) -0.0139(19) C12 0.027(3) 0.043(4) 0.031(4) 0.005(3) -0.012(3) -0.019(3) O12 0.041(3) 0.033(3) 0.038(3) 0.001(2) -0.022(2) -0.012(2) C13 0.037(4) 0.036(4) 0.027(4) 0.006(3) -0.009(3) -0.018(3) O13 0.050(3) 0.094(5) 0.037(3) -0.027(3) 0.006(2) -0.049(3) C14 0.040(4) 0.034(4) 0.021(3) 0.006(3) -0.011(3) -0.018(3) O14 0.036(3) 0.097(5) 0.047(3) -0.007(3) 0.001(2) -0.045(3) O15 0.030(2) 0.025(2) 0.033(2) 0.0014(19) -0.0110(19) -0.017(2) C15 0.029(3) 0.024(3) 0.014(3) 0.001(2) -0.005(2) -0.012(3) O16 0.026(2) 0.029(3) 0.034(2) 0.0029(19) -0.0108(19) -0.0178(19) C16 0.023(3) 0.028(4) 0.022(3) 0.003(3) -0.004(3) -0.013(3) O17 0.040(3) 0.057(3) 0.042(3) 0.008(2) -0.017(2) -0.029(3) O18 0.039(3) 0.046(3) 0.050(3) 0.010(2) -0.019(2) -0.027(2) Ti3 0.0215(5) 0.0237(6) 0.0225(6) 0.0019(4) -0.0089(4) -0.0123(5) Ti4 0.0233(6) 0.0248(6) 0.0225(6) 0.0032(4) -0.0082(4) -0.0151(5) C17 0.024(3) 0.024(3) 0.018(3) -0.004(2) -0.002(2) -0.010(3) C18 0.029(3) 0.022(3) 0.020(3) -0.005(2) -0.008(3) -0.015(3) C19 0.035(4) 0.022(4) 0.039(4) 0.006(3) -0.019(3) -0.012(3) O19 0.093(4) 0.059(4) 0.040(3) 0.029(3) -0.031(3) -0.050(3) C20 0.040(4) 0.018(3) 0.038(4) 0.001(3) -0.022(3) -0.012(3) O20 0.042(3) 0.034(3) 0.027(2) 0.0062(19) -0.009(2) -0.024(2) C21 0.045(4) 0.026(4) 0.030(3) 0.000(3) -0.019(3) -0.022(3) O21 0.024(2) 0.028(2) 0.017(2) 0.0014(17) -0.0054(17) -0.0162(18) C22 0.031(4) 0.026(4) 0.042(4) -0.008(3) -0.016(3) -0.003(3) O22 0.034(2) 0.046(3) 0.024(2) -0.009(2) 0.004(2) -0.019(2) C23 0.041(4) 0.027(4) 0.039(4) 0.008(3) -0.022(3) -0.015(3) O23 0.024(2) 0.027(2) 0.032(2) -0.0030(19) -0.0087(18) -0.0115(19) C24 0.041(4) 0.033(4) 0.039(4) 0.013(3) -0.026(3) -0.014(3) O24 0.023(2) 0.030(2) 0.022(2) 0.0004(18) -0.0065(17) -0.0140(18) O25 0.027(2) 0.028(2) 0.025(2) 0.0059(18) -0.0106(18) -0.0188(19) O26 0.064(3) 0.041(3) 0.051(3) 0.019(2) -0.040(3) -0.037(3) O27 0.057(3) 0.055(3) 0.036(3) 0.014(2) -0.023(2) -0.037(3) O28 0.032(2) 0.021(2) 0.027(2) 0.0052(17) -0.0157(18) -0.0162(19) O29 0.030(2) 0.024(2) 0.035(3) -0.0049(19) -0.005(2) -0.009(2) O30 0.044(3) 0.040(3) 0.070(4) -0.023(3) -0.001(3) -0.014(3) O31 0.034(2) 0.029(3) 0.035(3) 0.008(2) -0.021(2) -0.016(2) O32 0.098(5) 0.076(4) 0.055(4) 