Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2002 data_amt186 _database_code_CSD 172710 _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name 'Fornies, Juan' 'Pablo J. Alonso' 'Garcia-Monforte,M. Angeles ' 'Antonio Martin' 'Babil Menjon' _publ_contact_author_name 'Prof Juan Fornies' _publ_contact_author_address ; Química Inorganica Instituto de Ciencia de Materiales de Aragon Facultad de Ciencias (Edificio D) Zaragoza E-50009 SPAIN ; _publ_contact_author_email 'FORNIESJ@POSTA.UNIZAR.ES' _publ_section_title ; The first structurally characterised homoleptic sigma-organotitanium(III) compound ; _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C41 H38 Cl22 Li O4 Ti' _chemical_formula_weight 1429.45 _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' 'Li' 'Li' -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.1484 0.1585 '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 'C 2/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 16.748(5) _cell_length_b 19.1546(15) _cell_length_c 17.580(2) _cell_angle_alpha 90.00 _cell_angle_beta 91.58(3) _cell_angle_gamma 90.00 _cell_volume 5637.6(18) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 10.2 _cell_measurement_theta_max 15.6 _exptl_crystal_description parallelepiped _exptl_crystal_colour yellow _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.33 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.684 _exptl_crystal_density_method ? _exptl_crystal_F_000 2860 _exptl_absorpt_coefficient_mu 1.235 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_correction_T_min 0.747 _exptl_absorpt_correction_T_max 0.792 _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Enraf-Nonius CAD-4' _diffrn_measurement_method 'omega scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 300 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 4548 _diffrn_reflns_av_R_equivalents 0.0281 _diffrn_reflns_av_sigmaI/netI 0.0506 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.01 _diffrn_reflns_theta_max 25.02 _reflns_number_total 4368 _reflns_number_observed 3363 _reflns_observed_criterion >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 1 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^)+(0.0651P)^2^+20.0030P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4367 _refine_ls_number_parameters 313 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0761 _refine_ls_R_factor_obs 0.0484 _refine_ls_wR_factor_all 0.1385 _refine_ls_wR_factor_obs 0.1202 _refine_ls_goodness_of_fit_all 1.037 _refine_ls_goodness_of_fit_obs 1.049 _refine_ls_restrained_S_all 1.051 _refine_ls_restrained_S_obs 1.049 _refine_ls_shift/esd_max 0.000 _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 