Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_2 _journal_coden_Cambridge 186 _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name _publ_author_address 'Fandos, R.' ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad de Castilla-La Mancha Facultad de Ciencias del Medio Ambiente Avda. Carlos III, s/n 45071, Toledo Spain ; 'Hernandez, C.' ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad de Castilla-La Mancha Facultad de Ciencias del Medio Ambiente Avda. Carlos III, s/n 45071, Toledo Spain ; 'Otero, A.' ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad de Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071, Ciudad Real Spain ; 'Rodriguez, A.' ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad de Castilla-La Mancha ETS Ingenieros Industriales Avda. Camilo Jose Cela,3 13071, Ciudad Real Spain ; 'Ruiz, M.J.' ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad de Castilla-La Mancha Facultad de Ciencias del Medio Ambiente Avda. Carlos III, s/n 45071, Toledo Spain ; 'Terreros, P.' ; Instituto de Catalisis y Petroleoquimica CSIC, Cantoblanco 28049, Madrid Spain ; _publ_contact_author_name 'Prof Antonio Otero' _publ_contact_author_address ; Dept de Quimica Inorg. Organica y B Facultad de Ciencias Quimicas Univ. de Castilla-La-Mancha CUIDAD REAL 13017 SPAIN ; _publ_contact_author_email 'AOTERO@QINO-CR.UCLM.ES' _publ_section_title ; Isolation and characterization of the first bis(2-pyridyl)carbyltitanium (IV) complex derived from the C-O bond cleavage of the alkoxide ligand in Cp*TiMe2(OCMePy2). X-ray crystal structure of [Cp*Ti(u2-O)(CMePy2)]2(Cp*=C5Me5) ; _database_code_CSD 173685 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C44 H56 N4 O2 Ti2' _chemical_formula_weight 764.70 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 monoclinic _symmetry_space_group_name_H-M P21/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 11.034(2) _cell_length_b 10.346(3) _cell_length_c 16.992(7) _cell_angle_alpha 90.00 _cell_angle_beta 103.960(10) _cell_angle_gamma 90.00 _cell_volume 1882.5(10) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.349 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 808 _exptl_absorpt_coefficient_mu 0.468 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'four circle diffractometer Nonius-Mach3' _diffrn_measurement_method '\w/2\q scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% ? _diffrn_reflns_number 2288 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.1562 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.32 _diffrn_reflns_theta_max 22.00 _reflns_number_total 2288 _reflns_number_gt 1051 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius (control program)' _computing_cell_refinement 'Nonius (control program)' _computing_data_reduction 'XRAY80 (Stewart, 1976)' _computing_structure_solution 'SIR92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1135P)^2^+4.8819P] 