0.034(3) -0.056(3) -0.059(4) O33 0.024(2) 0.037(3) 0.036(3) -0.009(2) -0.0024(19) -0.014(2) O34 0.028(2) 0.034(3) 0.037(3) -0.005(2) -0.005(2) -0.019(2) O35 0.037(3) 0.044(3) 0.037(3) 0.009(2) -0.012(2) -0.027(2) O36 0.035(2) 0.043(3) 0.035(3) 0.009(2) -0.014(2) -0.027(2) Li1 0.051(3) 0.049(3) 0.049(3) -0.0035(10) -0.0062(11) -0.0198(16) Li2 0.057(4) 0.055(4) 0.055(4) -0.0032(10) -0.0063(11) -0.0213(17) N1 0.120(7) 0.095(7) 0.068(5) 0.020(5) -0.037(5) -0.074(6) N2 0.066(5) 0.119(7) 0.036(4) -0.013(4) -0.004(3) -0.073(5) N3 0.062(4) 0.050(4) 0.067(5) 0.029(3) -0.029(4) -0.041(3) N4 0.080(5) 0.046(4) 0.092(6) 0.016(4) -0.007(5) -0.035(4) OW1 0.054(3) 0.060(4) 0.044(3) -0.004(3) -0.013(3) -0.029(3) OW2 0.053(3) 0.091(5) 0.045(3) 0.010(3) -0.011(3) -0.037(3) OW3 0.055(4) 0.089(5) 0.065(4) -0.001(3) -0.002(3) -0.034(3) OW4 0.091(5) 0.106(6) 0.079(5) 0.020(4) -0.019(4) -0.063(5) OW5 0.171(12) 0.161(12) 0.39(2) -0.127(13) -0.066(13) -0.065(10) _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 O16 1.855(4) . ? Ti1 O15 1.859(4) . ? Ti1 O6 2.014(4) 2_665 ? Ti1 O3 2.016(4) . ? Ti1 O8 2.019(4) . ? Ti1 O10 2.057(4) . ? Ti1 O11 2.092(4) . ? Ti1 Ti2 3.2174(18) . ? Ti2 O17 1.865(5) . ? Ti2 O18 1.870(5) . ? Ti2 O1 2.008(4) . ? Ti2 O10 2.008(4) . ? Ti2 O3 2.052(4) . ? Ti2 O7 2.065(4) 2_665 ? Ti2 O4 2.078(4) . ? C1 O2 1.224(7) . ? C1 O1 1.276(7) . ? C1 C2 1.511(8) . ? C2 C3 1.525(8) . ? O3 C3 1.437(7) . ? C3 C6 1.508(7) . ? C3 C4 1.535(8) . ? C4 O5 1.247(8) . ? C4 O4 1.276(7) . ? C5 O7 1.263(7) . ? C5 O6 1.283(7) . ? C5 C6 1.514(8) . ? O6 Ti1 2.014(4) 2_665 ? C7 O9 1.220(8) . ? C7 O8 1.292(7) . ? C7 C8 1.530(9) . ? O7 Ti2 2.065(4) 2_665 ? C8 C9 1.542(9) . ? C9 O10 1.433(7) . ? C9 C10 1.505(8) . ? C9 C11 1.511(8) . ? C10 O12 1.247(7) . ? C10 O11 1.277(7) . ? C11 C12 1.489(9) . ? C12 O13 1.206(8) . ? C12 O14 1.309(7) . ? C13 O19 1.223(8) . ? C13 O20 1.286(8) . ? C13 C14 1.499(9) . ? C14 C15 1.538(8) . ? O15 O16 1.450(6) . ? C15 O21 1.416(7) . ? C15 C17 1.520(8) . ? C15 C16 1.536(8) . ? C16 O22 1.236(7) . ? C16 O23 1.300(7) . ? O17 O18 1.448(7) . ? Ti3 O34 1.873(4) . ? Ti3 O33 1.875(4) . ? Ti3 O21 2.005(4) . ? Ti3 O24 2.007(4) 2_766 ? Ti3 O31 2.015(4) . ? Ti3 O29 2.078(4) . ? Ti3 O28 2.084(4) . ? Ti3 Ti4 