# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Prof C. Cummins' _publ_contact_author_address ; Department of Chemistry Massachusetts Institute of Technology room 2-227 77 Massachusetts Avenue Cambridge MA 02139-4307 UNITED STATES OF AMERICA ; _publ_contact_author_email CCUMMINS@MIT.EDU _publ_section_title ; Synthesis of a four-coordinate titanium(IV) oxoanion via deprotonation and decarbonylation of complexed formate ; loop_ _publ_author_name 'C. Cummins' 'Joshua S. Figueroa' 'Arjun Mendiratta' data_04030m _database_code_depnum_ccdc_archive 'CCDC 267713' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common (O(H)CO)Ti(N(t-Bu)Ar)3 _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C37 H54 N3 O2 Ti' _chemical_formula_weight 620.73 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Rhombohedral _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 15.7365(7) _cell_length_b 15.7365(7) _cell_length_c 24.686(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 5294.1(6) _cell_formula_units_Z 6 _cell_measurement_temperature 193(2) _cell_measurement_reflns_used 3769 _cell_measurement_theta_min 2.23 _cell_measurement_theta_max 28.24 _exptl_crystal_description Block _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.11 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.168 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2010 _exptl_absorpt_coefficient_mu 0.277 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.444572 _exptl_absorpt_correction_T_max 1 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 193(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_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4300 _diffrn_reflns_av_R_equivalents 0.0434 _diffrn_reflns_av_sigmaI/netI 0.0550 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 1.71 _diffrn_reflns_theta_max 23.99 _reflns_number_total 1423 _reflns_number_gt 1338 _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, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _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^)+(0.0347P)^2^+18.8315P] 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 1423 _refine_ls_number_parameters 136 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0580 _refine_ls_R_factor_gt 0.0542 _refine_ls_wR_factor_ref 0.1337 _refine_ls_wR_factor_gt 0.1316 _refine_ls_goodness_of_fit_ref 1.091 _refine_ls_restrained_S_all 1.091 _refine_ls_shift/su_max 0.113 _refine_ls_shift/su_mean 0.011 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 0.6667 0.3333 0.04286(3) 0.0258(3) Uani 1 3 d S . . N1 N 0.78097(19) 0.44821(19) 0.07051(9) 0.0282(6) Uani 1 1 d . . . O1 O 0.6667 0.3333 -0.03306(15) 0.0513(12) Uani 1 3 d S . . C11 C 0.8344(2) 0.4424(2) 0.11645(11) 0.0270(7) Uani 1 1 d . . . C12 C 0.8061(2) 0.4505(2) 0.16870(12) 0.0300(7) Uani 1 1 d . . . H12A H 0.7527 0.4598 0.1736 0.036 Uiso 1 1 calc R . . C13 C 0.8563(2) 0.4450(2) 0.21367(13) 0.0345(8) Uani 1 1 d . . . C14 C 0.9358(3) 0.4308(2) 0.20587(13) 0.0383(8) Uani 1 1 d . . . H14A H 0.9690 0.4261 0.2359 0.046 