Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global #============================================================================== _journal_coden_Cambridge 222 loop_ _publ_author_name 'Kendall Thomson' 'Andrew E. Fenwick' 'Thomas Manz' 'Khamphee Phomphrai' 'Ian Rothwell' _publ_contact_author_name 'Prof Kendall Thomson' _publ_contact_author_address ; School of Chemical Engineering Purdue University West Lafayette IN 47907 UNITED STATES OF AMERICA ; _publ_contact_author_email THOMSONK@PURDUE.EDU _publ_requested_journal 'Dalton Transactions' _publ_section_title ; The Nature of Aryloxide and Arylsulfide Ligand Bonding in Dimethyltitanium Complexes Containing Cyclopentadienyl Ligation ; _publ_section_references ; P. T. Beurskens, G. Beurskens, R. deGelder,S. Garcia-Granda, R. O. Gould, R. Israel, J. M. M. Smits, '(1999). The DIRDIF-99 Program System. 'Crystallography Laboratory, Univ. of Nijmegen, The Netherlands. Enraf-Nonius (1993), CAD4 Express, Enraf-Nonius, Delft, The Netherlands. Johnson, C.K. (1976). ORTEP. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Nonius(1998), Collect Users Manual, Nonius 'Delft, The Netherlands. Otwinowski Z. & Minor, W. (1997). Methods Enzymol., 276, 307-327. Sheldrick, G.M. (1997). SHELXL97, Program for the Refinement of Crystal Structures. Univ. of Gottingen, Germany. Spek A.L.(1997) PLATON. Program. Univ. of Ultrecht, The Netherlands ; data_AF3118 _database_code_depnum_ccdc_archive 'CCDC 247467' _audit_creation_date 3-10-03 _audit_creation_method from_MolEN_and_SHELXL _audit_update_record ; ? ; # 5. CRYSTAL DATA _chemical_compound_source ? _exptl_crystal_description chunk _exptl_crystal_colour orange _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.34 _exptl_crystal_size_min 0.30 _chemical_name_systematic ; ? ; _exptl_crystal_density_method ? _chemical_formula_sum 'C16 H22 S1 Ti1' _chemical_formula_moiety 'C16 H22 S1 Ti1' _chemical_formula_structural ? _chemical_formula_weight 294.32 _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 6.9470(11) _cell_length_b 7.8874(13) _cell_length_c 15.0380(18) _cell_angle_alpha 75.487(8) _cell_angle_beta 80.377(7) _cell_angle_gamma 80.912(9) _cell_volume 780.6(2) _cell_measurement_reflns_used 12026 _cell_measurement_theta_min 2 _cell_measurement_theta_max 27 _cell_formula_units_z 2 _exptl_crystal_density_diffrn 1.25 _exptl_crystal_density_meas ? _diffrn_radiation_type MO-K\a _diffrn_radiation_wavelength 0.71073 _exptl_absorpt_coefficient_mu 0.652 _cell_measurement_temperature 150 _exptl_crystal_F_000 312 # 6. DATA COLLECTION _diffrn_ambient_temperature 150 _diffrn_measurement_device_type Nonius_KappaCCD _diffrn_measurement_method \w _exptl_absorpt_correction_type multi-scan_(Otwinowski_&_Minor,_1 _exptl_absorpt_correction_T_min 0.6746 _exptl_absorpt_correction_T_max 0.8223 _diffrn_reflns_number 12026 _diffrn_measured_fraction_theta_max 0.8816 _diffrn_reflns_theta_full 20.2 _diffrn_measured_fraction_theta_full 0.9550 _reflns_number_total 3659 _reflns_number_gt 3177 _reflns_threshold_expression >2.0\s(I) _diffrn_reflns_av_R_equivalents 0.047 _diffrn_reflns_theta_min 2.69 _diffrn_reflns_theta_max 27.86 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_max 19 _diffrn_special_details 'mosaicity from Denzo/Scalepack is 0.62' # 7. REFINEMENT DATA _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating R_factor_obs 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_R_factor_all 0.059 _refine_ls_R_factor_gt 0.045 _refine_ls_wR_factor_ref 0.129 _refine_ls_wR_factor_gt 0.123 _refine_ls_hydrogen_treatment H_atoms_riding _refine_ls_number_reflns 3659 _refine_ls_number_parameters 168 _refine_ls_number_restraints 0 _refine_ls_goodness_of_fit_ref 1.059 _refine_ls_weighting_scheme 'calc ' _refine_ls_weighting_details '1/[\s^2^(Fo^2^)+(0.0732P)^2^+0.2936P] where P=(Fo^2^+2Fc^2^)/3 ' _refine_ls_shift/su_max 0.000 _refine_diff_density_max 0.42 _refine_diff_density_min -0.56 _refine_ls_extinction_method none _atom_type_scat_source 'International Tables for Crystallography (Vol C)' # 8. COMPUTING DATA _computing_data_collection Collect_(Nonius,_1998) _computing_cell_refinement DENZO/SCALEPACK_(Otwinowski,_1996) _computing_data_reduction DENZO/SCALEPACK_(Otwinowski,_1996) _computing_structure_solution PATTY_(DIRDIF99,_Beurskins,_1999) _computing_structure_refinement SHELX97_(Sheldrick,_1997) _computing_molecular_graphics ; ORTEP (Johnson, 1976) PLATON (Spek, 1997) ; _computing_publication_material CIF_VAX_MolEN_(Fair,_1990) # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS 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 Ti Ti 0.16988(6) -0.23921(5) -0.32585(3) 0.02554(14) Uani 1 1 d . . . S S -0.17110(8) -0.20197(8) -0.29325(4) 0.02882(16) Uani 1 1 d . . . C(1) C 0.3179(6) -0.4727(4) -0.3948(2) 0.0596(10) Uani 1 1 d . . . C(2) C 0.1315(5) -0.4271(4) -0.4199(2) 0.0527(8) Uani 1 1 d . . . C(3) C 0.1220(5) -0.2578(4) -0.47475(18) 0.0499(8) Uani 1 1 d . . . C(4) C 0.2986(6) -0.1972(5) -0.48405(19) 0.0573(9) Uani 1 1 d . . . C(5) C 0.4233(5) -0.3289(6) -0.4344(3) 0.0672(11) Uani 1 1 d . . . C(6) C 0.2917(4) -0.3954(4) -0.20847(17) 0.0368(6) Uani 1 1 d . . . C(7) C 0.2708(3) 0.0077(3) -0.33360(15) 0.0297(5) Uani 1 1 d . . . C(11) C -0.1977(3) -0.1351(3) -0.18599(14) 0.0243(4) Uani 1 1 d . . . C(12) C -0.2053(3) -0.2631(3) -0.10154(15) 0.0267(5) Uani 1 1 d . . . C(13) C -0.2289(3) -0.2078(3) -0.01928(16) 0.0302(5) Uani 1 1 d . . . C(14) C -0.2489(3) -0.0313(3) -0.01649(15) 0.0294(5) Uani 1 1 d . . . C(15) C -0.2487(3) 0.0926(3) -0.10064(16) 0.0295(5) Uani 1 1 d . . . C(16) C -0.2241(3) 0.0453(3) -0.18525(15) 0.0266(5) Uani 1 1 d . . . C(17) C -0.1991(4) -0.4561(3) -0.09736(18) 0.0362(6) Uani 1 1 d . . . C(18) C -0.2719(4) 0.0244(4) 0.07343(17) 0.0401(6) Uani 1 1 d . . . C(19) C -0.2349(4) 0.1875(3) -0.27298(17) 