3.203(2) . ? Ti4 O35 1.838(4) . ? Ti4 O36 1.856(4) . ? Ti4 O28 1.938(4) . ? Ti4 O23 1.991(4) . ? Ti4 O21 2.075(4) . ? Ti4 O25 2.113(4) 2_766 ? Ti4 O20 2.139(4) . ? C17 C18 1.500(8) . ? C18 O25 1.247(7) . ? C18 O24 1.282(7) . ? C19 O27 1.198(8) . ? C19 O26 1.349(7) . ? C19 C20 1.498(9) . ? C20 C21 1.502(8) . ? C21 O28 1.421(8) . ? C21 C22 1.520(10) . ? C21 C23 1.556(9) . ? C22 O30 1.243(8) . ? C22 O29 1.285(8) . ? C23 C24 1.499(9) . ? C24 O32 1.231(8) . ? C24 O31 1.277(7) . ? O24 Ti3 2.007(4) 2_766 ? O25 Ti4 2.113(4) 2_766 ? O33 O34 1.472(6) . ? O35 O36 1.470(6) . ? 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 O16 Ti1 O15 45.96(18) . . ? O16 Ti1 O6 99.69(17) . 2_665 ? O15 Ti1 O6 98.52(17) . 2_665 ? O16 Ti1 O3 86.53(16) . . ? O15 Ti1 O3 132.27(17) . . ? O6 Ti1 O3 83.08(16) 2_665 . ? O16 Ti1 O8 93.03(18) . . ? O15 Ti1 O8 92.54(17) . . ? O6 Ti1 O8 166.90(16) 2_665 . ? O3 Ti1 O8 94.67(17) . . ? O16 Ti1 O10 159.57(18) . . ? O15 Ti1 O10 153.31(18) . . ? O6 Ti1 O10 85.32(15) 2_665 . ? O3 Ti1 O10 74.35(15) . . ? O8 Ti1 O10 81.66(15) . . ? O16 Ti1 O11 124.07(17) . . ? O15 Ti1 O11 78.14(17) . . ? O6 Ti1 O11 88.68(17) 2_665 . ? O3 Ti1 O11 149.30(15) . . ? O8 Ti1 O11 86.75(17) . . ? O10 Ti1 O11 75.54(16) . . ? O16 Ti1 Ti2 124.59(13) . . ? O15 Ti1 Ti2 168.96(13) . . ? O6 Ti1 Ti2 76.37(11) 2_665 . ? O3 Ti1 Ti2 38.13(10) . . ? O8 Ti1 Ti2 93.87(12) . . ? O10 Ti1 Ti2 37.15(11) . . ? O11 Ti1 Ti2 111.18(12) . . ? O17 Ti2 O18 45.6(2) . . ? O17 Ti2 O1 97.8(2) . . ? O18 Ti2 O1 98.9(2) . . ? O17 Ti2 O10 132.09(19) . . ? O18 Ti2 O10 86.56(18) . . ? O1 Ti2 O10 91.64(17) . . ? O17 Ti2 O3 153.15(19) . . ? O18 Ti2 O3 161.18(19) . . ? O1 Ti2 O3 81.82(15) . . ? O10 Ti2 O3 74.62(15) . . ? O17 Ti2 O7 95.41(19) . 2_665 ? O18 Ti2 O7 95.55(19) . 2_665 ? O1 Ti2 O7 164.90(16) . 2_665 ? O10 Ti2 O7 84.96(16) . 2_665 ? O3 Ti2 O7 83.09(15) . 2_665 ? O17 Ti2 O4 77.17(19) . . ? O18 Ti2 O4 122.79(18) . . ? O1 Ti2 O4 85.98(18) . . ? O10 Ti2 O4 150.59(15) . . ? O3 Ti2 O4 76.02(15) . . ? O7 Ti2 O4 89.78(17) 2_665 . ? O17 Ti2 Ti1 166.69(17) . . ? O18 Ti2 Ti1 124.07(15) . . ? O1 Ti2 Ti1 92.18(12) . . ? O10 Ti2 Ti1 38.20(11) . . ? O3 Ti2 Ti1 37.35(11) . . ? O7 Ti2 Ti1 76.07(11) 2_665 . ? O4 Ti2 Ti1 112.52(12) . . ? O2 C1 O1 