Uiso 1 1 calc R . . C15 C 0.9668(2) 0.4235(2) 0.15440(13) 0.0357(8) Uani 1 1 d . . . C16 C 0.9148(2) 0.4291(2) 0.11005(13) 0.0329(7) Uani 1 1 d . . . H16A H 0.9344 0.4238 0.0753 0.039 Uiso 1 1 calc R . . C17 C 0.8260(2) 0.5502(2) 0.04686(13) 0.0356(8) Uani 1 1 d . . . C18 C 0.7585(3) 0.5513(3) 0.00257(15) 0.0476(9) Uani 1 1 d . . . H18A H 0.6953 0.5322 0.0178 0.071 Uiso 1 1 calc R . . H18B H 0.7514 0.5061 -0.0256 0.071 Uiso 1 1 calc R . . H18C H 0.7864 0.6162 -0.0123 0.071 Uiso 1 1 calc R . . C19 C 0.8371(3) 0.6234(3) 0.09064(15) 0.0476(9) Uani 1 1 d . . . H19A H 0.8792 0.6236 0.1188 0.071 Uiso 1 1 calc R . . H19B H 0.7738 0.6049 0.1056 0.071 Uiso 1 1 calc R . . H19C H 0.8651 0.6878 0.0751 0.071 Uiso 1 1 calc R . . C21 C 0.6667 0.3333 -0.0851(3) 0.075(3) Uani 1 3 d S . . C110 C 0.9255(3) 0.5800(3) 0.02185(17) 0.0556(11) Uani 1 1 d . . . H11A H 0.9688 0.5802 0.0493 0.083 Uiso 1 1 calc R . . H11B H 0.9529 0.6445 0.0065 0.083 Uiso 1 1 calc R . . H11C H 0.9177 0.5341 -0.0061 0.083 Uiso 1 1 calc R . . C131 C 0.8268(3) 0.4572(3) 0.26999(14) 0.0484(9) Uani 1 1 d . . . H13A H 0.8689 0.4512 0.2960 0.073 Uiso 1 1 calc R . . H13B H 0.7601 0.4074 0.2766 0.073 Uiso 1 1 calc R . . H13C H 0.8328 0.5207 0.2732 0.073 Uiso 1 1 calc R . . C151 C 1.0546(3) 0.4109(3) 0.14661(17) 0.0554(11) Uani 1 1 d . . . H15A H 1.0806 0.4082 0.1813 0.083 Uiso 1 1 calc R . . H15B H 1.1038 0.4654 0.1263 0.083 Uiso 1 1 calc R . . H15C H 1.0354 0.3512 0.1272 0.083 Uiso 1 1 calc R . . O2 O 0.6158(12) 0.2481(11) -0.1065(5) 0.120(5) Uani 0.33 1 d P . . 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 0.0282(4) 0.0282(4) 0.0212(5) 0.000 0.000 0.0141(2) N1 0.0290(14) 0.0272(14) 0.0272(12) 0.0055(10) 0.0037(10) 0.0132(12) O1 0.0646(19) 0.0646(19) 0.0246(19) 0.000 0.000 0.0323(10) C11 0.0261(16) 0.0185(15) 0.0303(15) 0.0007(11) -0.0019(12) 0.0067(13) C12 0.0272(17) 0.0236(16) 0.0334(15) 0.0010(12) 0.0018(12) 0.0084(14) C13 0.0363(19) 0.0229(17) 0.0335(17) -0.0002(12) -0.0030(13) 0.0068(14) C14 0.044(2) 0.0288(18) 0.0386(17) -0.0017(13) -0.0143(15) 0.0161(16) C15 0.0351(19) 0.0297(18) 0.0429(18) -0.0013(13) -0.0067(14) 0.0166(16) C16 0.0358(19) 0.0295(18) 0.0331(16) -0.0015(13) 0.0008(13) 0.0161(16) C17 0.0285(18) 0.0318(18) 0.0437(18) 0.0129(14) 0.0048(14) 0.0130(15) C18 0.052(2) 0.043(2) 0.048(2) 0.0179(16) 0.0021(17) 0.0234(19) C19 0.046(2) 0.030(2) 0.062(2) 0.0019(16) -0.0090(17) 0.0152(17) C21 0.095(4) 0.095(4) 0.034(4) 0.000 0.000 0.048(2) C110 0.040(2) 0.051(2) 0.072(3) 0.035(2) 0.0207(19) 0.020(2) C131 0.053(2) 0.053(2) 0.0321(17) -0.0005(15) -0.0026(16) 0.021(2) C151 0.054(2) 0.067(3) 0.061(2) -0.002(2) -0.0085(19) 0.042(2) O2 0.153(13) 0.141(12) 0.064(6) -0.061(7) -0.033(7) 0.073(11) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.874(4) . ? Ti1 N1 1.928(3) 3_665 ? Ti1 N1 1.928(3) . ? Ti1 N1 1.928(3) 2_655 ? N1 C11 1.442(4) . ? N1 C17 1.511(4) . ? O1 C21 1.285(8) . ? C11 C16 1.391(5) . ? C11 C12 1.391(4) . ? C12 C13 1.390(5) . ? C13 C14 1.391(5) . ? C13 C131 1.508(5) . ? C14 C15 1.387(5) . ? C15 C16 1.396(5) . ? C15 C151 1.502(5) . ? C17 C110 1.523(5) . ? C17 C19 1.525(5) . ? C17 C18 1.530(5) . ? C21 O2 1.282(13) 2_655 ? C21 O2 1.282(13) . ? C21 O2 1.282(13) 3_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 Ti1 N1 110.74(7) . 