Ti Ti 0.0000 0.17223(6) 0.2500 0.0203(3) Uani 1 d S . Cl2 Cl -0.05903(8) 0.07613(6) 0.37483(6) 0.0290(3) Uani 1 d . . Cl3 Cl -0.18971(9) -0.03924(8) 0.37814(8) 0.0478(4) Uani 1 d . . Cl4 Cl -0.28217(10) -0.07930(8) 0.22757(10) 0.0568(5) Uani 1 d . . Cl5 Cl -0.25800(10) 0.00847(8) 0.08082(8) 0.0494(4) Uani 1 d . . Cl6 Cl -0.12935(8) 0.12446(7) 0.07873(6) 0.0336(3) Uani 1 d . . Cl8 Cl -0.13056(8) 0.27368(7) 0.18385(7) 0.0306(3) Uani 1 d . . Cl9 Cl -0.12798(10) 0.38236(8) 0.05158(9) 0.0517(4) Uani 1 d . . Cl10 Cl 0.03055(11) 0.40874(8) -0.03277(8) 0.0554(5) Uani 1 d . . Cl11 Cl 0.18343(8) 0.32523(7) 0.01275(7) 0.0357(3) Uani 1 d . . Cl12 Cl 0.18087(7) 0.21864(6) 0.14443(6) 0.0286(3) Uani 1 d . . C1 C -0.0978(3) 0.0970(2) 0.2283(2) 0.0217(10) Uani 1 d . . C2 C -0.1154(3) 0.0572(2) 0.2921(3) 0.0238(11) Uani 1 d . . C3 C -0.1723(3) 0.0046(2) 0.2942(3) 0.0290(12) Uani 1 d . . C4 C -0.2147(3) -0.0111(3) 0.2280(3) 0.0348(13) Uani 1 d . . C5 C -0.2015(3) 0.0275(3) 0.1621(3) 0.0313(12) Uani 1 d . . C6 C -0.1444(3) 0.0791(2) 0.1635(3) 0.0257(11) Uani 1 d . . C7 C 0.0236(3) 0.2479(2) 0.1586(3) 0.0225(11) Uani 1 d . . C8 C -0.0427(3) 0.2873(2) 0.1342(3) 0.0246(11) Uani 1 d . . C9 C -0.0423(3) 0.3359(3) 0.0759(3) 0.0320(13) Uani 1 d . . C10 C 0.0275(3) 0.3477(3) 0.0386(3) 0.0332(13) Uani 1 d . . C11 C 0.0961(3) 0.3111(2) 0.0602(3) 0.0280(12) Uani 1 d . . C12 C 0.0927(3) 0.2624(2) 0.1190(3) 0.0224(11) Uani 1 d . . Li Li 0.0000 0.2225(7) 0.7500 0.046(4) Uani 1 d S . O1 O -0.0855(3) 0.2756(2) 0.7949(3) 0.0585(12) Uani 1 d . . C13 C -0.1545(5) 0.2379(4) 0.8208(4) 0.072(2) Uani 1 d . . H13A H -0.1530(5) 0.1896(4) 0.8008(4) 0.087 Uiso 1 calc R . H13B H -0.2036(5) 0.2604(4) 0.8000(4) 0.087 Uiso 1 calc R . C14 C -0.1578(6) 0.2356(5) 0.9038(4) 0.087(3) Uani 1 d . . H14A H -0.2053(6) 0.2096(5) 0.9185(4) 0.131 Uiso 1 calc R . H14B H -0.1604(6) 0.2832(5) 0.9238(4) 0.131 Uiso 1 calc R . H14C H -0.1098(6) 0.2123(5) 0.9246(4) 0.131 Uiso 1 calc R . C15 C -0.0998(5) 0.3486(4) 0.7938(5) 0.079(2) Uani 1 d . . H15A H -0.0477(5) 0.3728(4) 0.7988(5) 0.095 Uiso 1 calc R . H15B H -0.1308(5) 0.3608(4) 0.8390(5) 0.095 Uiso 1 calc R . C16 C -0.1437(5) 0.3765(4) 0.7239(5) 0.080(2) Uani 1 d . . H16A H -0.1505(5) 0.4271(4) 0.7288(5) 0.120 Uiso 1 calc R . H16B H -0.1963(5) 0.3541(4) 0.7190(5) 0.120 Uiso 1 calc R . H16C H -0.1129(5) 0.3662(4) 0.6787(5) 0.120 Uiso 1 calc R . O2 O 0.0516(2) 0.1608(2) 0.8223(2) 0.0425(10) Uani 1 d . . C17 C 0.1060(5) 0.1876(4) 0.8804(3) 0.074(3) Uani 1 d . . H17A H 0.1618(5) 0.1830(4) 0.8640(3) 0.089 Uiso 1 calc R . H17B H 0.0950(5) 0.2377(4) 0.8896(3) 0.089 Uiso 1 calc R . C18 C 0.0948(6) 0.1486(4) 0.9479(4) 0.090(3) Uani 1 d . . H18A H 0.0687(6) 0.1781(4) 0.9862(4) 