122.0(5) . . ? O2 C1 C2 117.5(6) . . ? O1 C1 C2 120.5(5) . . ? C1 O1 Ti2 135.4(4) . . ? C1 C2 C3 115.2(5) . . ? C3 O3 Ti1 138.1(3) . . ? C3 O3 Ti2 112.0(3) . . ? Ti1 O3 Ti2 104.52(17) . . ? O3 C3 C6 111.6(4) . . ? O3 C3 C2 108.0(4) . . ? C6 C3 C2 111.2(4) . . ? O3 C3 C4 107.3(4) . . ? C6 C3 C4 111.2(5) . . ? C2 C3 C4 107.3(5) . . ? O5 C4 O4 123.4(6) . . ? O5 C4 C3 120.4(5) . . ? O4 C4 C3 116.2(5) . . ? C4 O4 Ti2 114.5(4) . . ? O7 C5 O6 123.9(5) . . ? O7 C5 C6 119.6(5) . . ? O6 C5 C6 116.5(5) . . ? C3 C6 C5 112.1(4) . . ? C5 O6 Ti1 132.5(4) . 2_665 ? O9 C7 O8 122.5(6) . . ? O9 C7 C8 117.9(5) . . ? O8 C7 C8 119.6(5) . . ? C5 O7 Ti2 130.8(4) . 2_665 ? C7 C8 C9 115.6(5) . . ? C7 O8 Ti1 136.1(4) . . ? O10 C9 C10 107.5(4) . . ? O10 C9 C11 112.5(5) . . ? C10 C9 C11 110.0(5) . . ? O10 C9 C8 106.8(5) . . ? C10 C9 C8 109.5(5) . . ? C11 C9 C8 110.5(5) . . ? C9 O10 Ti2 139.9(3) . . ? C9 O10 Ti1 112.3(3) . . ? Ti2 O10 Ti1 104.65(17) . . ? O12 C10 O11 122.4(6) . . ? O12 C10 C9 120.3(5) . . ? O11 C10 C9 117.1(5) . . ? C12 C11 C9 113.3(5) . . ? C10 O11 Ti1 114.8(4) . . ? O13 C12 O14 121.6(6) . . ? O13 C12 C11 124.7(6) . . ? O14 C12 C11 113.7(5) . . ? O19 C13 O20 121.2(6) . . ? O19 C13 C14 118.2(6) . . ? O20 C13 C14 120.6(5) . . ? C13 C14 C15 115.3(5) . . ? O16 O15 Ti1 66.9(2) . . ? O21 C15 C17 112.1(4) . . ? O21 C15 C16 107.0(4) . . ? C17 C15 C16 110.4(5) . . ? O21 C15 C14 109.2(5) . . ? C17 C15 C14 110.8(5) . . ? C16 C15 C14 107.1(5) . . ? O15 O16 Ti1 67.2(2) . . ? O22 C16 O23 123.5(5) . . ? O22 C16 C15 120.6(5) . . ? O23 C16 C15 115.9(5) . . ? O18 O17 Ti2 67.3(3) . . ? O17 O18 Ti2 67.0(3) . . ? O34 Ti3 O33 46.25(19) . . ? O34 Ti3 O21 86.73(18) . . ? O33 Ti3 O21 132.76(18) . . ? O34 Ti3 O24 99.58(18) . 2_766 ? O33 Ti3 O24 97.18(18) . 2_766 ? O21 Ti3 O24 84.83(16) . 2_766 ? O34 Ti3 O31 93.00(18) . . ? O33 Ti3 O31 92.89(18) . . ? O21 Ti3 O31 94.06(18) . . ? O24 Ti3 O31 167.27(16) 2_766 . ? O34 Ti3 O29 124.61(18) . . ? O33 Ti3 O29 78.40(18) . . ? O21 Ti3 O29 148.58(16) . . ? O24 Ti3 O29 87.35(17) 2_766 . ? O31 Ti3 O29 87.06(18) . . ? O34 Ti3 O28 159.18(18) . . ? O33 Ti3 O28 153.26(19) . . ? O21 Ti3 O28 73.88(16) . . ? O24 Ti3 O28 86.39(15) 2_766 . ? O31 Ti3 O28 81.13(16) . . ? O29 Ti3 O28 75.29(17) . . ? O34 