3_665 ? O1 Ti1 N1 110.74(7) . . ? N1 Ti1 N1 108.18(7) 3_665 . ? O1 Ti1 N1 110.73(7) . 2_655 ? N1 Ti1 N1 108.18(7) 3_665 2_655 ? N1 Ti1 N1 108.18(7) . 2_655 ? C11 N1 C17 113.1(2) . . ? C11 N1 Ti1 121.29(19) . . ? C17 N1 Ti1 125.55(19) . . ? C21 O1 Ti1 180.0 . . ? C16 C11 C12 118.4(3) . . ? C16 C11 N1 121.6(3) . . ? C12 C11 N1 120.0(3) . . ? C13 C12 C11 121.1(3) . . ? C12 C13 C14 119.0(3) . . ? C12 C13 C131 120.6(3) . . ? C14 C13 C131 120.4(3) . . ? C15 C14 C13 121.5(3) . . ? C14 C15 C16 118.1(3) . . ? C14 C15 C151 120.9(3) . . ? C16 C15 C151 121.0(3) . . ? C11 C16 C15 121.8(3) . . ? N1 C17 C110 110.3(3) . . ? N1 C17 C19 110.1(3) . . ? C110 C17 C19 110.1(3) . . ? N1 C17 C18 109.2(3) . . ? C110 C17 C18 108.6(3) . . ? C19 C17 C18 108.4(3) . . ? O1 C21 O2 114.3(7) . 2_655 ? O1 C21 O2 114.3(7) . . ? O2 C21 O2 104.3(8) 2_655 . ? O1 C21 O2 114.3(7) . 3_665 ? O2 C21 O2 104.3(8) 2_655 3_665 ? O2 C21 O2 104.3(8) . 3_665 ? _diffrn_measured_fraction_theta_max 0.770 _diffrn_reflns_theta_full 23.99 _diffrn_measured_fraction_theta_full 0.770 _refine_diff_density_max 0.298 _refine_diff_density_min -0.192 _refine_diff_density_rms 0.047 #===END data_04160-m _database_code_depnum_ccdc_archive 'CCDC 267714' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ((Et2O)2Li)(OTi(N(t-Bu)Ar)3) _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C44 H68 Li N3 O3 Ti' _chemical_formula_weight 741.85 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 orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 13.3553(10) _cell_length_b 13.3843(9) _cell_length_c 25.8835(18) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4626.7(6) _cell_formula_units_Z 4 _cell_measurement_temperature 193(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 0.12 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.065 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1608 _exptl_absorpt_coefficient_mu 0.222 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.839157 _exptl_absorpt_correction_T_max 1 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 193(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_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 30248 _diffrn_reflns_av_R_equivalents 0.0393 _diffrn_reflns_av_sigmaI/netI 0.0454 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 1.57 _diffrn_reflns_theta_max 26.00 _reflns_number_total 8968 _reflns_number_gt 7779 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _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^)+(0.1002P)^2^+0.9959P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.00(3) _refine_ls_number_reflns 8968 _refine_ls_number_parameters 488 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0697 _refine_ls_R_factor_gt 0.0587 _refine_ls_wR_factor_ref 0.1573 _refine_ls_wR_factor_gt 0.1493 