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 0.0015(12) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2288 _refine_ls_number_parameters 236 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1913 _refine_ls_R_factor_gt 0.0971 _refine_ls_wR_factor_ref 0.2910 _refine_ls_wR_factor_gt 0.2134 _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_restrained_S_all 1.067 _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 0.92633(19) 0.3926(2) 1.01444(14) 0.0392(8) Uani 1 1 d . . . O1 O 0.9408(6) 0.5039(7) 0.9321(5) 0.038(2) Uani 1 1 d . . . N1 N 0.8658(9) 0.4035(9) 1.1257(6) 0.044(3) Uani 1 1 d . . . N2 N 0.7249(8) 0.4126(10) 0.9627(6) 0.045(3) Uani 1 1 d . . . C1 C 0.9515(12) 0.4441(13) 1.1930(8) 0.053(4) Uani 1 1 d . . . H1 H 1.0266 0.4773 1.1860 0.063 Uiso 1 1 calc . . . C2 C 0.9350(15) 0.4395(14) 1.2695(7) 0.063(4) Uani 1 1 d . . . H2 H 0.9949 0.4753 1.3119 0.076 Uiso 1 1 calc . . . C3 C 0.8313(16) 0.3830(16) 1.2849(9) 0.073(5) Uani 1 1 d . . . H3 H 0.8228 0.3751 1.3378 0.087 Uiso 1 1 calc . . . C4 C 0.7418(14) 0.3389(16) 1.2225(10) 0.069(5) Uani 1 1 d . . . H4 H 0.6706 0.3006 1.2322 0.082 Uiso 1 1 calc . . . C5 C 0.7555(12) 0.3507(12) 1.1414(9) 0.051(4) Uani 1 1 d . . . C6 C 0.6568(13) 0.3160(13) 1.0759(9) 0.054(4) Uani 1 1 d . . . C7 C 0.5556(13) 0.2274(14) 1.0974(11) 0.079(5) Uani 1 1 d . . . H7A H 0.5802 0.2046 1.1537 0.118 Uiso 1 1 calc . . . H7B H 0.5469 0.1504 1.0650 0.118 Uiso 1 1 calc . . . H7C H 0.4773 0.2725 1.0867 0.118 Uiso 1 1 calc . . . C8 C 0.6315(10) 0.3584(12) 0.9957(8) 0.042(3) Uani 1 1 d . . . C9 C 0.5071(11) 0.3617(13) 0.9457(9) 0.055(4) Uani 1 1 d . . . H9 H 0.4439 0.3287 0.9675 0.066 Uiso 1 1 calc . . . C10 C 0.4752(11) 0.4075(15) 0.8719(10) 0.065(4) Uani 1 1 d . . . H10 H 0.3930 0.4029 0.8416 0.078 Uiso 1 1 calc . . . C11 C 0.5681(11) 0.4635(13) 0.8400(7) 0.049(4) Uani 1 1 d . . . H11 H 0.5491 0.5006 0.7887 0.059 Uiso 1 1 calc . . . C12 C 0.6886(13) 0.4619(14) 0.8869(8) 0.060(4) Uani 1 1 d . . . H12 H 0.7501 0.4977 0.8647 0.072 Uiso 1 1 calc . . . C13 C 0.8656(11) 0.1643(13) 0.9733(9) 0.050(4) Uani 1 1 d . . . C14 C 0.9463(14) 0.2157(12) 0.9279(8) 0.058(5) Uani 1 1 d . . . C15 C 1.0640(9) 0.2390(11) 0.9815(7) 0.028(3) Uani 1 1 d . . . C16 C 1.0546(12) 0.2098(12) 1.0586(8) 0.049(4) Uani 1 1 d . . . C17 C 0.9362(11) 0.1536(12) 1.0541(9) 0.049(4) Uani 1 1 d . . . C18 C 0.7397(12) 0.1081(13) 0.9366(11) 0.085(6) Uani 1 1 d . . . H18A H 0.7474 0.0238 0.9153 0.127 Uiso 1 1 calc R . . H18B H 0.6933 0.1634 0.8954 0.127 Uiso 1 1 calc R . . H18C H 0.6943 0.0999 0.9794 0.127 Uiso 1 1 calc R . . C19 C 0.9121(13) 0.2336(13) 0.8372(9) 0.063(4) Uani 1 1 d . . . H19A H 0.8502 0.3006 0.8218 0.097 Uiso 1 1 calc R . . H19B H 0.8809 0.1549 0.8103 0.097 Uiso 1 1 calc R . . H19C H 0.9860 0.2597 0.8192 0.097 Uiso 1 1 calc R . . C20 C 1.1812(11) 0.2796(11) 0.9576(8) 0.049(4) Uani 1 1 d . . . H20A H 1.2287 0.3374 0.9977 0.074 Uiso 1 1 calc R . . H20B H 1.1616 