# Copyright The Royal Society of Chemistry, 1998 # CCDC Number 186/1146 # Halide Titanium (IV) Schiff base chemistry revisited: # New Flouride and Bromide derivatives: X-ray structure of # [TiF2(salen)]. Evidence for a new seven-coordinate # chloride intermediate. data_2 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common TiF2(salen) _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16 H14 F2 N2 O2 Ti' _chemical_formula_weight 352.19 _chemical_melting_point ? _chemical_compound_source ? 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' 'O' 'O' 0.0106 0.0060 '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' 'F' 'F' 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ti' 'Ti' 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 14.285(2) _cell_length_b 8.881(3) _cell_length_c 12.3799(11) _cell_angle_alpha 90.00 _cell_angle_beta 109.733(9) _cell_angle_gamma 90.00 _cell_volume 1478.3(6) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 50 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Block _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.215 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.582 _exptl_crystal_density_method ? _exptl_crystal_F_000 720 _exptl_absorpt_coefficient_mu 0.611 _exptl_absorpt_correction_type DIFABS _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'FAST TV Area detector' _diffrn_measurement_method 'Phi scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4608 _diffrn_reflns_av_R_equivalents 0.0381 _diffrn_reflns_av_sigmaI/netI 0.0538 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 24.76 _reflns_number_total 2139 _reflns_number_observed 1746 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'MADNES (Pflugrath 1989)' _computing_cell_refinement 'refine algorith in MADNES' _computing_data_reduction 'ABSURD' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-92 (Sheldrick, 1993)' _computing_molecular_graphics 'SNOOPI' _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 2 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_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0359P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment 'Riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2137 _refine_ls_number_parameters 216 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0401 _refine_ls_R_factor_obs 0.0310 _refine_ls_wR_factor_all 0.0750 _refine_ls_wR_factor_obs 0.0705 _refine_ls_goodness_of_fit_all 0.959 _refine_ls_goodness_of_fit_obs 1.050 _refine_ls_restrained_S_all 0.998 _refine_ls_restrained_S_obs 1.050 _refine_ls_shift/esd_max 0.004 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti1 Ti 0.21457(3) 0.25294(5) 0.97012(3) 0.01507(14) Uani 1 d . . F1 F 0.27873(10) 0.1111(2) 1.07859(10) 0.0236(3) Uani 1 d . . F2 F 0.15428(10) 0.3742(2) 