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.036 _refine_ls_shift/su_max 0.104 _refine_ls_shift/su_mean 0.004 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 -0.78454(3) -0.91341(4) -0.130679(18) 0.02508(14) Uani 1 1 d . . . O1 O -0.72354(15) -0.81879(17) -0.16256(8) 0.0327(5) Uani 1 1 d . . . N1 N -0.88797(18) -0.9698(2) -0.17744(10) 0.0353(7) Uani 1 1 d . A . Li1 Li -0.6385(4) -0.7387(5) -0.1972(2) 0.0403(13) Uani 1 1 d . . . N2 N -0.85003(17) -0.85969(19) -0.06752(9) 0.0263(5) Uani 1 1 d . . . O2 O -0.5431(2) -0.6517(2) -0.16368(10) 0.0484(6) Uani 1 1 d . . . N3 N -0.68446(17) -1.0178(2) -0.11258(10) 0.0294(6) Uani 1 1 d . . . O3 O -0.6320(2) -0.7295(2) -0.27274(10) 0.0589(8) Uani 1 1 d . . . C11 C -0.9769(2) -1.0082(3) -0.15326(12) 0.0328(7) Uani 1 1 d . . . C18 C -0.9228(8) -1.0872(9) -0.2543(3) 0.047(3) Uani 0.57(2) 1 d P A 1 C110 C -0.9591(6) -0.9005(12) -0.2565(3) 0.052(3) Uani 0.57(2) 1 d P A 1 C18' C -0.9669(12) -1.0243(19) -0.2611(4) 0.077(8) Uani 0.43(2) 1 d P A 2 C11' C -0.9381(9) -0.8318(16) -0.2458(4) 0.054(5) Uani 0.43(2) 1 d P A 2 C12 C -1.0603(2) -0.9463(3) -0.14408(12) 0.0360(8) Uani 1 1 d . . . H12A H -1.0584 -0.8787 -0.1553 0.043 Uiso 1 1 calc R . . C13 C -1.1461(2) -0.9818(3) -0.11876(13) 0.0407(8) Uani 1 1 d . . . C14 C -1.1479(2) -1.0813(3) -0.10235(12) 0.0405(8) Uani 1 1 d . . . H14A H -1.2051 -1.1057 -0.0845 0.049 Uiso 1 1 calc R . . C15 C -1.0674(2) -1.1457(3) -0.11157(13) 0.0406(8) Uani 1 1 d . . . C16 C -0.9822(2) -1.1075(3) -0.13700(12) 0.0351(7) Uani 1 1 d . . . H16A H -0.9269 -1.1505 -0.1432 0.042 Uiso 1 1 calc R . . C17 C -0.8941(3) -0.9649(5) -0.23540(14) 0.0744(17) Uani 1 1 d . . . C19 C -0.7879(3) -0.9565(3) -0.25712(13) 0.0499(10) Uani 1 1 d . A . H19A H -0.7581 -0.8931 -0.2461 0.075 Uiso 1 1 calc R . . H19B H -0.7903 -0.9589 -0.2949 0.075 Uiso 1 1 calc R . . H19C H -0.7472 -1.0121 -0.2442 0.075 Uiso 1 1 calc R . . C21 C -0.8460(2) -0.9237(2) -0.02281(11) 0.0282(6) Uani 1 1 d . . . C22 C -0.9209(2) -0.9956(2) -0.01352(12) 0.0316(7) Uani 1 1 d . . . H22A H -0.9766 -0.9998 -0.0363 0.038 Uiso 1 1 calc R . . C23 C -0.9151(2) -1.0606(2) 0.02828(13) 0.0369(8) Uani 1 1 d . . . C24 C -0.8326(3) -1.0549(3) 0.06143(13) 0.0397(8) Uani 1 1 d . . . H24A H -0.8280 -1.0998 0.0898 0.048 Uiso 1 1 calc R . . C25 C -0.7570(2) -0.9849(3) 0.05373(13) 0.0380(8) Uani 1 1 d . . . C26 C -0.7652(2) -0.9205(3) 0.01171(11) 0.0334(7) Uani 1 1 d . . . H26A H -0.7140 -0.8724 0.0062 0.040 Uiso 1 1 calc R . . C27 C -0.8972(2) -0.7599(2) -0.05756(12) 0.0341(7) Uani 1 1 d . . . C28 C -0.9047(3) -0.7029(3) -0.10916(14) 0.0425(8) Uani 1 1 d . . . H28A H -0.8375 -0.6938 -0.1236 0.064 Uiso 1 1 calc R . . H28B H -0.9354 -0.6374 -0.1032 0.064 Uiso 1 1 calc R . . H28C H -0.9459 -0.7411 -0.1334 0.064 Uiso 1 1 calc R . . C29 C -0.8344(3) -0.6980(3) -0.01940(15) 0.0528(10) Uani 1 1 d . . . H29A H -0.7667 -0.6893 -0.0332 0.079 Uiso 1 1 calc R . . H29B H -0.8310 -0.7328 0.0139 0.079 Uiso 1 1 calc R . . H29C H -0.8657 -0.6324 -0.0145 0.079 Uiso 1 1 calc R . . C31 C -0.7169(2) -1.1207(2) -0.11434(12) 0.0341(7) Uani 1 1 d . . . C32 C -0.7227(2) -1.1737(3) -0.16084(14) 0.0438(8) Uani 1 1 d . . . H32A H -0.7016 -1.1422 -0.1919 0.053 Uiso 1 1 calc R . . C33 C -0.7587(3) -1.2715(3) -0.16301(18) 0.0580(12) Uani 1 1 d . . . C34 C -0.7867(3) -1.3179(3) -0.11628(19) 0.0603(12) Uani 1 1 d . . . H34A H -0.8110 -1.3846 -0.1171 0.072 Uiso 1 1 calc R . . C35 C -0.7798(3) -1.2691(3) -0.06918(16) 0.0486(9) Uani 1 1 d . . . C36 C -0.7469(2) -1.1694(3) -0.06905(14) 0.0382(8) Uani 1 1 d . . . H36A H -0.7449 -1.1340 -0.0373 0.046 Uiso 1 1 calc R . . C37 C -0.5726(2) -1.0070(3) -0.10652(16) 0.0455(9) Uani 1 1 d . . . C38 C -0.5306(4) -1.0778(5) -0.0678(3) 0.146(4) Uani 1 1 d . . . H38A H -0.5625 -1.0662 -0.0342 0.218 Uiso 1 1 calc R . . H38B H -0.4583 -1.0672 -0.0648 0.218 Uiso 1 1 calc R . . H38C H -0.5436 -1.1465 -0.0790 0.218 Uiso 1 1 calc R . . C39 C -0.5230(3) -1.0222(5) -0.1606(3) 0.106(3) Uani 1 1 d . . . H39A H -0.5368 -1.0900 -0.1729 0.159 Uiso 1 1 calc R . . H39B H -0.4504 -1.0126 -0.1577 0.159 Uiso 1 1 calc R . . H39C H -0.5505 -0.9736 -0.1851 0.159 Uiso 1 1 calc R . . C41 C -0.6443(5) -0.5505(6) -0.1064(3) 0.107(2) Uani 1 1 d . . . H41A H -0.6547 -0.5330 -0.0701 0.161 Uiso 1 1 calc R . . H41B H -0.7061 -0.5787 -0.1207 0.161 Uiso 1 1 calc R . . H41C H -0.6260 -0.4904 -0.1259 0.161 Uiso 1 1 calc R . . C42 C -0.5650(6) -0.6229(4) -0.11037(18) 0.102(2) Uani 1 1 d . . . H42A H -0.5840 -0.6833 -0.0906 0.123 Uiso 1 1 calc R . . H42B H -0.5037 -0.5949 -0.0945 0.123 Uiso 1 1 calc R . . C43 C -0.4475(3) -0.6212(3) -0.1834(2) 0.0689(13) Uani 1 1 d . . . H43A H -0.4343 -0.5513 -0.1730 0.083 Uiso 1 1 calc R . . H43B H -0.4488 -0.6238 -0.2217 0.083 Uiso 1 1 calc R . . C44 C -0.3645(3) -0.6871(4) -0.1638(2) 0.0804(15) Uani 1 1 d . . . H44A H -0.3003 -0.6635 -0.1774 0.121 Uiso 1 1 calc R . . H44B H -0.3761 -0.7560 -0.1751 0.121 Uiso 1 1 calc R . . H44C H -0.3631 -0.6848 -0.1259 0.121 Uiso 1 1 calc R . . C51 C -0.4936(5) -0.8427(7) -0.2807(4) 0.147(4) Uani 1 1 d . . . H51A H -0.4601 -0.8898 -0.3040 0.220 Uiso 1 1 calc R . . H51B H -0.5155 -0.8780 -0.2496 0.220 Uiso 1 1 calc R . . H51C H -0.4469 -0.7894 -0.2712 0.220 Uiso 1 1 calc R . . C52 C -0.5783(5) -0.8005(4) -0.30613(18) 0.084(2) Uani 1 1 d . . . H52A H -0.6245 -0.8547 -0.3166 0.101 Uiso 1 1 calc R . . H52B H -0.5559 -0.7657 -0.3378 0.101 Uiso 1 1 calc R . . C53 C -0.7130(4) -0.6803(5) -0.29807(19) 0.0820(16) Uani 1 1 d . . . H53A H -0.7638 -0.7298 -0.3091 0.098 Uiso 1 1 calc R . . H53B H -0.6883 -0.6448 -0.3291 0.098 Uiso 1 1 calc R . . C54 C -0.7574(4) -0.6089(4) -0.2618(2) 0.0913(18) Uani 1 1 d . . . H54A H -0.8138 -0.5749 -0.2784 0.137 Uiso 1 1 calc R . . H54B H -0.7069 -0.5595 -0.2516 0.137 Uiso 1 1 calc R . . H54C H -0.7811 -0.6446 -0.2311 0.137 Uiso 1 1 calc R . . C131 C -1.2344(3) -0.9137(4) -0.10821(18) 0.0625(11) Uani 1 1 d . . . H13A H -1.2868 -0.9512 -0.0901 0.094 Uiso 1 1 calc R . . H13B H -1.2610 -0.8884 -0.1410 0.094 Uiso 1 1 calc R . . H13C H -1.2127 -0.8575 -0.0867 0.094 Uiso 1 1 calc R . . C151 C -1.0728(3) -1.2538(3) -0.09544(16) 0.0528(10) Uani 1 1 d . . . H15A H -1.1372 -1.2665 -0.0786 0.079 Uiso 1 1 calc R . . H15B H -1.0183 -1.2684 -0.0713 0.079 Uiso 1 1 calc R . . H15C H -1.0665 -1.2966 -0.1260 0.079 Uiso 1 1 calc R . . C210 C -1.0046(3) -0.7725(3) -0.03552(14) 0.0466(9) Uani 1 1 d . . . H21A H -1.0013 -0.8077 -0.0024 0.070 Uiso 1 1 calc R . . H21B H -1.0452 -0.8112 -0.0599 0.070 Uiso 1 1 calc R . . H21C H -1.0349 -0.7066 -0.0305 0.070 Uiso 1 1 calc R . . C231 C -0.9975(3) -1.1388(3) 0.03672(17) 0.0530(10) Uani 1 1 d . . . H23A H -1.0486 -1.1319 0.0098 0.080 Uiso 1 1 calc R . . H23B H -1.0283 -1.1285 0.0707 0.080 Uiso 1 1 calc R . . H23C H -0.9683 -1.2059 0.0351 0.080 Uiso 1 1 calc R . . C251 C -0.6660(3) -0.9790(3) 0.08964(15) 0.0552(10) Uani 1 1 d . . . H25A H -0.6727 -1.0288 0.1171 0.083 Uiso 1 1 calc R . . H25B H -0.6622 -0.9121 0.1049 0.083 Uiso 1 1 calc R . . H25C H -0.6049 -0.9922 0.0698 0.083 Uiso 1 1 calc R . . C310 C -0.5484(2) -0.9004(3) -0.08988(15) 0.0447(9) Uani 1 1 d . . . H31A H -0.5761 -0.8882 -0.0554 0.067 Uiso 1 1 calc R . . H31B H -0.5780 -0.8533 -0.1145 0.067 Uiso 1 1 calc R . . H31C H -0.4756 -0.8912 -0.0890 0.067 Uiso 1 1 calc R . . C331 C -0.7705(4) -1.3261(5) -0.2140(2) 0.098(2) Uani 1 1 d . . . H33A H -0.7960 -1.3936 -0.2075 0.147 Uiso 1 1 calc R . . H33B H -0.7054 -1.3303 -0.2313 0.147 Uiso 1 1 calc R . . H33C H -0.8177 -1.2897 -0.2360 0.147 Uiso 1 1 calc R . . C351 C -0.8085(3) -1.3213(4) -0.0196(2) 0.0721(14) Uani 1 1 d . . . H35A H -0.7998 -1.2754 0.0096 0.108 Uiso 1 1 calc R . . H35B H -0.7657 -1.3800 -0.0146 0.108 Uiso 1 1 calc R . . H35C H -0.8787 -1.3425 -0.0215 0.108 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 0.0211(2) 0.0347(3) 0.0195(2) -0.0004(2) 0.00014(19) -0.0002(2) O1 0.0295(10) 0.0436(13) 0.0250(10) 0.0019(9) 0.0016(8) -0.0037(10) N1 0.0236(11) 0.0586(19) 0.0238(14) -0.0051(13) -0.0020(10) -0.0064(12) Li1 0.034(3) 0.056(4) 0.030(3) 0.007(3) 0.002(2) -0.012(2) N2 0.0285(11) 0.0304(14) 0.0201(12) -0.0018(11) 0.0000(9) 0.0037(10) O2 0.0575(14) 0.0516(16) 0.0360(13) -0.0091(12) -0.0076(11) -0.0029(12) N3 0.0239(11) 0.0349(15) 0.0295(13) -0.0033(12) 0.0001(9) 0.0014(10) O3 0.0622(16) 0.077(2) 0.0371(15) 0.0023(14) 0.0028(12) -0.0259(15) C11 0.0251(13) 0.053(2) 0.0203(14) -0.0111(15) -0.0016(11) -0.0044(13) C18 0.048(5) 0.064(6) 0.029(4) -0.017(4) 0.004(3) -0.021(5) C110 0.056(4) 0.073(10) 0.029(4) 0.009(5) -0.004(3) 0.010(5) C18' 0.060(8) 0.14(2) 0.033(5) -0.014(7) -0.012(5) -0.029(11) C11' 0.060(6) 0.081(13) 0.022(5) 0.020(6) 0.003(4) 0.027(7) C12 0.0249(13) 0.048(2) 0.0352(18) -0.0023(14) -0.0020(12) -0.0024(13) C13 0.0234(13) 0.057(2) 0.042(2) -0.0096(17) 0.0032(12) -0.0011(14) C14 0.0270(13) 0.063(2) 0.0317(17) -0.0088(18) 0.0046(11) -0.0115(15) C15 0.0357(16) 0.052(2) 0.0342(18) -0.0037(16) -0.0050(13) -0.0082(15) C16 0.0267(13) 0.048(2) 0.0310(17) -0.0078(15) 0.0002(12) -0.0028(12) C17 0.0393(19) 0.166(5) 0.0177(17) -0.005(2) 0.0004(14) -0.036(3) C19 0.0479(18) 0.079(3) 0.0224(16) -0.0055(16) 0.0096(15) -0.0204(19) C21 