0.108 Uiso 1 calc R . H18B H 0.1472(6) 0.1334(4) 0.9694(4) 0.108 Uiso 1 calc R . C19 C 0.0444(4) 0.0867(3) 0.9305(3) 0.0394(14) Uani 1 d . . H19A H -0.0049(4) 0.0874(3) 0.9604(3) 0.047 Uiso 1 calc R . H19B H 0.0739(4) 0.0429(3) 0.9418(3) 0.047 Uiso 1 calc R . C20 C 0.0246(3) 0.0932(3) 0.8456(3) 0.0327(13) Uani 1 d . . H20A H 0.0521(3) 0.0561(3) 0.8170(3) 0.039 Uiso 1 calc R . H20B H -0.0336(3) 0.0886(3) 0.8358(3) 0.039 Uiso 1 calc R . Cl13 Cl -0.01926(14) 0.51784(9) 0.83017(10) 0.0730(6) Uani 1 d . . C21 C 0.0000 0.5690(5) 0.7500 0.065(3) Uani 1 d S . 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 Ti 0.0248(8) 0.0180(6) 0.0182(6) 0.000 0.0027(5) 0.000 Cl2 0.0382(8) 0.0319(6) 0.0168(5) 0.0013(5) 0.0016(5) 0.0020(6) Cl3 0.0466(10) 0.0519(8) 0.0454(8) 0.0228(7) 0.0131(7) -0.0093(7) Cl4 0.0426(11) 0.0489(9) 0.0785(11) 0.0115(8) -0.0050(8) -0.0237(7) Cl5 0.0468(10) 0.0553(9) 0.0450(8) -0.0044(7) -0.0179(7) -0.0145(7) Cl6 0.0429(9) 0.0389(7) 0.0189(6) 0.0042(5) -0.0031(5) -0.0033(6) Cl8 0.0246(8) 0.0367(7) 0.0306(6) 0.0014(5) 0.0038(5) 0.0045(5) Cl9 0.0510(11) 0.0579(9) 0.0460(8) 0.0167(7) 0.0023(7) 0.0278(8) Cl10 0.0774(13) 0.0488(9) 0.0408(8) 0.0249(7) 0.0181(8) 0.0183(8) Cl11 0.0401(9) 0.0382(7) 0.0294(6) 0.0037(5) 0.0126(6) -0.0084(6) Cl12 0.0221(8) 0.0361(6) 0.0277(6) 0.0026(5) 0.0035(5) 0.0025(5) C1 0.021(3) 0.021(2) 0.023(2) 0.001(2) 0.002(2) 0.003(2) C2 0.023(3) 0.028(2) 0.021(2) 0.003(2) 0.003(2) 0.006(2) C3 0.024(3) 0.030(3) 0.033(3) 0.011(2) 0.008(2) 0.001(2) C4 0.024(3) 0.031(3) 0.049(3) 0.003(2) 0.002(3) -0.009(2) C5 0.029(3) 0.030(3) 0.034(3) -0.004(2) -0.006(2) -0.003(2) C6 0.031(3) 0.027(2) 0.019(2) 0.001(2) 0.001(2) 0.004(2) C7 0.023(3) 0.019(2) 0.025(2) 0.001(2) -0.003(2) -0.004(2) C8 0.025(3) 0.025(2) 0.025(2) -0.003(2) 0.004(2) 0.000(2) C9 0.039(4) 0.032(3) 0.025(3) 0.003(2) 0.000(2) 0.014(2) C10 0.046(4) 0.027(3) 0.027(3) 0.006(2) 0.004(2) 0.006(2) C11 0.038(4) 0.025(2) 0.022(2) -0.004(2) 0.007(2) -0.005(2) C12 0.021(3) 0.022(2) 0.024(2) -0.004(2) 0.000(2) 0.001(2) Li 0.078(11) 0.035(7) 0.027(6) 0.000 0.001(7) 0.000 O1 0.065(3) 0.041(2) 0.070(3) -0.018(2) 0.018(2) -0.013(2) C13 0.070(6) 0.087(6) 0.060(5) -0.009(4) 0.006(4) -0.010(4) C14 0.093(7) 0.109(7) 0.059(5) -0.002(5) 0.012(4) -0.008(6) C15 0.073(6) 0.067(5) 0.096(6) -0.013(4) -0.014(5) 0.005(4) C16 0.075(6) 0.065(5) 0.099(6) -0.007(5) -0.014(5) 0.000(4) O2 0.060(3) 0.038(2) 0.029(2) 0.009(2) -0.015(2) -0.019(2) C17 0.103(6) 0.083(5) 0.035(3) 0.012(3) -0.027(4) -0.059(5) C18 0.149(8) 0.074(5) 0.044(4) 0.015(4) -0.041(5) -0.064(5) C19 0.055(4) 0.042(3) 0.021(3) 0.003(2) -0.002(2) -0.010(3) C20 0.044(4) 0.030(3) 0.025(3) 0.000(2) -0.002(2) -0.006(2) Cl13 0.117(2) 0.0512(10) 