# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'D. W. Stephan' _publ_contact_author_email DSTEPHAN@CHEM.UTORONTO.CA _publ_section_title ; Phosphinimide Complexes with Pendant Hemilabile Donors: Synthesis, Structure and Ethylene Polymerization Activity ; loop_ _publ_author_name 'D. W. Stephan' 'Guangcai Bai.' 'Jenny S.J. McCahill' 'Krishan Yadav' # Attachment 'CIF.cif' data_CpTiCl2NPtBu2(CH2)3OCH2Ph _database_code_depnum_ccdc_archive 'CCDC 702186' _audit_creation_method SHELXL-97 _chemical_formula_sum 'C23 H36 Cl2 N O P Ti' _chemical_formula_weight 492.30 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' P P 0.1023 0.0942 '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 P2(1)/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 9.020(3) _cell_length_b 20.667(7) _cell_length_c 14.584(5) _cell_angle_alpha 90.00 _cell_angle_beta 106.219(4) _cell_angle_gamma 90.00 _cell_volume 2610.5(14) _cell_formula_units_Z 4 _cell_measurement_temperature 273(2) _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 25.0 _exptl_crystal_description blocks _exptl_crystal_colour yellow _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.20 _exptl_crystal_density_diffrn 1.253 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1040 _exptl_absorpt_coefficient_mu 0.608 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.847145 _exptl_absorpt_correction_T_max 1.00000 _diffrn_measurement_device_type 'Bruker SMART system' _diffrn_measurement_method CCD _diffrn_ambient_temperature 273(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_reflns_number 24680 _diffrn_reflns_av_R_equivalents 0.0496 _diffrn_reflns_av_sigmaI/netI 0.0383 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.76 _diffrn_reflns_theta_max 25.00 _reflns_number_total 4600 _reflns_number_gt 3014 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _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^)+(0.1003P)^2^+1.1993P] 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 constr _refine_ls_extinction_method none _refine_ls_number_reflns 4600 _refine_ls_number_parameters 262 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0919 _refine_ls_R_factor_gt 0.0582 _refine_ls_wR_factor_ref 0.1753 _refine_ls_wR_factor_gt 0.1482 _refine_ls_goodness_of_fit_ref 0.990 _refine_ls_restrained_S_all 0.990 _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 0.29595(8) 0.08662(3) 0.74398(5) 0.0512(2) Uani 1 1 d . . . Cl1 Cl 0.48278(15) 0.16254(7) 0.80702(11) 0.1057(5) Uani 1 1 d . . . Cl2 Cl 0.36255(18) 0.05551(7) 0.60950(9) 0.0960(5) Uani 1 1 d . . . P1 P -0.02024(11) 0.17787(5) 0.65869(6) 0.0458(3) Uani 1 1 d . . . N1 N 0.1311(3) 0.13451(13) 0.6990(2) 0.0487(7) Uani 1 1 d . . . O1 O 0.0197(4) 0.15197(19) 1.0067(2) 0.0918(11) Uani 1 1 d . . . C1 C 0.3713(13) -0.0202(4) 0.8034(8) 0.153(4) Uani 1 1 d . . . H1A H 0.4372 -0.0493 0.7788 0.184 Uiso 1 1 calc R . . C2 C 