0.0374(6) Uani 1 1 d . . . H(1) H 0.3661 -0.5821 -0.3572 0.072 Uiso 1 1 calc R . . H(2) H 0.0279 -0.4994 -0.4027 0.063 Uiso 1 1 calc R . . H(3) H 0.0100 -0.1939 -0.5017 0.060 Uiso 1 1 calc R . . H(4) H 0.3310 -0.0845 -0.5185 0.069 Uiso 1 1 calc R . . H(5) H 0.5559 -0.3225 -0.4284 0.081 Uiso 1 1 calc R . . H(13) H -0.2314 -0.2945 0.0375 0.036 Uiso 1 1 calc R . . H(15) H -0.2662 0.2143 -0.1002 0.035 Uiso 1 1 calc R . . H(6A) H 0.4331 -0.3870 -0.2167 0.055 Uiso 1 1 calc R . . H(6B) H 0.2708 -0.5186 -0.2007 0.055 Uiso 1 1 calc R . . H(6C) H 0.2280 -0.3535 -0.1534 0.055 Uiso 1 1 calc R . . H(7A) H 0.2083 0.0534 -0.2795 0.045 Uiso 1 1 calc R . . H(7B) H 0.2363 0.0922 -0.3902 0.045 Uiso 1 1 calc R . . H(7C) H 0.4139 -0.0096 -0.3346 0.045 Uiso 1 1 calc R . . H(17A) H -0.1899 -0.5238 -0.0337 0.054 Uiso 1 1 calc R . . H(17B) H -0.0843 -0.4938 -0.1385 0.054 Uiso 1 1 calc R . . H(17C) H -0.3192 -0.4765 -0.1172 0.054 Uiso 1 1 calc R . . H(18A) H -0.2927 -0.0778 0.1251 0.060 Uiso 1 1 calc R . . H(18B) H -0.3853 0.1152 0.0761 0.060 Uiso 1 1 calc R . . H(18C) H -0.1528 0.0722 0.0778 0.060 Uiso 1 1 calc R . . H(19A) H -0.2565 0.3035 -0.2579 0.056 Uiso 1 1 calc R . . H(19B) H -0.3441 0.1744 -0.3035 0.056 Uiso 1 1 calc R . . H(19C) H -0.1113 0.1770 -0.3146 0.056 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_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Ti 0.0267(2) 0.0298(2) 0.0208(2) -0.00149(16) -0.00236(15) -0.00879(15) S 0.0273(3) 0.0349(3) 0.0268(3) -0.0018(2) -0.0038(2) -0.0130(2) C(1) 0.089(3) 0.0484(18) 0.0374(15) 0.0302(18) -0.0115(16) -0.0237(13) C(2) 0.067(2) 0.062(2) 0.0412(15) -0.0237(16) 0.0107(14) -0.0351(14) C(3) 0.0603(19) 0.064(2) 0.0280(13) 0.0112(15) -0.0121(12) -0.0231(13) C(4) 0.089(3) 0.0551(19) 0.0278(13) -0.0209(18) 0.0181(14) -0.0185(13) C(5) 0.0344(15) 0.122(3) 0.062(2) -0.0039(18) 0.0088(14) -0.066(2) C(6) 0.0337(13) 0.0431(14) 0.0301(12) 0.0007(11) -0.0041(10) -0.0053(10) C(7) 0.0241(10) 0.0401(13) 0.0263(10) -0.0062(9) 0.0003(8) -0.0113(9) C(11) 0.0226(10) 0.0270(11) 0.0237(10) -0.0022(8) -0.0017(8) -0.0081(8) C(12) 0.0256(10) 0.0261(11) 0.0271(11) -0.0029(8) -0.0011(8) -0.0052(9) C(13) 0.0267(11) 0.0369(13) 0.0253(10) -0.0038(9) -0.0032(9) -0.0041(9) C(14) 0.0245(11) 0.0413(13) 0.0256(10) -0.0050(9) -0.0009(8) -0.0148(9) C(15) 0.0292(11) 0.0292(11) 0.0328(12) -0.0044(9) -0.0003(9) -0.0145(9) C(16) 0.0250(11) 0.0274(11) 0.0268(10) -0.0017(9) -0.0003(8) -0.0084(9) C(17) 0.0413(14) 0.0260(12) 0.0378(13) -0.0048(10) -0.0035(11) -0.0015(10) C(18) 0.0331(13) 0.0618(18) 0.0331(13) -0.0083(12) -0.0020(10) -0.0248(12) C(19) 0.0465(15) 0.0270(12) 0.0345(13) -0.0001(11) -0.0017(11) -0.0044(10) # 10. MOLECULAR GEOMETRY _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 Ti C(6) 2.105(2) . ? Ti C(7) 2.142(2) . ? Ti S 2.3242(8) . ? Ti C(5) 2.343(3) . ? Ti C(1) 2.351(3) . ? Ti C(4) 2.357(3) . ? Ti C(2) 2.361(3) . ? Ti C(3) 2.361(3) . ? S C(11) 1.792(2) . ? C(1) C(2) 1.378(5) . ? C(1) C(5) 1.399(6) . ? C(2) C(3) 1.380(5) . ? C(3) C(4) 1.359(5) . ? C(4) C(5) 1.390(5) . ? C(11) C(16) 1.409(3) . ? C(11) C(12) 1.410(3) . ? C(12) C(13) 1.388(3) . ? C(12) C(17) 1.501(3) . ? C(13) C(14) 1.388(4) . ? C(14) C(15) 1.392(3) . ? C(14) C(18) 1.500(3) . ? C(15) C(16) 1.390(3) . ? C(16) C(19) 1.506(3) . ? 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 C(6) Ti C(7) 100.23(10) . . ? C(6) Ti S 109.74(7) . . ? C(7) Ti S 107.62(6) . . ? C(6) Ti C(5) 95.54(13) . . ? C(7) Ti C(5) 95.62(13) . . ? S Ti C(5) 141.29(9) . . ? C(6) Ti C(1) 83.89(11) . . ? C(7) Ti C(1) 129.86(12) . . ? S Ti C(1) 117.89(11) . . ? C(5) Ti C(1) 34.68(14) . . ? C(6) Ti C(4) 129.74(12) . . ? C(7) Ti C(4) 85.52(10) . . ? S Ti C(4) 115.84(10) . . ? C(5) Ti C(4) 34.40(13) . . ? C(1) Ti C(4) 57.02(12) . . ? C(6) Ti C(2) 108.07(12) . . ? C(7) Ti C(2) 141.60(10) . . ? S Ti C(2) 86.89(9) . . ? C(5) Ti C(2) 56.91(12) . . ? C(1) Ti C(2) 34.01(12) . . ? C(4) Ti C(2) 56.46(11) . . ? C(6) Ti C(3) 139.80(11) . . ? C(7) Ti C(3) 109.89(11) . . ? S Ti C(3) 86.21(8) . . ? C(5) Ti C(3) 56.44(12) . . ? C(1) Ti C(3) 56.46(11) . . ? C(4) Ti C(3) 33.48(12) . . ? C(2) Ti C(3) 34.00(12) . . ? C(11) S Ti 99.78(7) . . ? C(2) C(1) C(5) 107.6(3) . . ? C(2) C(1) Ti 73.40(16) . . ? C(5) C(1) Ti 72.36(17) . . ? C(1) C(2) C(3) 107.8(3) . . ? C(1) C(2) Ti 72.60(17) . . ? C(3) C(2) Ti 73.02(17) . . ? C(4) C(3) C(2) 109.1(3) . . ? C(4) C(3) Ti 73.09(16) . . ? C(2) C(3) Ti 72.98(16) . . ? C(3) C(4) C(5) 108.0(3) . . ? C(3) C(4) Ti 73.43(16) . . ? C(5) C(4) Ti 72.24(17) . . ? C(4) C(5) C(1) 107.4(3) . . ? C(4) C(5) Ti 73.36(17) . . ? C(1) C(5) Ti 72.96(17) . . ? C(16) C(11) C(12) 119.7(2) . . ? C(16) C(11) S 120.28(16) . . ? C(12) C(11) S 119.84(17) . . ? C(13) C(12) C(11) 118.8(2) . . ? C(13) C(12) C(17) 118.9(2) . . ? C(11) C(12) C(17) 122.2(2) . . ? C(14) C(13) C(12) 122.8(2) . . ? C(13) C(14) C(15) 117.3(2) . . ? C(13) C(14) C(18) 121.6(2) . . ? C(15) C(14) C(18) 121.2(2) . . ? C(16) C(15) C(14) 122.6(2) . . ? C(15) C(16) C(11) 118.8(2) . . ? C(15) C(16) C(19) 119.4(2) . . ? C(11) C(16) C(19) 121.8(2) . . ? 