0.84369(10) 0.0257(3) Uani 1 d . . N1 N 0.12287(14) 0.0743(2) 0.86977(14) 0.0166(5) Uani 1 d . . N2 N 0.30265(14) 0.1593(2) 0.87635(14) 0.0178(5) Uani 1 d . . O1 O 0.11111(11) 0.2831(2) 1.02695(12) 0.0215(4) Uani 1 d . . O2 O 0.32119(11) 0.3860(2) 1.03304(12) 0.0209(4) Uani 1 d . . C1 C 0.0129(2) 0.2576(3) 0.9886(2) 0.0163(5) Uani 1 d . . C2 C -0.0487(2) 0.3399(3) 1.0338(2) 0.0200(6) Uani 1 d . . H2 H -0.0211(2) 0.4116(3) 1.0905(2) 0.024 Uiso 1 calc R . C3 C -0.1503(2) 0.3158(3) 0.9951(2) 0.0196(6) Uani 1 d . . H3 H -0.1907(2) 0.3729(3) 1.0246(2) 0.024 Uiso 1 calc R . C4 C -0.1925(2) 0.2069(3) 0.9126(2) 0.0209(6) Uani 1 d . . H4 H -0.2609(2) 0.1910(3) 0.8872(2) 0.025 Uiso 1 calc R . C5 C -0.1330(2) 0.1222(3) 0.8681(2) 0.0176(5) Uani 1 d . . H5 H -0.1616(2) 0.0478(3) 0.8142(2) 0.021 Uiso 1 calc R . C6 C -0.0297(2) 0.1469(3) 0.9032(2) 0.0156(5) Uani 1 d . . C7 C 0.0294(2) 0.0564(3) 0.8528(2) 0.0167(5) Uani 1 d . . H7 H -0.0039(15) -0.0150(24) 0.8042(17) 0.006(5) Uiso 1 d . . C8 C 0.1733(2) -0.0263(3) 0.8131(2) 0.0211(6) Uani 1 d . . H8A H 0.1252(2) -0.0729(3) 0.7465(2) 0.025 Uiso 1 calc R . H8B H 0.2082(2) -0.1051(3) 0.8654(2) 0.025 Uiso 1 calc R . C9 C 0.2463(2) 0.0675(3) 0.7768(2) 0.0228(6) Uani 1 d . . H9A H 0.2910(2) 0.0027(3) 0.7538(2) 0.027 Uiso 1 calc R . H9B H 0.2111(2) 0.1317(3) 0.7125(2) 0.027 Uiso 1 calc R . C10 C 0.3972(2) 0.1669(3) 0.9091(2) 0.0214(6) Uani 1 d . . H10 H 0.4358(17) 0.1064(29) 0.8635(19) 0.033(7) Uiso 1 d . . C11 C 0.4597(2) 0.2554(3) 1.0068(2) 0.0196(6) Uani 1 d . . C12 C 0.5634(2) 0.2409(3) 1.0402(2) 0.0243(6) Uani 1 d . . H12 H 0.5904(2) 0.1712(3) 1.0028(2) 0.029 Uiso 1 calc R . C13 C 0.6260(2) 0.3270(3) 1.1265(2) 0.0276(6) Uani 1 d . . H13 H 0.6945(2) 0.3145(3) 1.1481(2) 0.033 Uiso 1 calc R . C14 C 0.5862(2) 0.4338(3) 1.1820(2) 0.0250(6) Uani 1 d . . H14 H 0.6284(2) 0.4927(3) 1.2404(2) 0.030 Uiso 1 calc R . C15 C 0.4846(2) 0.4523(3) 1.1506(2) 0.0215(6) Uani 1 d . . H15 H 0.4590(2) 0.5241(3) 1.1876(2) 0.026 Uiso 1 calc R . C16 C 0.4194(2) 0.3637(3) 1.0633(2) 0.0191(6) Uani 1 d . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.0134(3) 0.0182(2) 0.0134(2) -0.0012(2) 0.0043(2) 0.0006(2) F1 0.0216(8) 0.0281(8) 0.0180(6) 0.0053(6) 0.0026(6) -0.0002(7) F2 0.0266(8) 0.0247(8) 0.0224(6) 0.0045(6) 0.0038(6) 0.0056(7) N1 0.0179(12) 0.0190(11) 0.0122(9) -0.0020(9) 0.0039(8) 0.0033(9) N2 0.0161(13) 0.0213(12) 0.0159(9) 0.0006(9) 0.0055(9) 0.0000(9) O1 0.0150(10) 0.0298(11) 0.0203(8) -0.0093(8) 0.0067(7) -0.0049(8) O2 0.0143(10) 0.0238(10) 0.0255(8) -0.0041(8) 0.0078(7) -0.0012(8) C1 0.0154(14) 0.0190(14) 0.0139(10) 0.0013(11) 0.0040(10) -0.0019(12) C2 0.023(2) 0.0194(14) 0.0203(11) -0.0037(11) 0.0106(11) -0.0032(12) C3 0.0195(15) 0.0198(14) 0.0235(12) 0.0013(11) 0.0124(11) 0.0012(11) C4 0.0131(14) 0.0237(14) 0.0256(12) 