0.2151(11) -0.0187(3) 0.7722(5) 0.117(2) Uani 1 1 d . . . H2A H 0.1499 -0.0475 0.7242 0.141 Uiso 1 1 calc R . . C3 C 0.1656(7) 0.0223(2) 0.8286(4) 0.0829(14) Uani 1 1 d . . . H3A H 0.0572 0.0280 0.8275 0.099 Uiso 1 1 calc R . . C4 C 0.2854(9) 0.0488(3) 0.8933(4) 0.0979(18) Uani 1 1 d . . . H4A H 0.2793 0.0758 0.9473 0.118 Uiso 1 1 calc R . . C5 C 0.4232(10) 0.0211(5) 0.8798(7) 0.156(4) Uani 1 1 d . . . H5A H 0.5289 0.0257 0.9211 0.188 Uiso 1 1 calc R . . C6 C 0.0450(5) 0.25789(19) 0.6277(3) 0.0621(11) Uani 1 1 d . . . C7 C -0.0886(6) 0.3022(3) 0.5753(5) 0.116(2) Uani 1 1 d . . . H7A H -0.0479 0.3427 0.5609 0.174 Uiso 1 1 calc R . . H7B H -0.1553 0.3098 0.6152 0.174 Uiso 1 1 calc R . . H7C H -0.1460 0.2818 0.5170 0.174 Uiso 1 1 calc R . . C8 C 0.1578(6) 0.2477(3) 0.5669(3) 0.0889(15) Uani 1 1 d . . . H8A H 0.1922 0.2890 0.5506 0.133 Uiso 1 1 calc R . . H8B H 0.1064 0.2248 0.5096 0.133 Uiso 1 1 calc R . . H8C H 0.2450 0.2230 0.6026 0.133 Uiso 1 1 calc R . . C9 C 0.1350(6) 0.2898(2) 0.7213(4) 0.0863(15) Uani 1 1 d . . . H9A H 0.1714 0.3315 0.7081 0.130 Uiso 1 1 calc R . . H9B H 0.2215 0.2631 0.7525 0.130 Uiso 1 1 calc R . . H9C H 0.0687 0.2949 0.7621 0.130 Uiso 1 1 calc R . . C10 C -0.1581(5) 0.1348(2) 0.5589(3) 0.0755(13) Uani 1 1 d . . . C11 C -0.0939(8) 0.1297(4) 0.4729(4) 0.131(3) Uani 1 1 d . . . H11A H -0.1667 0.1073 0.4221 0.197 Uiso 1 1 calc R . . H11B H 0.0017 0.1062 0.4906 0.197 Uiso 1 1 calc R . . H11C H -0.0763 0.1723 0.4519 0.197 Uiso 1 1 calc R . . C12 C -0.3184(6) 0.1680(3) 0.5318(4) 0.122(2) Uani 1 1 d . . . H12A H -0.3872 0.1449 0.4800 0.183 Uiso 1 1 calc R . . H12B H -0.3081 0.2118 0.5126 0.183 Uiso 1 1 calc R . . H12C H -0.3592 0.1678 0.5859 0.183 Uiso 1 1 calc R . . C13 C -0.1755(7) 0.0670(3) 0.5964(4) 0.119(2) Uani 1 1 d . . . H13A H -0.2460 0.0423 0.5473 0.178 Uiso 1 1 calc R . . H13B H -0.2147 0.0702 0.6510 0.178 Uiso 1 1 calc R . . H13C H -0.0767 0.0460 0.6143 0.178 Uiso 1 1 calc R . . C14 C -0.1233(5) 0.1903(2) 0.7482(3) 0.0717(12) Uani 1 1 d . . . H14A H -0.1791 0.2309 0.7345 0.086 Uiso 1 1 calc R . . H14B H -0.1991 0.1561 0.7416 0.086 Uiso 1 1 calc R . . C15 C -0.0246(6) 0.1917(3) 0.8510(3) 0.0791(13) Uani 1 1 d . . . H15A H 0.0788 0.1773 0.8536 0.095 Uiso 1 1 calc R . . H15B H -0.0173 0.2360 0.8740 0.095 Uiso 1 1 calc R . . C16 C -0.0844(6) 0.1515(3) 0.9138(4) 0.107(2) Uani 1 1 d . . . H16A H -0.1842 0.1677 0.9161 0.128 Uiso 1 1 calc R . . H16B H -0.0980 0.1076 0.8895 0.128 Uiso 1 1 calc R . . C17 C -0.0147(7) 0.1048(3) 1.0645(4) 0.1061(19) Uani 1 1 d . . . H17A H -0.0016 0.0623 1.0396 0.127 Uiso 1 1 calc R . . H17B H -0.1212 0.1090 1.0657 0.127 Uiso 1 1 calc R . . C18 C 0.0916(5) 0.1122(2) 1.1639(3) 0.0710(12) Uani 1 1 d . . . C19 C 0.1988(6) 0.0654(3) 1.1999(6) 0.1033(19) Uani 1 1 d . . . H19A H 0.2126 0.0308 1.1625 0.124 Uiso 1 1 calc R . . C20 C 0.2917(7) 0.0717(4) 1.2998(7) 0.131(3) Uani 1 1 d . . . H20A