0.3196 0.9059 0.074 Uiso 1 1 calc R . . H20C H 1.2324 0.2031 0.9556 0.074 Uiso 1 1 calc R . . C21 C 1.1584(12) 0.2138(13) 1.1355(9) 0.060(4) Uani 1 1 d . . . H21A H 1.1613 0.1320 1.1634 0.091 Uiso 1 1 calc R . . H21B H 1.1424 0.2813 1.1705 0.091 Uiso 1 1 calc R . . H21C H 1.2368 0.2286 1.1225 0.091 Uiso 1 1 calc R . . C22 C 0.8909(12) 0.0975(13) 1.1217(10) 0.069(5) Uani 1 1 d . . . H22A H 0.8010 0.0917 1.1071 0.100 Uiso 1 1 calc R . . H22B H 0.9170 0.1500 1.1689 0.100 Uiso 1 1 calc R . . H22C H 0.9246 0.0114 1.1332 0.100 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 0.0257(12) 0.0386(14) 0.0557(16) -0.0026(13) 0.0144(10) 0.0027(11) O1 0.029(4) 0.034(5) 0.051(5) -0.008(4) 0.008(4) -0.011(4) N1 0.039(6) 0.038(6) 0.053(7) -0.002(5) 0.008(5) 0.004(5) N2 0.033(6) 0.044(6) 0.058(7) -0.006(6) 0.011(5) 0.004(5) C1 0.045(8) 0.067(10) 0.046(9) 0.002(8) 0.010(7) 0.012(7) C2 0.091(12) 0.072(11) 0.030(8) 0.008(7) 0.021(8) 0.032(9) C3 0.082(12) 0.085(12) 0.071(11) 0.011(10) 0.059(10) 0.034(10) C4 0.064(10) 0.079(12) 0.078(12) 0.040(10) 0.046(9) 0.011(9) C5 0.046(8) 0.043(8) 0.072(10) 0.009(7) 0.027(8) 0.018(7) C6 0.059(9) 0.047(9) 0.065(10) -0.002(8) 0.029(8) 0.014(7) C7 0.053(9) 0.054(10) 0.133(16) 0.033(10) 0.028(10) 0.003(8) C8 0.028(7) 0.039(8) 0.061(9) -0.008(7) 0.012(6) 0.000(6) C9 0.036(8) 0.055(10) 0.076(11) -0.002(8) 0.018(8) -0.018(7) C10 0.028(7) 0.078(11) 0.083(12) -0.004(10) 0.002(8) -0.004(8) C11 0.031(7) 0.060(9) 0.050(8) 0.005(7) -0.001(7) -0.002(7) C12 0.058(10) 0.058(10) 0.053(9) 0.005(8) -0.006(8) -0.006(7) C13 0.030(7) 0.058(9) 0.073(10) -0.021(8) 0.039(8) -0.005(7) C14 0.089(11) 0.036(8) 0.035(8) -0.022(6) -0.013(8) 0.042(8) C15 0.012(6) 0.050(7) 0.026(7) -0.019(6) 0.011(5) 0.007(5) C16 0.056(9) 0.039(8) 0.050(9) -0.013(7) 0.012(7) 0.026(7) C17 0.027(7) 0.031(7) 0.086(11) 0.004(7) 0.007(7) -0.008(6) C18 0.046(8) 0.030(8) 0.161(16) -0.037(10) -0.007(10) -0.010(7) C19 0.053(9) 0.056(9) 0.080(11) -0.019(8) 0.015(8) 0.013(7) C20 0.048(8) 0.029(7) 0.080(10) -0.010(7) 0.036(7) -0.003(6) C21 0.048(8) 0.052(9) 0.075(11) -0.018(8) 0.006(8) 0.018(7) C22 0.061(9) 0.031(8) 0.130(14) 0.002(9) 0.054(10) 0.008(7) _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 1.848(8) . ? Ti1 O1 1.865(7) 3_767 ? Ti1 N1 2.155(10) . ? Ti1 N2 2.194(9) . ? Ti1 C15 2.357(10) . ? Ti1 C16 2.372(12) . ? Ti1 C14 2.391(11) . ? Ti1 C13 2.508(13) . ? Ti1 C17 2.558(13) . ? Ti1 Ti1 2.865(4) 3_767 ? O1 Ti1 1.865(7) 3_767 ? N1 C1 1.363(15) . ? N1 C5 1.417(15) . ? N2 C12 1.353(15) . ? N2 C8 1.402(15) . ? C1 C2 1.357(16) . ? C2 C3 1.37(2) . ? C3 C4 1.34(2) . ? C4 C5 1.428(18) . ? C5 C6 1.403(18) . ? C6 C8 1.395(17) . ? C6 C7 1.554(19) . ? C8 C9 1.430(16) . ? C9 C10 1.306(17) . ? C10 C11 1.396(18) . ? C11 C12 1.375(16) . ? C13 C17 1.410(17) . ? C13 C14 1.414(19) . ? C13 C18 1.496(17) . ? C14 C15 1.415(16) . ? C14 C19 1.508(19) . ? C15 C16 1.372(16) . ? C15 C20 1.505(15) . ? C16 C17 1.415(17) . ? C16 C21 1.517(17) . ? C17 C22 1.477(18) . ? 