Ti3 Ti4 125.77(14) . . ? O33 Ti3 Ti4 170.53(14) . . ? O21 Ti3 Ti4 39.07(11) . . ? O24 Ti3 Ti4 78.42(11) 2_766 . ? O31 Ti3 Ti4 92.71(13) . . ? O29 Ti3 Ti4 109.52(12) . . ? O28 Ti3 Ti4 35.68(12) . . ? O35 Ti4 O36 46.88(19) . . ? O35 Ti4 O28 104.8(2) . . ? O36 Ti4 O28 104.15(19) . . ? O35 Ti4 O23 101.4(2) . . ? O36 Ti4 O23 100.20(19) . . ? O28 Ti4 O23 152.28(16) . . ? O35 Ti4 O21 155.58(18) . . ? O36 Ti4 O21 157.48(17) . . ? O28 Ti4 O21 75.47(16) . . ? O23 Ti4 O21 76.96(16) . . ? O35 Ti4 O25 123.78(18) . 2_766 ? O36 Ti4 O25 76.91(17) . 2_766 ? O28 Ti4 O25 85.40(17) . 2_766 ? O23 Ti4 O25 87.40(17) . 2_766 ? O21 Ti4 O25 80.63(14) . 2_766 ? O35 Ti4 O20 76.21(18) . . ? O36 Ti4 O20 122.97(17) . . ? O28 Ti4 O20 91.89(17) . . ? O23 Ti4 O20 85.78(18) . . ? O21 Ti4 O20 79.37(15) . . ? O25 Ti4 O20 159.86(15) 2_766 . ? O35 Ti4 Ti3 141.69(16) . . ? O36 Ti4 Ti3 134.30(15) . . ? O28 Ti4 Ti3 38.84(11) . . ? O23 Ti4 Ti3 113.48(12) . . ? O21 Ti4 Ti3 37.52(11) . . ? O25 Ti4 Ti3 74.82(11) 2_766 . ? O20 Ti4 Ti3 90.61(12) . . ? C18 C17 C15 114.0(4) . . ? O25 C18 O24 125.5(5) . . ? O25 C18 C17 119.0(5) . . ? O24 C18 C17 115.5(5) . . ? O27 C19 O26 122.4(6) . . ? O27 C19 C20 126.0(6) . . ? O26 C19 C20 111.7(5) . . ? C19 C20 C21 113.6(5) . . ? C13 O20 Ti4 134.6(4) . . ? O28 C21 C20 110.9(5) . . ? O28 C21 C22 106.6(5) . . ? C20 C21 C22 112.0(5) . . ? O28 C21 C23 109.0(5) . . ? C20 C21 C23 109.7(5) . . ? C22 C21 C23 108.6(5) . . ? C15 O21 Ti3 140.3(3) . . ? C15 O21 Ti4 112.1(3) . . ? Ti3 O21 Ti4 103.42(18) . . ? O30 C22 O29 123.5(7) . . ? O30 C22 C21 120.0(6) . . ? O29 C22 C21 116.3(6) . . ? C24 C23 C21 115.9(5) . . ? C16 O23 Ti4 116.1(4) . . ? O32 C24 O31 120.5(6) . . ? O32 C24 C23 117.9(6) . . ? O31 C24 C23 121.6(6) . . ? C18 O24 Ti3 130.2(4) . 2_766 ? C18 O25 Ti4 131.0(4) . 2_766 ? C21 O28 Ti4 139.3(4) . . ? C21 O28 Ti3 112.4(3) . . ? Ti4 O28 Ti3 105.47(18) . . ? C22 O29 Ti3 116.7(4) . . ? C24 O31 Ti3 135.9(4) . . ? O34 O33 Ti3 66.8(2) . . ? O33 O34 Ti3 67.0(2) . . ? O36 O35 Ti4 67.2(2) . . ? O35 O36 Ti4 65.9(2) . . ? _diffrn_measured_fraction_theta_max 0.950 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.950 _refine_diff_density_max 2.483 _refine_diff_density_min -0.972 _refine_diff_density_rms 0.138