H 0.3666 0.0416 1.3290 0.157 Uiso 1 1 calc R . . C21 C 0.2589(7) 0.1271(4) 1.3484(4) 0.106(2) Uani 1 1 d . . . H21A H 0.3128 0.1333 1.4122 0.127 Uiso 1 1 calc R . . C22 C 0.1554(7) 0.1695(3) 1.3062(4) 0.1075(19) Uani 1 1 d . . . H22A H 0.1392 0.2056 1.3403 0.129 Uiso 1 1 calc R . . C23 C 0.0732(6) 0.1629(3) 1.2166(4) 0.0896(15) Uani 1 1 d . . . H23A H 0.0003 0.1943 1.1893 0.107 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 0.0509(4) 0.0497(4) 0.0508(4) 0.0100(3) 0.0105(3) 0.0056(3) Cl1 0.0669(8) 0.1127(11) 0.1127(11) 0.0029(8) -0.0158(7) -0.0257(7) Cl2 0.1179(11) 0.1058(10) 0.0743(8) 0.0068(7) 0.0432(8) 0.0329(8) P1 0.0444(5) 0.0518(6) 0.0377(5) 0.0052(4) 0.0055(4) 0.0001(4) N1 0.0510(18) 0.0422(16) 0.0485(17) 0.0022(13) 0.0068(14) -0.0037(14) O1 0.078(2) 0.124(3) 0.069(2) 0.024(2) 0.0136(17) -0.013(2) C1 0.179(9) 0.101(6) 0.228(11) 0.100(6) 0.137(9) 0.084(6) C2 0.204(8) 0.047(3) 0.123(5) 0.009(3) 0.082(6) -0.014(4) C3 0.106(4) 0.066(3) 0.087(4) 0.020(3) 0.045(3) -0.004(3) C4 0.142(6) 0.096(4) 0.052(3) 0.023(3) 0.022(3) -0.018(4) C5 0.098(5) 0.201(10) 0.144(7) 0.128(7) -0.009(6) 0.016(6) C6 0.071(3) 0.051(2) 0.063(2) 0.0146(19) 0.017(2) 0.006(2) C7 0.099(4) 0.086(4) 0.151(6) 0.057(4) 0.015(4) 0.024(3) C8 0.099(4) 0.092(4) 0.083(3) 0.012(3) 0.038(3) -0.020(3) C9 0.109(4) 0.054(3) 0.094(4) -0.006(2) 0.026(3) -0.017(3) C10 0.069(3) 0.094(3) 0.049(2) -0.003(2) -0.009(2) -0.021(3) C11 0.135(5) 0.191(7) 0.062(3) -0.048(4) 0.016(3) -0.051(5) C12 0.062(3) 0.166(6) 0.106(4) 0.032(4) -0.029(3) -0.019(4) C13 0.118(5) 0.091(4) 0.113(5) -0.007(3) -0.022(4) -0.049(4) C14 0.057(3) 0.104(4) 0.059(3) 0.010(2) 0.024(2) 0.005(2) C15 0.081(3) 0.110(4) 0.049(2) -0.006(2) 0.022(2) -0.009(3) C16 0.072(3) 0.179(6) 0.069(3) 0.024(4) 0.017(3) -0.004(4) C17 0.110(5) 0.119(5) 0.090(4) 0.014(3) 0.029(4) -0.021(4) C18 0.066(3) 0.083(3) 0.069(3) 0.020(3) 0.027(2) -0.004(3) C19 0.071(4) 0.076(3) 0.175(6) 0.021(4) 0.053(4) 0.001(3) C20 0.055(3) 0.124(6) 0.211(8) 0.106(6) 0.031(5) 0.009(4) C21 0.081(4) 0.142(6) 0.085(4) 0.041(4) 0.008(3) -0.014(4) C22 0.094(4) 0.150(6) 0.081(4) 0.020(4) 0.030(3) -0.002(4) C23 0.079(3) 0.102(4) 0.095(4) 0.016(3) 0.036(3) 0.000(3) _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 N1 1.754(3) . ? Ti1 Cl2 2.2977(15) . ? Ti1 Cl1 2.2981(15) . ? Ti1 C4 2.340(5) . ? Ti1 C3 2.342(5) . ? Ti1 C2 2.368(5) . ? Ti1 C1 2.400(6) . ? Ti1 C5 2.409(6) . ? P1 N1 1.601(3) . ? P1 C14 1.819(4) . ? P1 C6 1.853(4) . ? P1 C10 1.856(4) . ? O1 C17 1.380(6) . ? O1 C16 1.417(5) . ? C1 C2 1.355(11) . ? C1 C5 1.378(12) . ? C2 C3 1.341(8) . ? C3 C4 1.337(7) . ? C4 C5 1.431(11) . ? C6 C9 1.530(6) . ? C6 C7 1.536(6) . ? C6 C8 1.539(6) . ? C10 C11 1.525(7) . ? C10 C13 1.527(7) . ? C10 C12 1.548(7) . ? C14 C15 1.516(6) . ? C15 C16 1.447(7) . ? C17 C18 1.506(7) . ? C18 C23 1.338(7) . ? C18 C19 1.364(7) . ? C19 C20 1.469(10) . ? C20 C21 1.421(10) . ? C21 C22 1.303(8) . ? C22 C23 1.317(7) . ? 