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 C(6) Ti S C(11) 49.49(11) . . . . ? C(7) Ti S C(11) -58.69(10) . . . . ? C(5) Ti S C(11) 177.2(2) . . . . ? C(1) Ti S C(11) 143.04(11) . . . . ? C(4) Ti S C(11) -152.29(12) . . . . ? C(2) Ti S C(11) 157.58(12) . . . . ? C(3) Ti S C(11) -168.37(11) . . . . ? C(6) Ti C(1) C(2) 135.7(2) . . . . ? C(7) Ti C(1) C(2) -126.0(2) . . . . ? S Ti C(1) C(2) 26.6(2) . . . . ? C(5) Ti C(1) C(2) -115.3(3) . . . . ? C(4) Ti C(1) C(2) -77.5(2) . . . . ? C(3) Ti C(1) C(2) -37.25(19) . . . . ? C(6) Ti C(1) C(5) -109.0(2) . . . . ? C(7) Ti C(1) C(5) -10.8(3) . . . . ? S Ti C(1) C(5) 141.9(2) . . . . ? C(4) Ti C(1) C(5) 37.7(2) . . . . ? C(2) Ti C(1) C(5) 115.3(3) . . . . ? C(3) Ti C(1) C(5) 78.0(2) . . . . ? C(5) C(1) C(2) C(3) 0.3(3) . . . . ? Ti C(1) C(2) C(3) 65.03(19) . . . . ? C(5) C(1) C(2) Ti -64.7(2) . . . . ? C(6) Ti C(2) C(1) -46.9(2) . . . . ? C(7) Ti C(2) C(1) 88.5(3) . . . . ? S Ti C(2) C(1) -156.6(2) . . . . ? C(5) Ti C(2) C(1) 37.9(2) . . . . ? C(4) Ti C(2) C(1) 79.3(2) . . . . ? C(3) Ti C(2) C(1) 115.5(3) . . . . ? C(6) Ti C(2) C(3) -162.41(19) . . . . ? C(7) Ti C(2) C(3) -27.0(3) . . . . ? S Ti C(2) C(3) 87.83(19) . . . . ? C(5) Ti C(2) C(3) -77.7(2) . . . . ? C(1) Ti C(2) C(3) -115.5(3) . . . . ? C(4) Ti C(2) C(3) -36.2(2) . . . . ? C(1) C(2) C(3) C(4) -0.1(3) . . . . ? Ti C(2) C(3) C(4) 64.7(2) . . . . ? C(1) C(2) C(3) Ti -64.7(2) . . . . ? C(6) Ti C(3) C(4) -90.4(3) . . . . ? C(7) Ti C(3) C(4) 45.8(2) . . . . ? S Ti C(3) C(4) 153.1(2) . . . . ? C(5) Ti C(3) C(4) -37.6(2) . . . . ? C(1) Ti C(3) C(4) -79.5(2) . . . . ? C(2) Ti C(3) C(4) -116.8(3) . . . . ? C(6) Ti C(3) C(2) 26.4(3) . . . . ? C(7) Ti C(3) C(2) 162.56(19) . . . . ? S Ti C(3) C(2) -90.06(19) . . . . ? C(5) Ti C(3) C(2) 79.2(2) . . . . ? C(1) Ti C(3) C(2) 37.3(2) . . . . ? C(4) Ti C(3) C(2) 116.8(3) . . . . ? C(2) C(3) C(4) C(5) -0.2(3) . . . . ? Ti C(3) C(4) C(5) 64.4(2) . . . . ? C(2) C(3) C(4) Ti -64.6(2) . . . . ? C(6) Ti C(4) C(3) 122.9(2) . . . . ? C(7) Ti C(4) C(3) -137.5(2) . . . . ? S Ti C(4) C(3) -30.1(2) . . . . ? C(5) Ti C(4) C(3) 115.8(3) . . . . ? C(1) Ti C(4) C(3) 77.7(2) . . . . ? C(2) Ti C(4) C(3) 36.78(19) . . . . ? C(6) Ti C(4) C(5) 7.2(3) . . . . ? C(7) Ti C(4) C(5) 106.8(2) . . . . ? S Ti C(4) C(5) -145.8(2) . . . . ? C(1) Ti C(4) C(5) -38.0(2) . . . . ? C(2) Ti C(4) C(5) -79.0(2) . . . . ? C(3) Ti C(4) C(5) -115.8(3) . . . . ? C(3) C(4) C(5) C(1) 0.3(3) . . . . ? Ti C(4) C(5) C(1) 65.5(2) . . . . ? C(3) C(4) C(5) Ti -65.2(2) . . . . ? C(2) C(1) C(5) C(4) -0.4(3) . . . . ? Ti C(1) C(5) C(4) -65.8(2) . . . . ? C(2) C(1) C(5) Ti 65.4(2) . . . . ? C(6) Ti C(5) C(4) -174.5(2) . . . . ? C(7) Ti C(5) C(4) -73.6(2) . . . . ? S Ti C(5) C(4) 53.9(3) . . . . ? C(1) Ti C(5) C(4) 114.7(3) . . . . ? C(2) Ti C(5) C(4) 77.6(2) . . . . ? C(3) Ti C(5) C(4) 36.6(2) . . . . ? C(6) Ti C(5) C(1) 70.8(2) . . . . ? C(7) Ti C(5) C(1) 171.7(2) . . . . ? S Ti C(5) C(1) -60.7(3) . . . . ? C(4) Ti C(5) C(1) -114.7(3) . . . . ? C(2) Ti C(5) C(1) -37.13(19) . . . . ? C(3) Ti C(5) C(1) -78.1(2) . . . . ? Ti S C(11) C(16) 93.96(18) . . . . ? Ti S C(11) C(12) -90.26(17) . . . . ? C(16) C(11) C(12) C(13) -3.3(3) . . . . ? S C(11) C(12) C(13) -179.07(17) . . . . ? C(16) C(11) C(12) C(17) 173.6(2) . . . . ? S C(11) C(12) C(17) -2.2(3) . . . . ? C(11) C(12) C(13) C(14) 1.2(3) . . . . ? C(17) C(12) C(13) C(14) -175.7(2) . . . . ? C(12) C(13) C(14) C(15) 1.3(3) . . . . ? C(12) C(13) C(14) C(18) -179.3(2) . . . . ? C(13) C(14) C(15) C(16) -1.9(3) . . . . ? C(18) C(14) C(15) C(16) 178.8(2) . . . . ? C(14) C(15) C(16) C(11) -0.2(3) . . . . ? C(14) C(15) C(16) C(19) 177.2(2) . . . . ? C(12) C(11) C(16) C(15) 2.8(3) . . . . ? S C(11) C(16) C(15) 178.54(17) . . . . ? C(12) C(11) C(16) C(19) -174.6(2) . . . . ? S C(11) C(16) C(19) 1.2(3) . . . . ? data_AF3113 _database_code_depnum_ccdc_archive 'CCDC 247468' _audit_creation_date 2-10-03 _audit_creation_method from_MolEN_and_SHELXL _audit_update_record ; ? ; # 5. CRYSTAL DATA _chemical_compound_source ? _exptl_crystal_description plate _exptl_crystal_colour colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.08 _chemical_name_systematic ; ? ; _exptl_crystal_density_method ? _chemical_absolute_configuration ad _chemical_formula_sum 'C22 H34 S1 Ti1' _chemical_formula_moiety 'C22 H34 S1 Ti1' _chemical_formula_structural ? _chemical_formula_weight 378.48 _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 1 2 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 32.440(3) _cell_length_b 8.3708(3) _cell_length_c 15.9783(13) _cell_angle_alpha 90.00 _cell_angle_beta 102.689(3) _cell_angle_gamma 90.00 _cell_volume 4232.9(5) _cell_measurement_reflns_used 11077 _cell_measurement_theta_min 1 _cell_measurement_theta_max 23 _cell_formula_units_z 8 _exptl_crystal_density_diffrn 1.19 _exptl_crystal_density_meas ? _diffrn_radiation_type MO-K\a _diffrn_radiation_wavelength 0.71073 _exptl_absorpt_coefficient_mu 0.495 _cell_measurement_temperature 150 _exptl_crystal_F_000 1632 # 6. DATA COLLECTION _diffrn_ambient_temperature 150 _diffrn_measurement_device_type Nonius_KappaCCD _diffrn_measurement_method \w _exptl_absorpt_correction_type multi-scan_(Otwinowski_&_Minor,_1 _exptl_absorpt_correction_T_min 0.8866 _exptl_absorpt_correction_T_max 0.9636 _diffrn_reflns_number 11077 _diffrn_measured_fraction_theta_max 0.9259 _reflns_number_total 5986 _reflns_Friedel_coverage 0.8443 _reflns_number_gt 5338 _reflns_threshold_expression >2.0\s(I) _diffrn_reflns_av_R_equivalents 0.076 _diffrn_reflns_theta_min 1.29 _diffrn_reflns_theta_max 23.77 _diffrn_reflns_limit_h_min -35 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_h_max 36 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_max 18 _diffrn_special_details 'mosaicity from Denzo/Scalepack is 0.47' # 7. REFINEMENT DATA _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating R_factor_obs 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_R_factor_all 0.098 _refine_ls_R_factor_gt 0.077 _refine_ls_wR_factor_ref 0.204 _refine_ls_wR_factor_gt 0.187 _refine_ls_hydrogen_treatment H_atoms_riding _refine_ls_number_reflns 5986 _refine_ls_number_parameters 484 _refine_ls_number_restraints 13 _refine_ls_goodness_of_fit_ref 1.034 _refine_ls_weighting_scheme 'calc ' _refine_ls_weighting_details '1/[\s^2^(Fo^2^)+(0.1354P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3 ' _refine_ls_shift/su_max 0.001 _refine_diff_density_max 1.90 _refine_diff_density_min -0.45 _refine_ls_extinction_method none _atom_type_scat_source 'International Tables for Crystallography (Vol