0.0031(12) 0.0060(11) 0.0001(11) C5 0.0183(14) 0.0162(13) 0.0167(11) -0.0007(10) 0.0038(10) -0.0048(11) C6 0.0204(14) 0.0135(12) 0.0129(11) 0.0032(10) 0.0056(10) 0.0003(11) C7 0.019(2) 0.0160(14) 0.0118(11) -0.0001(11) 0.0011(11) -0.0031(11) C8 0.0182(14) 0.0237(14) 0.0203(12) -0.0082(11) 0.0051(11) 0.0012(12) C9 0.0213(14) 0.033(2) 0.0139(11) -0.0043(11) 0.0055(11) 0.0046(12) C10 0.023(2) 0.0220(14) 0.0221(12) 0.0043(11) 0.0114(11) 0.0037(12) C11 0.0206(14) 0.0210(14) 0.0182(11) 0.0036(11) 0.0078(11) -0.0002(12) C12 0.0192(15) 0.0268(15) 0.0275(13) 0.0036(12) 0.0084(11) 0.0049(13) C13 0.0154(15) 0.032(2) 0.0308(14) 0.0063(13) 0.0021(12) 0.0015(13) C14 0.020(2) 0.028(2) 0.0223(12) 0.0045(12) 0.0009(11) -0.0035(12) C15 0.025(2) 0.0209(14) 0.0198(12) -0.0006(11) 0.0087(11) -0.0013(12) C16 0.0170(15) 0.0218(14) 0.0198(11) 0.0072(11) 0.0081(11) 0.0009(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 F1 1.8438(13) . ? Ti1 F2 1.8550(13) . ? Ti1 O1 1.8582(15) . ? Ti1 O2 1.876(2) . ? Ti1 N2 2.147(2) . ? Ti1 N1 2.163(2) . ? N1 C7 1.290(3) . ? N1 C8 1.467(3) . ? N2 C10 1.274(3) . ? N2 C9 1.470(3) . ? O1 C1 1.341(3) . ? O2 C16 1.339(3) . ? C1 C2 1.398(3) . ? C1 C6 1.421(3) . ? C2 C3 1.383(3) . ? C3 C4 1.388(3) . ? C4 C5 1.381(3) . ? C5 C6 1.408(3) . ? C6 C7 1.450(3) . ? C8 C9 1.517(3) . ? C10 C11 1.466(3) . ? C11 C12 1.404(3) . ? C11 C16 1.421(3) . ? C12 C13 1.372(3) . ? C13 C14 1.400(3) . ? C14 C15 1.379(3) . ? C15 C16 1.405(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 F1 Ti1 F2 170.48(6) . . ? F1 Ti1 O1 94.94(6) . . ? F2 Ti1 O1 91.93(7) . . ? F1 Ti1 O2 89.64(7) . . ? F2 Ti1 O2 93.75(7) . . ? O1 Ti1 O2 112.95(7) . . ? F1 Ti1 N2 83.76(6) . . ? F2 Ti1 N2 87.62(6) . . ? O1 Ti1 N2 161.24(7) . . ? O2 Ti1 N2 85.78(7) . . ? F1 Ti1 N1 88.44(7) . . ? F2 Ti1 N1 85.56(7) . . ? O1 Ti1 N1 85.32(7) . . ? O2 Ti1 N1 161.73(7) . . ? N2 Ti1 N1 75.95(7) . . ? C7 N1 C8 119.7(2) . . ? C7 N1 Ti1 125.2(2) . . ? C8 N1 Ti1 114.93(14) . . ? C10 N2 C9 121.1(2) . . ? C10 N2 Ti1 124.0(2) . . ? C9 N2 Ti1 114.41(14) . . ? C1 O1 Ti1 135.49(13) . . ? C16 O2 Ti1 130.6(2) . . ? O1 C1 C2 119.6(2) . . ? O1 C1 C6 120.9(2) . . ? C2 C1 C6 119.4(2) . . ? C3 C2 C1 120.6(2) . . ? C2 C3 C4 120.5(2) . . ? C5 C4 C3 120.0(2) . . ? C4 C5 C6 121.0(2) . . ? C5 C6 C1 118.5(2) . . ? C5 C6 C7 118.9(2) . . ? C1 C6 C7 122.6(2) . . ? N1 C7 C6 125.6(2) . . ? N1 C8 C9 107.8(2) . . ? N2 C9 C8 107.0(2) . . ? N2 C10 C11 125.1(2) . . ? C12 C11 C16 118.7(2) . . ? C12 C11 C10 118.8(2) . . ? C16 C11 C10 122.3(2) . . ? C13 C12 C11 121.6(2) . . ? C12 C13 C14 119.6(2) . . ? C15 C14 C13 120.3(2) . . ? C14 C15 C16 120.8(2) . . ? O2 C16 C15 119.5(2) . . ? O2 C16 C11 121.5(2) . . ? C15 C16 C11 118.9(2) . . ? _refine_diff_density_max 0.299 _refine_diff_density_min -0.248 _refine_diff_density_rms 0.057 #=END