0.0294(13) 0.0337(17) 0.0216(14) -0.0027(14) 0.0058(10) 0.0032(13) C22 0.0317(14) 0.0393(19) 0.0236(15) -0.0050(14) 0.0049(11) 0.0006(13) C23 0.0435(17) 0.035(2) 0.0324(18) -0.0026(14) 0.0110(13) -0.0025(13) C24 0.0535(19) 0.041(2) 0.0249(16) 0.0052(14) 0.0070(14) 0.0048(15) C25 0.0424(16) 0.042(2) 0.0293(17) 0.0050(15) -0.0010(13) 0.0010(14) C26 0.0363(15) 0.0390(18) 0.0248(14) 0.0026(14) 0.0000(11) -0.0041(14) C27 0.0410(16) 0.0353(19) 0.0260(16) -0.0014(14) -0.0012(13) 0.0068(14) C28 0.0455(18) 0.040(2) 0.042(2) 0.0071(16) -0.0019(15) 0.0076(15) C29 0.076(3) 0.038(2) 0.044(2) -0.0042(18) -0.0091(19) 0.0062(19) C31 0.0219(12) 0.0399(17) 0.0406(17) -0.0058(14) 0.0021(12) 0.0015(13) C32 0.0311(15) 0.054(2) 0.047(2) -0.0155(17) 0.0081(15) -0.0043(16) C33 0.0334(17) 0.060(3) 0.081(3) -0.038(2) 0.0110(18) -0.0035(16) C34 0.0375(17) 0.0335(19) 0.110(4) -0.008(2) 0.015(2) -0.0029(16) C35 0.0351(16) 0.038(2) 0.072(3) 0.0056(19) 0.0089(18) 0.0060(16) C36 0.0312(14) 0.0352(19) 0.048(2) 0.0025(16) 0.0007(13) 0.0075(13) C37 0.0248(15) 0.039(2) 0.073(3) -0.0024(19) -0.0044(15) 0.0019(13) C38 0.064(3) 0.111(5) 0.263(10) 0.122(6) -0.094(5) -0.041(3) C39 0.038(2) 0.140(5) 0.139(5) -0.089(5) 0.035(3) -0.034(3) C41 0.086(4) 0.131(6) 0.104(5) -0.053(4) 0.030(3) -0.027(4) C42 0.206(7) 0.062(3) 0.039(2) -0.015(2) -0.041(4) 0.052(4) C43 0.063(3) 0.051(3) 0.093(4) 0.018(2) -0.021(2) -0.023(2) C44 0.058(3) 0.089(4) 0.094(4) 0.016(3) -0.009(3) -0.006(3) C51 0.072(4) 0.171(8) 0.196(9) -0.114(7) -0.022(5) 0.036(5) C52 0.125(4) 0.078(4) 0.051(3) -0.031(3) 0.048(3) -0.057(3) C53 0.092(3) 0.100(4) 0.054(3) 0.029(3) -0.020(3) -0.022(3) C54 0.089(4) 0.089(4) 0.095(4) 0.016(3) -0.031(3) 0.029(3) C131 0.0328(18) 0.078(3) 0.076(3) -0.010(3) 0.0054(17) 0.0083(19) C151 0.050(2) 0.061(3) 0.047(2) 0.003(2) 0.0001(17) -0.0124(19) C210 0.051(2) 0.052(2) 0.037(2) 0.0009(18) 0.0091(15) 0.0203(17) C231 0.056(2) 0.047(2) 0.056(2) 0.004(2) 0.0122(18) -0.0116(18) C251 0.062(2) 0.066(3) 0.038(2) 0.017(2) -0.0179(18) -0.006(2) C310 0.0300(15) 0.051(2) 0.053(2) -0.0114(19) -0.0091(14) -0.0040(15) C331 0.075(3) 0.108(4) 0.110(4) -0.074(4) 0.030(3) -0.037(3) C351 0.061(3) 0.052(3) 0.103(4) 0.036(3) 0.003(2) 0.003(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.717(2) . ? Ti1 N1 1.986(3) . ? Ti1 N2 1.989(2) . ? Ti1 N3 1.990(3) . ? O1 Li1 1.801(6) . ? N1 C11 1.438(4) . ? N1 C17 1.504(4) . ? Li1 O2 1.933(6) . ? Li1 O3 1.960(6) . ? N2 C21 1.441(4) . ? N2 C27 1.499(4) . ? O2 C43 1.434(5) . ? O2 C42 1.462(6) . ? N3 C31 1.445(4) . ? N3 C37 1.509(4) . ? O3 C53 1.425(6) . ? O3 C52 1.472(6) . ? C11 C16 1.396(5) . ? C11 C12 1.408(4) . ? C18 C17 1.751(11) . ? C110 C17 1.341(11) . ? C18' C17 1.421(12) . ? C11' C17 1.896(19) . ? C12 C13 1.404(4) . ? C13 C14 1.398(6) . ? C13 C131 1.515(5) . ? C14 C15 1.398(5) . ? C15 C16 1.411(4) . ? C15 C151 1.507(6) . ? C17 C19 1.530(5) . ? C21 C26 1.401(4) . ? C21 C22 1.409(4) . ? C22 C23 1.390(5) . ? C23 C24 1.399(5) . ? C23 C231 1.534(5) . ? C24 C25 1.391(5) . ? C25 C26 1.392(5) . ? C25 C251 