C)' # 8. COMPUTING DATA _computing_data_collection Collect_(Nonius,_1998) _computing_cell_refinement DENZO/SCALEPACK_(Otwinowski,_1996) _computing_data_reduction DENZO/SCALEPACK_(Otwinowski,_1996) _computing_structure_solution Direct_methods_(SIR2002,_Burla_et_al.,_2003) _computing_structure_refinement SHELX97_(Sheldrick,_1997) _computing_molecular_graphics ; ORTEP (Johnson, 1976) PLATON (Spek, 1997) ; _computing_publication_material CIF_VAX_MolEN_(Fair,_1990) _refine_ls_abs_structure_details 'Flack H. D. (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.01(6) # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS 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 Ti(1) Ti 0.65667(4) 0.18333(15) 0.37710(8) 0.0274(3) Uani 1 1 d . . . Ti(2) Ti 0.65409(4) -0.30608(16) 0.75798(8) 0.0318(4) Uani 1 1 d . . . S(2) S 0.66380(6) -0.0340(2) 0.74013(12) 0.0285(4) Uani 1 1 d . . . S(1]) S 0.66671(6) 0.4545(2) 0.40638(12) 0.0273(4) Uani 1 1 d . . . C(11) C 0.7226(2) 0.1443(9) 0.4741(5) 0.0324(18) Uani 1 1 d . . . C(12) C 0.6913(3) 0.1467(9) 0.5234(5) 0.039(2) Uani 1 1 d . . . C(13) C 0.6644(3) 0.0186(9) 0.4979(5) 0.041(2) Uani 1 1 d . . . C(14) C 0.6787(3) -0.0658(10) 0.4339(5) 0.041(2) Uani 1 1 d . . . C(15) C 0.7147(2) 0.0096(9) 0.4204(5) 0.0346(18) Uani 1 1 d . . . C(16) C 0.5923(3) 0.1356(10) 0.3591(6) 0.044(2) Uani 1 1 d . . . C(17) C 0.6621(3) 0.1345(10) 0.2530(5) 0.039(2) Uani 1 1 d . . . C(21) C 0.7184(2) -0.3344(10) 0.7142(5) 0.0392(19) Uani 1 1 d . . . C(22) C 0.7137(3) -0.4687(11) 0.7636(7) 0.049(2) Uani 1 1 d . . . C(23) C 0.6790(3) -0.5547(10) 0.7211(5) 0.044(2) Uani 1 1 d . . . C(24) C 0.6618(3) -0.4727(9) 0.6433(6) 0.044(2) Uani 1 1 d . . . C(25) C 0.6863(3) -0.3381(11) 0.6393(5) 0.043(2) Uani 1 1 d . . . C(26) C 0.5902(3) -0.3592(11) 0.7228(6) 0.053(2) Uani 1 1 d . . . C(27) C 0.6619(3) -0.3526(11) 0.8871(5) 0.048(2) Uani 1 1 d . . . C(111) C 0.6311(2) 0.5423(8) 0.3177(5) 0.0314(18) Uani 1 1 d . . . C(112) C 0.6449(3) 0.5816(9) 0.2435(5) 0.0355(19) Uani 1 1 d . . . C(113) C 0.6176(4) 0.6693(11) 0.1774(5) 0.060(3) Uani 1 1 d . . . C(114) C 0.5778(4) 0.7175(11) 0.1845(7) 0.067(3) Uani 1 1 d . D . C(115) C 0.5649(3) 0.6725(11) 0.2574(8) 0.065(3) Uani 1 1 d . . . C(116) C 0.5903(3) 0.5886(9) 0.3237(7) 0.045(2) Uani 1 1 d . . . C(121) C 0.7204(3) 0.6721(11) 0.2675(6) 0.045(2) Uani 1 1 d . . . C(122) C 0.6889(3) 0.5429(10) 0.2323(5) 0.044(2) Uani 1 1 d . . . C(123) C 0.6921(4) 0.4986(11) 0.1408(6) 0.070(3) Uani 1 1 d . . . C(142) C 0.5491(4) 0.8045(11) 0.1109(7) 0.084(4) Uani 1 1 d D . . C(14A) C 0.5751(6) 0.851(2) 0.0334(11) 0.051(5) Uani 0.50 1 d PD D 1 C(14B) C 0.5034(5) 0.853(2) 0.1406(12) 0.047(5) Uani 0.50 1 d PD D 2 C(15A) C 0.5339(6) 0.967(2) 0.1341(11) 0.056(5) Uani 0.50 1 d PD D 1 C(15B) C 0.5650(6) 0.979(2) 0.1020(15) 0.069(6) Uani 0.50 1 d PD D 2 C(161) C 0.5773(3) 0.6967(13) 0.4615(7) 0.060(3) Uani 1 1 d . . . C(162) C 0.5728(3) 0.5518(11) 0.4026(8) 0.060(3) Uani 1 1 d . . . C(163) C 0.5270(3) 0.4924(14) 0.3821(11) 0.098(5) Uani 1 1 d . . . C(211) C 0.6272(3) 0.0539(8) 0.7970(6) 0.0348(19) Uani 1 1 d . . . C(212) C 0.5867(3) 0.0932(10) 0.7536(7) 0.043(2) Uani 1 1 d . . . C(213) C 0.5607(3) 0.1772(12) 0.7969(9) 0.068(3) Uani 1 1 d . . . C(214) C 0.5740(4) 0.2242(11) 0.8813(10) 0.074(4) Uani 1 1 d . C . C(215) C 0.6145(5) 0.1793(12) 0.9238(6) 0.094(5) Uani 1 1 d . . . C(216) C 0.6422(4) 0.0933(10) 0.8834(6) 0.053(3) Uani 1 1 d . . . C(221) C 0.5759(3) 0.1942(13) 0.6052(6) 0.060(2) Uani 1 1 d . . . C(222) C 0.5699(3) 0.0537(11) 0.6598(7) 0.052(3) Uani 1 1 d . . . C(223) C 0.5236(3) -0.0022(14) 0.6383(11) 0.096(5) Uani 1 1 d . . . C(242) C 0.5457(4) 0.3095(12) 0.9312(8) 0.089(5) Uani 1 1 d D . . C(24A) C 0.5402(7) 0.4831(18) 0.8983(13) 0.053(5) Uani 0.50 1 d PD C 1 C(24B) C 0.5615(6) 0.4846(17) 0.9490(13) 0.049(5) Uani 0.50 1 d PD C 2 C(25A) C 0.5711(6) 0.340(2) 1.0346(10) 0.048(5) Uani 0.50 1 d PD C 1 C(25B) C 0.4989(5) 0.353(2) 0.8600(11) 0.049(5) Uiso 0.50 1 d PD C 2 C(261) C 0.7165(3) 0.1982(14) 0.9339(6) 0.065(3) Uani 1 1 d . . . C(262) C 0.6865(4) 0.0575(10) 0.9346(6) 0.060(3) Uani 1 1 d . . . C(263) C 0.6876(5) 0.0033(13) 1.0262(6) 0.096(5) Uani 1 1 d . . . H(11) H 0.7447 0.2196 0.4767 0.039 Uiso 1 1 calc R . . H(12) H 0.6891 0.2228 0.5664 0.047 Uiso 1 1 calc R . . H(13) H 0.6404 -0.0076 0.5201 0.049 Uiso 1 1 calc R . . H(14) H 0.6660 -0.1584 0.4050 0.049 Uiso 1 1 calc R . . H(15) H 0.7313 -0.0240 0.3814 0.042 Uiso 1 1 calc R . . H(21) H 0.7396 -0.2546 0.7289 0.047 Uiso 1 1 calc R . . H(22) H 0.7314 -0.4961 0.8173 0.059 Uiso 1 1 calc R . . H(23) H 0.6685 -0.6508 0.7404 0.053 Uiso 1 1 calc R . . H(24) H 0.6377 -0.5045 0.6012 0.052 Uiso 1 1 calc R . . H(25) H 0.6822 -0.2623 0.5940 0.051 Uiso 1 1 calc R . . H(113) H 0.6270 0.6954 0.1269 0.072 Uiso 1 1 calc R . . H(115) H 0.5372 0.7005 0.2624 0.078 Uiso 1 1 calc R . . H(122) H 0.6981 0.4460 0.2681 0.053 Uiso 1 1 calc R . . H(12A) H 0.7111 0.7736 0.2389 0.067 Uiso 1 1 calc R . . H(12B) H 0.7482 0.6435 0.2571 0.067 Uiso 1 1 calc R . . H(12C) H 0.7225 0.6832 0.3293 0.067 Uiso 1 1 calc R . . H(12D) H 0.6715 0.4148 0.1187 0.104 Uiso 1 1 calc R . . H(12E) H 0.7206 0.4595 0.1413 0.104 Uiso 1 1 calc R . . H(12F) H 0.6862 0.5930 0.1039 0.104 Uiso 1 1 calc R . . H(142) H 0.5242 0.7357 0.0862 0.101 Uiso 1 1 calc R A 1 H(14A) H 0.5994 0.9191 0.0575 0.076 Uiso 0.50 1 calc PR D 1 H(14B) H 0.5560 0.9084 -0.0130 0.076 Uiso 0.50 1 calc PR D 1 H(14C) H 0.5849 0.7529 0.0106 0.076 Uiso 0.50 1 calc PR D 1 H(14D) H 0.4891 0.7553 0.1525 0.071 Uiso 0.50 1 calc PR D 2 H(14E) H 0.4850 0.9124 0.0941 0.071 Uiso 0.50 1 calc PR D 2 H(14F) H 0.5099 0.9195 0.1923 0.071 Uiso 0.50 1 calc PR D 2 H(15A) H 0.5119 0.9529 0.1668 0.083 Uiso 0.50 1 calc PR D 1 H(15B) H 0.5224 1.0272 0.0816 0.083 Uiso 0.50 1 calc PR D 1 H(15C) H 0.5577 1.0261 0.1690 0.083 Uiso 0.50 1 