0.0496(10) 0.0039(8) -0.0131(10) 0.0057(10) C21 0.093(8) 0.042(5) 0.059(6) 0.000 0.022(6) 0.000 _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 C7 2.207(4) 2 ? Ti C1 2.207(5) . ? Ti C1 2.207(5) 2 ? Ti C7 2.207(4) . ? Cl2 C2 1.750(5) . ? Cl3 C3 1.730(5) . ? Cl4 C4 1.727(5) . ? Cl5 C5 1.731(5) . ? Cl6 C6 1.749(5) . ? Cl8 C8 1.751(5) . ? Cl9 C9 1.731(5) . ? Cl10 C10 1.716(5) . ? Cl11 C11 1.726(5) . ? Cl12 C12 1.746(5) . ? C1 C2 1.394(6) . ? C1 C6 1.406(6) . ? C2 C3 1.389(7) . ? C3 C4 1.380(7) . ? C4 C5 1.395(7) . ? C5 C6 1.376(7) . ? C7 C12 1.394(7) . ? C7 C8 1.400(7) . ? C8 C9 1.385(7) . ? C9 C10 1.376(8) . ? C10 C11 1.389(7) . ? C11 C12 1.395(6) . ? Li O2 1.923(9) . ? Li O2 1.923(9) 2_556 ? Li O1 1.942(8) . ? Li O1 1.942(8) 2_556 ? O1 C15 1.418(8) . ? O1 C13 1.446(8) . ? C13 C14 1.463(10) . ? C15 C16 1.512(11) . ? O2 C20 1.435(6) . ? O2 C17 1.444(7) . ? C17 C18 1.420(9) . ? C18 C19 1.483(8) . ? C19 C20 1.526(7) . ? Cl13 C21 1.754(5) . ? C21 Cl13 1.754(5) 2_556 ? 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 C7 Ti C1 114.0(2) 2 . ? C7 Ti C1 116.8(2) 2 2 ? C1 Ti C1 98.5(2) . 2 ? C7 Ti C7 97.9(2) 2 . ? C1 Ti C7 116.8(2) . . ? C1 Ti C7 114.0(2) 2 . ? C2 C1 C6 113.2(4) . . ? C2 C1 Ti 113.0(3) . . ? C6 C1 Ti 133.8(3) . . ? C3 C2 C1 125.3(4) . . ? C3 C2 Cl2 118.9(4) . . ? C1 C2 Cl2 115.8(4) . . ? C4 C3 C2 118.3(4) . . ? C4 C3 Cl3 121.3(4) . . ? C2 C3 Cl3 120.5(4) . . ? C3 C4 C5 119.7(5) . . ? C3 C4 Cl4 119.3(4) . . ? C5 C4 Cl4 121.0(4) . . ? C6 C5 C4 119.5(5) . . ? C6 C5 Cl5 121.9(4) . . ? C4 C5 Cl5 118.6(4) . . ? C5 C6 C1 124.0(4) . . ? C5 C6 Cl6 117.3(4) . . ? C1 C6 Cl6 118.6(4) . . ? C12 C7 C8 113.6(4) . . ? C12 C7 Ti 131.5(3) . . ? C8 C7 Ti 114.8(3) . . ? C9 C8 C7 124.7(5) . . ? C9 C8 Cl8 119.3(4) . . ? C7 C8 Cl8 116.0(3) . . ? C10 C9 C8 119.0(5) . . ? C10 C9 Cl9 120.5(4) . . ? C8 C9 Cl9 120.6(4) . . ? C9 C10 C11 119.6(4) . . ? C9 C10 Cl10 120.2(4) . . ? C11 C10 Cl10 120.2(4) . . ? C10 C11 C12 119.4(5) . . ? C10 C11 Cl11 119.6(4) . . ? C12 C11 Cl11 121.0(4) . . ? C7 C12 C11 123.7(4) . . ? C7 C12 Cl12 118.9(3) . . ? C11 C12 Cl12 117.3(4) . . ? O2 Li O2 104.2(6) . 2_556 ? O2 Li O1 112.1(2) . . ? O2 Li O1 105.5(2) 2_556 . ? O2 Li O1 105.5(2) . 2_556 ? O2 Li O1 112.1(2) 2_556 2_556 ? O1 Li O1 116.8(7) . 2_556 ? C15 O1 C13 111.2(6) . . ? C15 O1 Li 129.6(6) . . ? C13 O1 Li 118.0(5) . . ? O1 C13 C14 112.4(6) . . ? O1 C15 C16 115.9(7) . . ? C20 O2 C17 108.5(4) . . ? C20 O2 Li 127.1(4) . . ? C17 O2 Li 120.8(5) . . ? C18 C17 O2 108.0(5) . . ? C17 C18 C19 109.7(5) . . ? C18 C19 C20 104.1(4) . . ? O2 C20 C19 106.9(4) . . ? Cl13 C21 Cl13 112.0(5) . 2_556 ? _refine_diff_density_max 0.675 _refine_diff_density_min -0.711 _refine_diff_density_rms 0.089