1.532(5) . ? C27 C29 1.538(5) . ? C27 C28 1.542(5) . ? C27 C210 1.552(5) . ? C31 C32 1.399(5) . ? C31 C36 1.400(5) . ? C32 C33 1.394(6) . ? C33 C34 1.410(7) . ? C33 C331 1.516(6) . ? C34 C35 1.386(6) . ? C35 C36 1.405(5) . ? C35 C351 1.511(6) . ? C37 C38 1.488(6) . ? C37 C310 1.524(5) . ? C37 C39 1.562(7) . ? C41 C42 1.439(9) . ? C43 C44 1.506(6) . ? C51 C52 1.425(9) . ? C53 C54 1.465(8) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Ti1 N1 108.51(11) . . ? O1 Ti1 N2 109.70(10) . . ? N1 Ti1 N2 109.42(10) . . ? O1 Ti1 N3 108.21(11) . . ? N1 Ti1 N3 110.11(12) . . ? N2 Ti1 N3 110.85(10) . . ? Ti1 O1 Li1 167.8(2) . . ? C11 N1 C17 113.9(2) . . ? C11 N1 Ti1 116.46(19) . . ? C17 N1 Ti1 129.0(2) . . ? O1 Li1 O2 123.4(3) . . ? O1 Li1 O3 124.2(3) . . ? O2 Li1 O3 112.4(3) . . ? C21 N2 C27 114.1(2) . . ? C21 N2 Ti1 115.38(18) . . ? C27 N2 Ti1 130.42(19) . . ? C43 O2 C42 116.1(4) . . ? C43 O2 Li1 126.7(3) . . ? C42 O2 Li1 116.8(4) . . ? C31 N3 C37 113.1(3) . . ? C31 N3 Ti1 117.45(18) . . ? C37 N3 Ti1 128.4(2) . . ? C53 O3 C52 113.5(4) . . ? C53 O3 Li1 117.0(3) . . ? C52 O3 Li1 124.5(4) . . ? C16 C11 C12 118.0(3) . . ? C16 C11 N1 120.9(3) . . ? C12 C11 N1 121.1(3) . . ? C13 C12 C11 121.7(3) . . ? C14 C13 C12 118.6(3) . . ? C14 C13 C131 120.3(3) . . ? C12 C13 C131 121.1(4) . . ? C13 C14 C15 121.5(3) . . ? C14 C15 C16 118.4(3) . . ? C14 C15 C151 120.5(3) . . ? C16 C15 C151 121.1(3) . . ? C11 C16 C15 121.8(3) . . ? C110 C17 C18' 74.1(9) . . ? C110 C17 N1 118.1(6) . . ? C18' C17 N1 118.7(6) . . ? C110 C17 C19 113.7(5) . . ? C18' C17 C19 120.3(7) . . ? N1 C17 C19 108.6(3) . . ? C110 C17 C18 110.2(6) . . ? C18' C17 C18 36.5(8) . . ? N1 C17 C18 104.5(5) . . ? C19 C17 C18 99.7(5) . . ? C110 C17 C11' 30.2(5) . . ? C18' C17 C11' 104.3(9) . . ? N1 C17 C11' 101.5(5) . . ? C19 C17 C11' 99.5(5) . . ? C18 C17 C11' 140.4(5) . . ? C26 C21 C22 117.3(3) . . ? C26 C21 N2 121.5(3) . . ? C22 C21 N2 121.1(3) . . ? C23 C22 C21 121.3(3) . . ? C22 C23 C24 119.2(3) . . ? C22 C23 C231 119.8(3) . . ? C24 C23 C231 121.0(3) . . ? C25 C24 C23 121.3(3) . . ? C24 C25 C26 118.2(3) . . ? C24 C25 C251 121.5(3) . . ? C26 C25 C251 120.3(3) . . ? C25 C26 C21 122.6(3) . . ? N2 C27 C29 111.2(3) . . ? N2 C27 C28 108.6(3) . . ? C29 C27 C28 108.9(3) . . ? N2 C27 C210 110.8(3) . . ? C29 C27 C210 109.0(3) . . ? C28 C27 C210 108.2(3) . . ? C32 C31 C36 117.9(3) . . ? C32 C31 N3 121.8(3) . . ? C36 C31 N3 120.2(3) . . ? C33 C32 C31 122.0(4) . . ? C32 C33 C34 118.0(4) . . ? C32 C33 C331 121.5(5) . . ? C34 C33 C331 120.4(4) . . ? C35 C34 C33 122.0(3) . . ? C34 C35 C36 118.0(4) . . ? C34 C35 C351 120.8(4) . . ? C36 C35 C351 121.1(4) . . ? C31 C36 C35 122.0(4) . . ? C38 C37 N3 112.4(3) . . ? C38 C37 C310 109.0(4) . . ? N3 C37 C310 109.2(3) . . ? C38 C37 C39 111.1(5) . . ? N3 C37 C39 108.3(3) . . ? C310 C37 C39 106.6(4) . . ? C41 C42 O2 113.1(4) . . ? O2 C43 C44 111.6(4) . . ? C51 C52 O3 111.9(4) . . ? O3 C53 C54 108.2(4) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.689 _refine_diff_density_min -0.349 _refine_diff_density_rms 0.070