calc PR D 1 H(15D) H 0.5710 1.0312 0.1583 0.104 Uiso 0.50 1 calc PR D 2 H(15E) H 0.5431 1.0396 0.0624 0.104 Uiso 0.50 1 calc PR D 2 H(15F) H 0.5908 0.9762 0.0797 0.104 Uiso 0.50 1 calc PR D 2 H(162) H 0.5906 0.4647 0.4349 0.072 Uiso 1 1 calc R . . H(16A) H 0.5765 0.2063 0.3144 0.065 Uiso 1 1 calc R . . H(16B) H 0.5832 0.1541 0.4129 0.065 Uiso 1 1 calc R . . H(16C) H 0.5869 0.0241 0.3414 0.065 Uiso 1 1 calc R . . H(16D) H 0.6071 0.7281 0.4779 0.091 Uiso 1 1 calc R . . H(16E) H 0.5671 0.6699 0.5131 0.091 Uiso 1 1 calc R . . H(16F) H 0.5607 0.7855 0.4314 0.091 Uiso 1 1 calc R . . H(16G) H 0.5206 0.4427 0.4333 0.147 Uiso 1 1 calc R . . H(16H) H 0.5233 0.4137 0.3356 0.147 Uiso 1 1 calc R . . H(16I) H 0.5079 0.5828 0.3642 0.147 Uiso 1 1 calc R . . H(17A) H 0.6575 0.0202 0.2413 0.058 Uiso 1 1 calc R . . H(17B) H 0.6904 0.1640 0.2463 0.058 Uiso 1 1 calc R . . H(17C) H 0.6410 0.1961 0.2125 0.058 Uiso 1 1 calc R . . H(213) H 0.5328 0.2031 0.7672 0.082 Uiso 1 1 calc R . . H(215) H 0.6238 0.2075 0.9825 0.112 Uiso 1 1 calc R . . H(222) H 0.5874 -0.0359 0.6450 0.062 Uiso 1 1 calc R . . H(22A) H 0.5626 0.2889 0.6239 0.090 Uiso 1 1 calc R . . H(22B) H 0.5629 0.1713 0.5450 0.090 Uiso 1 1 calc R . . H(22C) H 0.6062 0.2140 0.6110 0.090 Uiso 1 1 calc R . . H(22D) H 0.5049 0.0908 0.6340 0.143 Uiso 1 1 calc R . . H(22E) H 0.5186 -0.0734 0.6837 0.143 Uiso 1 1 calc R . . H(22F) H 0.5179 -0.0595 0.5835 0.143 Uiso 1 1 calc R . . H(242) H 0.5180 0.2538 0.9265 0.107 Uiso 1 1 calc R B 1 H(24A) H 0.5679 0.5281 0.8965 0.079 Uiso 0.50 1 calc PR C 1 H(24B) H 0.5272 0.5470 0.9370 0.079 Uiso 0.50 1 calc PR C 1 H(24C) H 0.5220 0.4846 0.8406 0.079 Uiso 0.50 1 calc PR C 1 H(24D) H 0.5873 0.4851 0.9945 0.073 Uiso 0.50 1 calc PR C 2 H(24E) H 0.5397 0.5481 0.9670 0.073 Uiso 0.50 1 calc PR C 2 H(24F) H 0.5676 0.5305 0.8966 0.073 Uiso 0.50 1 calc PR C 2 H(25A) H 0.5854 0.2412 1.0581 0.073 Uiso 0.50 1 calc PR C 1 H(25B) H 0.5506 0.3710 1.0684 0.073 Uiso 0.50 1 calc PR C 1 H(25C) H 0.5921 0.4251 1.0372 0.073 Uiso 0.50 1 calc PR C 1 H(25D) H 0.5049 0.4098 0.8104 0.073 Uiso 0.50 1 calc PR C 2 H(25E) H 0.4813 0.4200 0.8884 0.073 Uiso 0.50 1 calc PR C 2 H(25F) H 0.4839 0.2533 0.8407 0.073 Uiso 0.50 1 calc PR C 2 H(262) H 0.6975 -0.0333 0.9052 0.072 Uiso 1 1 calc R . . H(26A) H 0.5858 -0.4718 0.7351 0.080 Uiso 1 1 calc R . . H(26B) H 0.5800 -0.3391 0.6613 0.080 Uiso 1 1 calc R . . H(26C) H 0.5747 -0.2917 0.7554 0.080 Uiso 1 1 calc R . . H(26D) H 0.7067 0.2905 0.9620 0.097 Uiso 1 1 calc R . . H(26E) H 0.7169 0.2258 0.8745 0.097 Uiso 1 1 calc R . . H(26F) H 0.7450 0.1686 0.9647 0.097 Uiso 1 1 calc R . . H(26G) H 0.6801 0.0930 1.0593 0.143 Uiso 1 1 calc R . . H(26H) H 0.7162 -0.0338 1.0529 0.143 Uiso 1 1 calc R . . H(26I) H 0.6674 -0.0841 1.0254 0.143 Uiso 1 1 calc R . . H(27A) H 0.6433 -0.2825 0.9115 0.072 Uiso 1 1 calc R . . H(27B) H 0.6913 -0.3330 0.9161 0.072 Uiso 1 1 calc R . . H(27C) H 0.6547 -0.4643 0.8953 0.072 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_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Ti1 0.0284(7) 0.0226(7) 0.0301(7) -0.0014(6) 0.0040(5) 0.0034(6) Ti2 0.0418(8) 0.0236(7) 0.0349(7) 0.0015(7) 0.0191(6) -0.0005(7) S2 0.0332(11) 0.0247(9) 0.0306(10) 0.0002(8) 0.0133(8) -0.0014(8) S1] 0.0303(10) 0.0244(9) 0.0262(10) 0.0023(8) 0.0037(7) 0.0030(8) C11 0.031(4) 0.037(5) 0.024(4) 0.001(3) -0.004(3) 0.007(3) C12 0.054(5) 0.039(5) 0.022(4) 0.014(4) 0.004(4) 0.009(3) C13 0.056(6) 0.033(5) 0.036(5) 0.021(4) 0.016(4) 0.011(4) C14 0.056(6) 0.028(4) 0.042(5) 0.006(4) 0.020(4) 0.012(4) C15 0.035(5) 0.027(4) 0.043(5) 0.009(3) 0.013(4) 0.000(3) C16 0.038(5) 0.040(5) 0.051(5) -0.002(3) 0.005(4) 0.000(4) C17 0.040(5) 0.033(5) 0.037(5) -0.006(3) -0.005(4) -0.001(3) C21 0.034(4) 0.033(5) 0.056(5) 0.005(4) 0.022(4) -0.006(4) C22 0.051(6) 0.044(5) 0.054(6) 0.019(4) 0.014(5) 0.003(5) C23 0.066(6) 0.020(4) 0.046(5) 0.007(4) 0.016(4) -0.006(4) C24 0.068(6) 0.027(4) 0.040(5) 0.011(4) 0.020(4) -0.006(4) C25 0.049(5) 0.047(5) 0.037(5) 0.018(4) 0.020(4) -0.001(4) C26 0.056(6) 0.049(6) 0.060(6) -0.005(4) 0.024(5) -0.008(4) C27 0.067(6) 0.047(6) 0.038(5) 0.010(4) 0.030(4) 0.002(4) C111 0.037(5) 0.022(4) 0.031(4) -0.003(3) 0.000(3) 0.010(3) C112 0.056(5) 0.018(4) 0.030(4) -0.003(3) 0.004(4) -0.009(3) C113 0.112(9) 0.030(5) 0.026(4) 0.011(5) -0.012(5) 0.009(4) C114 0.079(8) 0.027(5) 0.067(7) -0.003(5) -0.044(6) 0.013(5) C115 0.031(5) 0.031(5) 0.113(9) -0.006(4) -0.024(5) 0.028(6) C116 0.034(5) 0.020(4) 0.078(7) -0.003(3) 0.007(4) 0.014(4) C121 0.054(5) 0.034(5) 0.053(5) 0.001(4) 0.028(4) -0.004(4) C122 0.080(7) 0.029(4) 0.031(5) 0.002(4) 0.026(5) -0.007(3) C123 0.142(11) 0.041(6) 0.039(6) -0.002(6) 0.048(6) -0.003(4) C142 0.098(9) 0.037(6) 0.084(9) -0.014(5) -0.050(7) 0.019(6) C14A 0.054(12) 0.051(11) 0.043(12) 0.012(9) 0.001(9) 0.025(9) C14B 0.032(10) 0.042(10) 0.059(12) 0.015(8) -0.009(8) 0.028(9) C15A 0.058(13) 0.073(14) 0.032(10) 0.002(11) 0.003(9) 0.014(10) C15B 0.032(11) 0.094(17) 0.073(15) 0.012(11) -0.006(10) 0.019(14) C161 0.052(6) 0.054(6) 0.079(7) 0.010(5) 0.025(5) 0.024(6) C162 0.028(5) 0.047(6) 0.106(9) 0.014(4) 0.019(5) 0.040(6) C163 0.031(6) 0.064(7) 0.206(16) -0.006(5) 0.041(8) 0.014(9) C211 0.044(5) 0.019(4) 0.050(5) -0.004(3) 0.030(4) -0.005(3) C212 0.029(5) 0.029(4) 0.079(7) -0.001(3) 0.028(4) 0.002(4) C213 0.049(6) 0.036(5) 0.136(10) -0.003(5) 0.055(6) -0.026(7) C214 0.108(10) 0.019(5) 0.123(11) 0.012(5) 0.084(9) 0.004(6) C215 0.233(16) 0.027(5) 0.047(6) 0.038(8) 0.086(8) 0.006(5) C216 0.108(9) 0.020(4) 0.043(6) 0.017(5) 0.040(6) 0.015(4) C221 0.057(6) 0.049(5) 0.070(6) -0.001(5) 0.007(5) 0.001(6) C222 0.025(5) 0.045(5) 0.082(8) 0.001(4) 0.004(5) -0.019(5) C223 0.025(5) 0.071(8) 0.185(15) 0.005(5) 0.011(7) -0.028(9) C242 0.118(11) 0.035(5) 0.149(13) -0.011(6) 0.106(10) -0.025(7) C24A 0.053(13) 0.060(13) 0.043(12) 0.023(10) 