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 O1 79.0(4) . 3_767 ? O1 Ti1 N1 137.1(4) . . ? O1 Ti1 N1 85.2(4) 3_767 . ? O1 Ti1 N2 84.4(4) . . ? O1 Ti1 N2 138.0(4) 3_767 . ? N1 Ti1 N2 81.3(4) . . ? O1 Ti1 C15 93.6(4) . . ? O1 Ti1 C15 91.5(3) 3_767 . ? N1 Ti1 C15 126.7(4) . . ? N2 Ti1 C15 128.1(4) . . ? O1 Ti1 C16 125.6(4) . . ? O1 Ti1 C16 88.0(4) 3_767 . ? N1 Ti1 C16 93.0(4) . . ? N2 Ti1 C16 132.1(4) . . ? C15 Ti1 C16 33.7(4) . . ? O1 Ti1 C14 88.5(4) . . ? O1 Ti1 C14 124.1(5) 3_767 . ? N1 Ti1 C14 132.4(5) . . ? N2 Ti1 C14 93.5(4) . . ? C15 Ti1 C14 34.7(4) . . ? C16 Ti1 C14 56.5(4) . . ? O1 Ti1 C13 116.2(4) . . ? O1 Ti1 C13 143.3(4) 3_767 . ? N1 Ti1 C13 100.1(4) . . ? N2 Ti1 C13 78.5(4) . . ? C15 Ti1 C13 56.1(4) . . ? C16 Ti1 C13 55.7(4) . . ? C14 Ti1 C13 33.5(4) . . ? O1 Ti1 C17 142.7(4) . . ? O1 Ti1 C17 116.6(4) 3_767 . ? N1 Ti1 C17 79.8(4) . . ? N2 Ti1 C17 99.8(4) . . ? C15 Ti1 C17 54.7(4) . . ? C16 Ti1 C17 33.1(4) . . ? C14 Ti1 C17 54.4(5) . . ? C13 Ti1 C17 32.3(4) . . ? O1 Ti1 Ti1 39.7(2) . 3_767 ? O1 Ti1 Ti1 39.3(2) 3_767 3_767 ? N1 Ti1 Ti1 114.7(3) . 3_767 ? N2 Ti1 Ti1 114.9(3) . 3_767 ? C15 Ti1 Ti1 93.3(3) . 3_767 ? C16 Ti1 Ti1 110.6(4) . 3_767 ? C14 Ti1 Ti1 110.4(4) . 3_767 ? C13 Ti1 Ti1 143.8(3) . 3_767 ? C17 Ti1 Ti1 143.6(3) . 3_767 ? Ti1 O1 Ti1 101.0(4) . 3_767 ? C1 N1 C5 114.5(11) . . ? C1 N1 Ti1 116.9(8) . . ? C5 N1 Ti1 127.4(9) . . ? C12 N2 C8 116.9(10) . . ? C12 N2 Ti1 117.1(8) . . ? C8 N2 Ti1 125.0(8) . . ? C2 C1 N1 124.5(13) . . ? C1 C2 C3 120.8(15) . . ? C4 C3 C2 119.0(13) . . ? C3 C4 C5 120.3(14) . . ? C6 C5 N1 119.2(12) . . ? C6 C5 C4 120.1(13) . . ? N1 C5 C4 120.7(13) . . ? C8 C6 C5 128.9(13) . . ? C8 C6 C7 115.5(13) . . ? C5 C6 C7 115.4(13) . . ? C6 C8 N2 121.6(11) . . ? C6 C8 C9 121.6(12) . . ? N2 C8 C9 116.5(11) . . ? C10 C9 C8 125.2(12) . . ? C9 C10 C11 118.0(12) . . ? C12 C11 C10 117.9(13) . . ? N2 C12 C11 125.4(13) . . ? C17 C13 C14 106.7(11) . . ? C17 C13 C18 127.9(13) . . ? C14 C13 C18 124.2(14) . . ? C17 C13 Ti1 75.8(7) . . ? C14 C13 Ti1 68.7(7) . . ? C18 C13 Ti1 129.9(9) . . ? C13 C14 C15 108.3(11) . . ? C13 C14 C19 124.6(14) . . ? C15 C14 C19 127.0(14) . . ? C13 C14 Ti1 77.8(7) . . ? C15 C14 Ti1 71.4(6) . . ? C19 C14 Ti1 119.8(8) . . ? C16 C15 C14 107.9(11) . . ? C16 C15 C20 125.9(11) . . ? C14 C15 C20 126.1(12) . . ? C16 C15 Ti1 73.7(6) . . ? C14 C15 Ti1 74.0(6) . . ? C20 C15 Ti1 121.3(8) . . ? C15 C16 C17 108.7(12) . . ? C15 C16 C21 127.0(12) . . ? C17 C16 C21 123.6(13) . . ? C15 C16 Ti1 72.5(7) . . ? C17 C16 Ti1 80.7(7) . . ? C21 C16 Ti1 121.3(8) . . ? C13 C17 C16 107.8(12) . . ? C13 C17 C22 125.2(11) . . ? C16 C17 C22 126.9(13) . . ? C13 C17 Ti1 71.9(8) . . ? C16 C17 Ti1 66.2(7) . . ? C22 C17 Ti1 125.7(9) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 22.00 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.431 _refine_diff_density_min -0.447 _refine_diff_density_rms 0.109