0.005(10) -0.008(10) C24B 0.047(12) 0.065(13) 0.039(11) 0.035(10) 0.018(9) -0.007(10) C25A 0.078(14) 0.038(10) 0.038(11) 0.021(9) 0.031(10) -0.007(8) C261 0.107(8) 0.053(6) 0.032(5) 0.025(6) 0.008(5) 0.015(5) C262 0.131(10) 0.029(5) 0.023(5) 0.033(5) 0.023(5) 0.005(4) C263 0.221(16) 0.047(7) 0.014(5) 0.021(8) 0.015(7) 0.015(4) # 10. MOLECULAR GEOMETRY _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 Ti(1) C(17) 2.070(8) . ? Ti(1) C(16) 2.084(8) . ? Ti(1) C(14) 2.324(8) . ? Ti(1) S(1]) 2.326(2) . ? Ti(1) C(13) 2.341(8) . ? Ti(1) C(15) 2.360(7) . ? Ti(1) C(11) 2.371(7) . ? Ti(1) C(12) 2.380(8) . ? Ti(2) C(27) 2.061(8) . ? Ti(2) C(26) 2.072(9) . ? Ti(2) S(2) 2.325(2) . ? Ti(2) C(22) 2.350(9) . ? Ti(2) C(21) 2.352(7) . ? Ti(2) C(23) 2.353(8) . ? Ti(2) C(24) 2.359(8) . ? Ti(2) C(25) 2.373(8) . ? S(2) C(211) 1.804(7) . ? S(1]) C(111) 1.779(7) . ? C(11) C(15) 1.406(11) . ? C(11) C(12) 1.415(11) . ? C(12) C(13) 1.386(12) . ? C(13) C(14) 1.403(12) . ? C(14) C(15) 1.386(12) . ? C(21) C(22) 1.401(12) . ? C(21) C(25) 1.402(12) . ? C(22) C(23) 1.382(13) . ? C(23) C(24) 1.423(12) . ? C(24) C(25) 1.389(13) . ? C(111) C(112) 1.397(11) . ? C(111) C(116) 1.403(11) . ? C(112) C(113) 1.423(12) . ? C(112) C(122) 1.513(13) . ? C(113) C(114) 1.381(15) . ? C(114) C(115) 1.374(15) . ? C(114) C(142) 1.516(13) . ? C(115) C(116) 1.383(13) . ? C(116) C(162) 1.522(14) . ? C(121) C(122) 1.509(12) . ? C(122) C(123) 1.533(12) . ? C(142) C(15A) 1.521(16) . ? C(142) C(15B) 1.568(16) . ? C(142) C(14A) 1.690(15) . ? C(142) C(14B) 1.701(15) . ? C(161) C(162) 1.523(16) . ? C(162) C(163) 1.531(14) . ? C(211) C(212) 1.382(12) . ? C(211) C(216) 1.400(13) . ? C(212) C(213) 1.393(12) . ? C(212) C(222) 1.515(14) . ? C(213) C(214) 1.379(17) . ? C(214) C(215) 1.390(18) . ? C(214) C(242) 1.520(13) . ? C(215) C(216) 1.415(14) . ? C(216) C(262) 1.517(16) . ? C(221) C(222) 1.502(14) . ? C(222) C(223) 1.537(13) . ? C(242) C(24A) 1.542(15) . ? C(242) C(24B) 1.558(15) . ? C(242) C(25A) 1.697(15) . ? C(242) C(25B) 1.724(15) . ? C(261) C(262) 1.529(15) . ? C(262) C(263) 1.525(12) . ? 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 C(17) Ti(1) C(16) 97.1(3) . . ? C(17) Ti(1) C(14) 96.5(3) . . ? C(16) Ti(1) C(14) 95.5(3) . . ? C(17) Ti(1) S(1]) 110.4(2) . . ? C(16) Ti(1) S(1]) 107.9(2) . . ? C(14) Ti(1) S(1]) 141.2(2) . . ? C(17) Ti(1) C(13) 131.1(3) . . ? C(16) Ti(1) C(13) 85.6(3) . . ? C(14) Ti(1) C(13) 35.0(3) . . ? S(1]) Ti(1) C(13) 115.1(2) . . ? C(17) Ti(1) C(15) 85.9(3) . . ? C(16) Ti(1) C(15) 129.3(3) . . ? C(14) Ti(1) C(15) 34.4(3) . . ? S(1]) Ti(1) C(15) 118.4(2) . . ? C(13) Ti(1) C(15) 57.4(3) . . ? C(17) Ti(1) C(11) 110.1(3) . . ? C(16) Ti(1) C(11) 142.8(3) . . ? C(14) Ti(1) C(11) 57.7(3) . . ? S(1]) Ti(1) C(11) 86.4(2) . . ? C(13) Ti(1) C(11) 57.4(3) . . ? C(15) Ti(1) C(11) 34.6(3) . . ? C(17) Ti(1) C(12) 142.6(3) . . ? C(16) Ti(1) C(12) 110.7(3) . . ? C(14) Ti(1) C(12) 57.5(3) . . ? S(1]) Ti(1) C(12) 85.0(2) . . ? C(13) Ti(1) C(12) 34.1(3) . . ? C(15) Ti(1) C(12) 57.2(3) . . ? C(11) Ti(1) C(12) 34.6(3) . . ? C(27) Ti(2) C(26) 97.3(4) . . ? C(27) Ti(2) S(2) 108.5(3) . . ? C(26) Ti(2) S(2) 109.3(3) . . ? C(27) Ti(2) C(22) 86.2(3) . . ? C(26) Ti(2) C(22) 130.6(4) . . ? S(2) Ti(2) C(22) 116.1(2) . . ? C(27) Ti(2) C(21) 110.9(3) . . ? C(26) Ti(2) C(21) 142.8(3) . . ? S(2) Ti(2) C(21) 84.8(2) . . ? C(22) Ti(2) C(21) 34.7(3) . . ? C(27) Ti(2) C(23) 96.3(3) . . ? C(26) Ti(2) C(23) 96.9(3) . . ? S(2) Ti(2) C(23) 140.6(2) . . ? C(22) Ti(2) C(23) 34.2(3) . . ? C(21) Ti(2) C(23) 57.4(3) . . ? C(27) Ti(2) C(24) 131.0(3) . . ? C(26) Ti(2) C(24) 86.1(4) . . ? S(2) Ti(2) C(24) 116.3(2) . . ? C(22) Ti(2) C(24) 57.4(3) . . ? C(21) Ti(2) C(24) 57.2(3) . . ? C(23) Ti(2) C(24) 35.2(3) . . ? C(27) Ti(2) C(25) 143.2(3) . . ? C(26) Ti(2) C(25) 110.4(3) . . ? S(2) Ti(2) C(25) 85.3(2) . . ? C(22) Ti(2) C(25) 57.5(3) . . ? C(21) Ti(2) C(25) 34.5(3) . . ? C(23) Ti(2) C(25) 57.6(3) . . ? C(24) Ti(2) C(25) 34.1(3) . . ? C(211) S(2) Ti(2) 102.5(2) . . ? C(111) S(1]) Ti(1) 101.8(2) . . ? C(15) C(11) C(12) 107.2(7) . . ? C(15) C(11) Ti(1) 72.3(4) . . ? C(12) C(11) Ti(1) 73.0(4) . . ? C(13) C(12) C(11) 107.9(7) . . ? C(13) C(12) Ti(1) 71.4(4) . . ? C(11) C(12) Ti(1) 72.3(4) . . ? C(12) C(13) C(14) 108.4(8) . . ? C(12) C(13) Ti(1) 74.5(5) . . ? C(14) C(13) Ti(1) 71.8(4) . . ? C(15) C(14) C(13) 108.0(8) . . ? C(15) C(14) Ti(1) 74.2(5) . . ? C(13) C(14) Ti(1) 73.1(5) . . ? C(14) C(15) C(11) 108.4(7) . . ? C(14) C(15) Ti(1) 71.4(5) . . ? C(11) C(15) Ti(1) 73.2(4) . . ? C(22) C(21) C(25) 108.1(8) . . ? C(22) C(21) Ti(2) 72.6(5) . . ? C(25) C(21) Ti(2) 73.6(4) . . ? C(23) C(22) C(21) 108.6(9) . . ? C(23) C(22) Ti(2) 73.0(5) . . ? C(21) C(22) Ti(2) 72.7(5) . . ? C(22) C(23) C(24) 107.4(8) . . ? C(22) C(23) Ti(2) 72.8(5) . . ? C(24) C(23) Ti(2) 72.7(4) . . ? C(25) C(24) C(23) 108.2(8) . . ? C(25) C(24) Ti(2) 73.5(5) . . ? C(23) C(24) Ti(2) 72.2(4) . . ? C(24) C(25) C(21) 107.7(8) . . ? C(24) C(25) Ti(2) 72.4(5) . . ? C(21) C(25) Ti(2) 71.9(4) . . ? C(112) C(111) C(116) 118.5(7) . . ? C(112) C(111) S(1]) 120.0(6) . . ? C(116) C(111) S(1]) 121.2(6) . . ? C(111) C(112) C(113) 119.1(9) . . ? C(111) C(112) C(122) 122.5(7) . . ? C(113) C(112) C(122) 118.2(8) . . ? C(114) C(113) C(112) 122.1(9) . . ? C(115) C(114) C(113) 116.9(8) . . ? C(115) C(114) C(142) 122.6(11) . . ? C(113) C(114) C(142) 120.2(11) . . ? C(114) C(115) C(116) 123.3(9) . . ? C(115) C(116) C(111) 120.0(9) . . ? C(115) C(116) C(162) 118.1(8) . . ? C(111) C(116) C(162) 121.9(7) . . ? C(121) C(122) C(112) 112.5(7) . . ? C(121) C(122) C(123) 110.3(8) . . ? C(112) C(122) C(123) 115.3(9) . . ? C(114) C(142) C(15A) 114.6(11) . . ? C(114) C(142) C(15B) 111.1(10) . . ? C(15A) C(142) C(15B) 47.0(11) . . ? C(114) C(142) C(14A) 111.0(10) . . ? C(15A) C(142) C(14A) 102.3(11) . . ? C(15B) C(142) C(14A) 59.4(12) . . ? C(114) C(142) C(14B) 108.8(10) . . ? C(15A) C(142) C(14B) 50.9(10) . . ? C(15B) C(142) C(14B) 97.2(11) . . ? C(14A) C(142) C(14B) 139.0(10) . . ? C(116) C(162) C(161) 110.4(7) . . ? C(116) C(162) C(163) 114.1(11) . . ? C(161) C(162) C(163) 110.4(9) . . ? C(212) C(211) C(216) 121.8(8) . . ? C(212) C(211) S(2) 120.1(7) . . ? C(216) C(211) S(2) 117.8(7) . . ? C(211) C(212) C(213) 118.8(10) . . ? C(211) C(212) C(222) 122.8(7) . . ? C(213) C(212) C(222) 118.4(9) . . ? C(214) C(213) C(212) 122.5(10) . . ? C(213) C(214) C(215) 117.3(9) . . ? C(213) C(214) C(242) 123.5(12) . . ? C(215) C(214) C(242) 119.0(12) . . ? C(214) C(215) C(216) 122.8(10) . . ? C(211) C(216) C(215) 116.8(10) . . ? C(211) C(216) C(262) 124.8(8) . . ? C(215) C(216) C(262) 118.4(9) . . ? C(221) C(222) C(212) 109.8(7) . . ? C(221) C(222) C(223) 110.8(9) . . ? C(212) C(222) C(223) 114.2(10) . . ? C(214) C(242) C(24A) 107.6(10) . . ? C(214) C(242) C(24B) 108.9(9) . . ? C(24A) C(242) C(24B) 35.4(9) . . ? C(214) C(242) C(25A) 111.2(11) . . ? C(24A) C(242) C(25A) 100.7(11) . . ? C(24B) C(242) C(25A) 67.1(11) . . ? C(214) C(242) C(25B) 107.4(11) . . ? C(24A) C(242) C(25B) 63.8(11) . . ? C(24B) C(242) C(25B) 97.5(11) . . ? C(25A) C(242) C(25B) 141.3(10) . . ? C(216) C(262) C(263) 113.4(10) . . ? C(216) C(262) C(261) 111.8(7) . . ? C(263) C(262) C(261) 110.8(9) . . ? 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 C(27) Ti(2) S(2) C(211) -53.8(4) . . . . ? C(26) Ti(2) S(2) C(211) 51.2(4) . . . . ? C(22) Ti(2) S(2) C(211) -148.7(4) . . . . ? C(21) Ti(2) S(2) C(211) -164.2(4) . . . . ? C(23) Ti(2) S(2) C(211) 180.0(5) . . . . ? C(24) Ti(2) S(2) C(211) 146.6(4) . . . . ? C(25) Ti(2) S(2) C(211) 161.2(4) . . . . ? C(17) Ti(1) S(1]) C(111) 51.2(4) . . . . ? C(16) Ti(1) S(1]) C(111) -53.8(4) . . . . ? C(14) Ti(1) S(1]) C(111) -177.9(4) . . . . ? C(13) Ti(1) S(1]) C(111) -147.4(4) . . . . ? C(15) Ti(1) S(1]) C(111) 147.7(4) . . . . ? C(11) Ti(1) S(1]) C(111) 161.3(3) . . . . ? C(12) Ti(1) S(1]) C(111) -164.0(3) . . . . ? C(17) Ti(1) C(11) C(15) -48.2(5) . . . . ? C(16) Ti(1) C(11) C(15) 86.3(7) . . . . ? C(14) Ti(1) C(11) C(15) 36.7(5) . . . . ? S(1]) Ti(1) C(11) C(15) -158.6(5) . . . . ? C(13) Ti(1) C(11) C(15) 78.5(5) . . . . ? C(12) Ti(1) C(11) C(15) 115.0(7) . . . . ? C(17) Ti(1) C(11) C(12) -163.2(5) . . . . ? C(16) Ti(1) C(11) C(12) -28.7(8) . . . . ? C(14) Ti(1) C(11) C(12) -78.3(5) . . . . ? S(1]) Ti(1) C(11) C(12) 86.5(4) . . . . ? C(13) Ti(1) C(11) C(12) -36.5(4) . . . . ? C(15) Ti(1) C(11) C(12) -115.0(7) . . . . ? C(15) C(11) C(12) C(13) -1.8(8) . . . . ? Ti(1) C(11) C(12) C(13) 62.9(5) . . . . ? C(15) C(11) C(12) Ti(1) -64.7(5) . . . . ? C(17) Ti(1) C(12) C(13) -90.0(7) . . . . ? C(16) Ti(1) C(12) C(13) 45.3(6) . . . . ? C(14) Ti(1) C(12) C(13) -37.8(5) . . . . ? S(1]) Ti(1) C(12) C(13) 152.5(5) . . . . ? C(15) Ti(1) C(12) C(13) -78.9(5) . . . . ? C(11) Ti(1) C(12) C(13) -116.6(7) . . . . ? C(17) Ti(1) C(12) C(11) 26.6(7) . . . . ? C(16) Ti(1) C(12) C(11) 161.9(5) . . . . ? C(14) Ti(1) C(12) C(11) 78.8(5) . . . . ? S(1]) Ti(1) C(12) C(11) -90.8(4) . . . . ? C(13) Ti(1) C(12) C(11) 116.6(7) . . . . ? C(15) Ti(1) C(12) C(11) 37.7(5) . . . . ? C(11) C(12) C(13) C(14) 0.8(9) . . . . ? Ti(1) C(12) C(13) C(14) 64.3(5) . . . . ? C(11) C(12) C(13) Ti(1) -63.5(5) . . . . ? C(17) Ti(1) C(13) C(12) 126.2(5) . . . . ? C(16) Ti(1) C(13) C(12) -138.2(5) . . . . ? C(14) Ti(1) C(13) C(12) 115.9(8) . . . . ? S(1]) Ti(1) C(13) C(12) -30.5(5) . . . . ? C(15) Ti(1) C(13) C(12) 78.4(5) . . . . ? C(11) Ti(1) C(13) C(12) 37.1(5) . . . . ? C(17) Ti(1) C(13) C(14) 10.4(7) . . . . ? C(16) Ti(1) C(13) C(14) 106.0(6) . . . . ? S(1]) Ti(1) C(13) C(14) -146.3(5) . . . . ? C(15) Ti(1) C(13) C(14) -37.5(5) . . . . ? C(11) Ti(1) C(13) C(14) -78.8(6) . . . . ? C(12) Ti(1) C(13) C(14) -115.9(8) . . . . ? C(12) C(13) C(14) C(15) 0.5(9) . . . . ? Ti(1) C(13) C(14) C(15) 66.6(6) . . . . ? C(12) C(13) C(14) Ti(1) -66.1(5) . . . . ? C(17) Ti(1) C(14) C(15) 72.9(5) . . . . ? C(16) Ti(1) C(14) C(15) 170.7(5) . . . . ? S(1]) Ti(1) C(14) C(15) -61.6(6) . . . . ? C(13) Ti(1) C(14) C(15) -114.9(8) . . . . ? C(11) Ti(1) C(14) C(15) -36.9(5) . . . . ? C(12) Ti(1) C(14) C(15) -78.2(5) . . . . ? C(17) Ti(1) C(14) C(13) -172.2(6) . . . . ? C(16) Ti(1) C(14) C(13) -74.4(6) . . . . ? S(1]) Ti(1) C(14) C(13) 53.3(7) . . . . ? C(15) Ti(1) C(14) C(13) 114.9(8) . . . . ? C(11) Ti(1) C(14) C(13) 78.1(6) . . . . ? C(12) Ti(1) C(14) C(13) 36.8(5) . . . . ? C(13) C(14) C(15) C(11) -1.6(9) . . . . ? Ti(1) C(14) C(15) C(11) 64.3(5) . . . . ? C(13) C(14) C(15) Ti(1) -65.9(6) . . . . ? C(12) C(11) C(15) C(14) 2.1(9) . . . . ? Ti(1) C(11) C(15) C(14) -63.1(6) . . . . ? C(12) C(11) C(15) Ti(1) 65.2(5) . . . . ? C(17) Ti(1) C(15) C(14) -107.8(5) . . . . ? C(16) Ti(1) C(15) C(14) -12.0(7) . . . . ? S(1]) Ti(1) C(15) C(14) 141.2(5) . . . . ? C(13) Ti(1) C(15) C(14) 38.1(5) . . . . ? C(11) Ti(1) C(15) C(14) 116.7(7) . . . . ? C(12) Ti(1) C(15) C(14) 78.9(5) . . . . ? C(17) Ti(1) C(15) C(11) 135.4(5) . . . . ? C(16) Ti(1) C(15) C(11) -128.7(5) . . . . ? C(14) Ti(1) C(15) C(11) -116.7(7) . . . . ? S(1]) Ti(1) C(15) C(11) 24.5(5) . . . . ? C(13) Ti(1) C(15) C(11) -78.6(5) . . . . ? C(12) Ti(1) C(15) C(11) -37.8(5) . . . . ? C(27) Ti(2) C(21) C(22) 47.3(6) . . . . ? C(26) Ti(2) C(21) C(22) -89.4(8) . . . . ? S(2) Ti(2) C(21) C(22) 155.2(6) . . . . ? C(23) Ti(2) C(21) C(22) -36.7(6) . . . . ? C(24) Ti(2) C(21) C(22) -78.8(6) . . . . ? C(25) Ti(2) C(21) C(22) -115.6(8) . . . . ? C(27) Ti(2) C(21) C(25) 162.9(5) . . . . ? C(26) Ti(2) C(21) C(25) 26.3(8) . . . . ? S(2) Ti(2) C(21) C(25) -89.2(5) . . . . ? C(22) Ti(2) C(21) C(25) 115.6(8) . . . . ? C(23) Ti(2) C(21) C(25) 78.9(6) . . . . ? C(24) Ti(2) C(21) C(25) 36.9(5) . . . . ? C(25) C(21) C(22) C(23) -0.8(10) . . . . ? Ti(2) C(21) C(22) C(23) 64.7(6) . . . . ? C(25) C(21) C(22) Ti(2) -65.5(5) . . . . ? C(27) Ti(2) C(22) C(23) 107.2(6) . . . . ? C(26) Ti(2) C(22) C(23) 10.9(8) . . . . ? S(2) Ti(2) C(22) C(23) -144.1(5) . . . . ? C(21) Ti(2) C(22) C(23) -116.3(8) . . . . ? C(24) Ti(2) C(22) C(23) -38.2(5) . . . . ? C(25) Ti(2) C(22) C(23) -79.0(6) . . . . ? C(27) Ti(2) C(22) C(21) -136.5(6) . . . . ? C(26) Ti(2) C(22) C(21) 127.2(6) . . . . ? S(2) Ti(2) C(22) C(21) -27.7(6) . . . . ? C(23) Ti(2) C(22) C(21) 116.3(8) . . . . ? C(24) Ti(2) C(22) C(21) 78.1(6) . . . . ? C(25) Ti(2) C(22) C(21) 37.3(5) . . . . ? C(21) C(22) C(23) C(24) 0.4(10) . . . . ? Ti(2) C(22) C(23) C(24) 64.9(6) . . . . ? C(21) C(22) C(23) Ti(2) -64.6(6) . . . . ? C(27) Ti(2) C(23) C(22) -73.6(6) . . . . ? C(26) Ti(2) C(23) C(22) -171.7(6) . . . . ? S(2) Ti(2) C(23) C(22) 56.1(7) . . . . ? C(21) Ti(2) C(23) C(22) 37.3(5) . . . . ? C(24) Ti(2) C(23) C(22) 115.1(8) . . . . ? C(25) Ti(2) C(23) C(22) 78.4(6) . . . . ? C(27) Ti(2) C(23) C(24) 171.3(6) . . . . ? C(26) Ti(2) C(23) C(24) 73.2(6) . . . . ? S(2) Ti(2) C(23) C(24) -59.0(7) . . . . ? C(22) Ti(2) C(23) C(24) -115.1(8) . . . . ? C(21) Ti(2) C(23) C(24) -77.9(6) . . . . ? C(25) Ti(2) C(23) C(24) -36.7(5) . . . . ? C(22) C(23) C(24) C(25) 0.1(9) . . . . ? Ti(2) C(23) C(24) C(25) 65.2(5) . . . . ? C(22) C(23) C(24) Ti(2) -65.0(6) . . . . ? C(27) Ti(2) C(24) C(25) -127.4(6) . . . . ? C(26) Ti(2) C(24) C(25) 136.3(6) . . . . ? S(2) Ti(2) C(24) C(25) 26.6(6) . . . . ? C(22) Ti(2) C(24) C(25) -78.8(6) . . . . ? C(21) Ti(2) C(24) C(25) -37.3(5) . . . . ? C(23) Ti(2) C(24) C(25) -116.0(8) . . . . ? C(27) Ti(2) C(24) C(23) -11.5(8) . . . . ? C(26) Ti(2) C(24) C(23) -107.7(6) . . . . ? S(2) Ti(2) C(24) C(23) 142.6(5) . . . . ? C(22) Ti(2) C(24) C(23) 37.2(5) . . . . ? C(21) Ti(2) C(24) C(23) 78.7(6) . . . . ? C(25) Ti(2) C(24) C(23) 116.0(8) . . . . ? C(23) C(24) C(25) C(21) -0.6(9) . . . . ? Ti(2) C(24) C(25) C(21) 63.7(5) . . . . ? C(23) C(24) C(25) Ti(2) -64.3(5) . . . . ? C(22) C(21) C(25) C(24) 0.8(9) . . . . ? Ti(2) C(21) C(25) C(24) -64.0(5) . . . . ? C(22) C(21) C(25) Ti(2) 64.8(6) . . . . ? C(27) Ti(2) C(25) C(24) 88.9(7) . . . . ? C(26) Ti(2) C(25) C(24) -47.3(6) . . . . ? S(2) Ti(2) C(25) C(24) -156.2(5) . . . . ? C(22) Ti(2) C(25) C(24) 78.6(6) . . . . ? C(21) Ti(2) C(25) C(24) 116.1(7) . . . . ? C(23) Ti(2) C(25) C(24) 37.8(5) . . . . ? C(27) Ti(2) C(25) C(21) -27.2(8) . . . . ? C(26) Ti(2) C(25) C(21) -163.4(5) . . . . ? S(2) Ti(2) C(25) C(21) 87.7(5) . . . . ? C(22) Ti(2) C(25) C(21) -37.5(5) . . . . ? C(23) Ti(2) C(25) C(21) -78.3(6) . . . . ? C(24) Ti(2) C(25) C(21) -116.1(7) . . . . ? Ti(1) S(1]) C(111) C(112) -90.9(6) . . . . ? Ti(1) S(1]) C(111) C(116) 95.8(6) . . . . ? C(116) C(111) C(112) C(113) 1.1(11) . . . . ? S(1]) C(111) C(112) C(113) -172.4(6) . . . . ? C(116) C(111) C(112) C(122) 177.5(7) . . . . ? S(1]) C(111) C(112) C(122) 4.1(10) . . . . ? C(111) C(112) C(113) C(114) 0.3(13) . . . . ? C(122) C(112) C(113) C(114) -176.3(8) . . . . ? C(112) C(113) C(114) C(115) -2.1(14) . . . . ? C(112) C(113) C(114) C(142) -177.4(8) . . . . ? C(113) C(114) C(115) C(116) 2.6(14) . . . . ? C(142) C(114) C(115) C(116) 177.8(9) . . . . ? C(114) C(115) C(116) C(111) -1.3(14) . . . . ? C(114) C(115) C(116) C(162) 177.6(9) . . . . ? C(112) C(111) C(116) C(115) -0.6(12) . . . . ? S(1]) C(111) C(116) C(115) 172.8(7) . . . . ? C(112) C(111) C(116) C(162) -179.5(8) . . . . ? S(1]) C(111) C(116) C(162) -6.1(11) . . . . ? C(111) C(112) C(122) C(121) -87.4(9) . . . . ? C(113) C(112) C(122) C(121) 89.0(9) . . . . ? C(111) C(112) C(122) C(123) 144.9(8) . . . . ? C(113) C(112) C(122) C(123) -38.6(11) . . . . ? C(115) C(114) C(142) C(15A) 61.8(15) . . . . ? C(113) C(114) C(142) C(15A) -123.2(13) . . . . ? C(115) C(114) C(142) C(15B) 112.9(14) . . . . ? C(113) C(114) C(142) C(15B) -72.1(15) . . . . ? C(115) C(114) C(142) C(14A) 177.1(11) . . . . ? C(113) C(114) C(142) C(14A) -7.9(14) . . . . ? C(115) C(114) C(142) C(14B) 7.0(13) . . . . ? C(113) C(114) C(142) C(14B) -178.0(10) . . . . ? C(115) C(116) C(162) C(161) -80.6(10) . . . . ? C(111) C(116) C(162) C(161) 98.3(9) . . . . ? C(115) C(116) C(162) C(163) 44.3(12) . . . . ? C(111) C(116) C(162) C(163) -136.8(9) . . . . ? Ti(2) S(2) C(211) C(212) -93.2(6) . . . . ? Ti(2) S(2) C(211) C(216) 92.4(6) . . . . ? C(216) C(211) C(212) C(213) 1.3(12) . . . . ? S(2) C(211) C(212) C(213) -172.8(7) . . . . ? C(216) C(211) C(212) C(222) 179.2(8) . . . . ? S(2) C(211) C(212) C(222) 5.0(11) . . . . ? C(211) C(212) C(213) C(214) 0.7(14) . . . . ? C(222) C(212) C(213) C(214) -177.2(9) . . . . ? C(212) C(213) C(214) C(215) -2.3(15) . . . . ? C(212) C(213) C(214) C(242) -177.3(9) . . . . ? C(213) C(214) C(215) C(216) 2.0(16) . . . . ? C(242) C(214) C(215) C(216) 177.2(9) . . . . ? C(212) C(211) C(216) C(215) -1.6(12) . . . . ? S(2) C(211) C(216) C(215) 172.7(7) . . . . ? C(212) C(211) C(216) C(262) -178.5(8) . . . . ? S(2) C(211) C(216) C(262) -4.3(11) . . . . ? C(214) C(215) C(216) C(211) -0.1(15) . . . . ? C(214) C(215) C(216) C(262) 177.0(10) . . . . ? C(211) C(212) C(222) C(221) -94.6(9) . . . . ? C(213) C(212) C(222) C(221) 83.3(10) . . . . ? C(211) C(212) C(222) C(223) 140.3(9) . . . . ? C(213) C(212) C(222) C(223) -41.8(12) . . . . ? C(213) C(214) C(242) C(24A) -74.0(15) . . . . ? C(215) C(214) C(242) C(24A) 111.2(14) . . . . ? C(213) C(214) C(242) C(24B) -111.3(13) . . . . ? C(215) C(214) C(242) C(24B) 73.8(14) . . . . ? C(213) C(214) C(242) C(25A) 176.6(11) . . . . ? C(215) C(214) C(242) C(25A) 1.8(14) . . . . ? C(213) C(214) C(242) C(25B) -6.8(14) . . . . ? C(215) C(214) C(242) C(25B) 178.4(11) . . . . ? C(211) C(216) C(262) C(263) -140.3(9) . . . . ? C(215) C(216) C(262) C(263) 42.8(12) . . . . ? C(211) C(216) C(262) C(261) 93.6(10) . . . . ? C(215) C(216) C(262) C(261) -83.3(10) . . . . ?