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 N1 Ti1 Cl2 103.62(11) . . ? N1 Ti1 Cl1 102.40(11) . . ? Cl2 Ti1 Cl1 101.26(7) . . ? N1 Ti1 C4 106.6(2) . . ? Cl2 Ti1 C4 142.08(18) . . ? Cl1 Ti1 C4 94.13(17) . . ? N1 Ti1 C3 91.09(17) . . ? Cl2 Ti1 C3 125.49(15) . . ? Cl1 Ti1 C3 126.64(16) . . ? C4 Ti1 C3 33.17(18) . . ? N1 Ti1 C2 108.3(3) . . ? Cl2 Ti1 C2 93.32(18) . . ? Cl1 Ti1 C2 141.7(2) . . ? C4 Ti1 C2 55.7(2) . . ? C3 Ti1 C2 33.08(19) . . ? N1 Ti1 C1 141.2(3) . . ? Cl2 Ti1 C1 86.3(2) . . ? Cl1 Ti1 C1 112.4(3) . . ? C4 Ti1 C1 55.8(3) . . ? C3 Ti1 C1 54.6(2) . . ? C2 Ti1 C1 33.0(3) . . ? N1 Ti1 C5 141.6(3) . . ? Cl2 Ti1 C5 111.5(3) . . ? Cl1 Ti1 C5 85.8(2) . . ? C4 Ti1 C5 35.0(3) . . ? C3 Ti1 C5 56.1(3) . . ? C2 Ti1 C5 55.9(3) . . ? C1 Ti1 C5 33.3(3) . . ? N1 P1 C14 111.65(18) . . ? N1 P1 C6 107.04(17) . . ? C14 P1 C6 108.0(2) . . ? N1 P1 C10 109.6(2) . . ? C14 P1 C10 105.4(2) . . ? C6 P1 C10 115.2(2) . . ? P1 N1 Ti1 179.5(2) . . ? C17 O1 C16 112.1(4) . . ? C2 C1 C5 110.1(8) . . ? C2 C1 Ti1 72.2(4) . . ? C5 C1 Ti1 73.7(4) . . ? C3 C2 C1 107.6(8) . . ? C3 C2 Ti1 72.4(3) . . ? C1 C2 Ti1 74.8(4) . . ? C4 C3 C2 110.4(6) . . ? C4 C3 Ti1 73.3(3) . . ? C2 C3 Ti1 74.5(3) . . ? C3 C4 C5 107.6(7) . . ? C3 C4 Ti1 73.5(3) . . ? C5 C4 Ti1 75.1(3) . . ? C1 C5 C4 104.3(7) . . ? C1 C5 Ti1 73.0(4) . . ? C4 C5 Ti1 69.9(3) . . ? C9 C6 C7 109.5(4) . . ? C9 C6 C8 107.6(4) . . ? C7 C6 C8 110.4(4) . . ? C9 C6 P1 107.0(3) . . ? C7 C6 P1 113.3(3) . . ? C8 C6 P1 108.9(3) . . ? C11 C10 C13 109.3(5) . . ? C11 C10 C12 111.2(4) . . ? C13 C10 C12 108.4(5) . . ? C11 C10 P1 110.7(3) . . ? C13 C10 P1 105.8(3) . . ? C12 C10 P1 111.2(4) . . ? C15 C14 P1 115.9(3) . . ? C16 C15 C14 113.3(4) . . ? O1 C16 C15 109.6(4) . . ? O1 C17 C18 108.9(5) . . ? C23 C18 C19 121.4(5) . . ? C23 C18 C17 119.0(5) . . ? C19 C18 C17 119.4(6) . . ? C18 C19 C20 117.8(6) . . ? C21 C20 C19 115.2(5) . . ? C22 C21 C20 121.8(6) . . ? C21 C22 C23 122.0(7) . . ? C22 C23 C18 121.7(6) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.467 _refine_diff_density_min -0.268 _refine_diff_density_rms 0.067 #===end data_C5Me5TiCl2NP(tBu)2(CH2)3OCH2Ph _database_code_depnum_ccdc_archive 'CCDC 702187' _audit_creation_method SHELXL-97 _chemical_formula_sum 'C28 H46 Cl2 N O P Ti' _chemical_formula_weight 562.43 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' P P 0.1023 0.0942 '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 P2(1)/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 10.6707(12) _cell_length_b 11.1671(12) _cell_length_c 25.817(3) _cell_angle_alpha 90.00 _cell_angle_beta 94.2680(10) _cell_angle_gamma 90.00 _cell_volume 3067.9(6) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 25.0 _exptl_crystal_description blocks _exptl_crystal_colour yellow _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.22 _exptl_crystal_density_diffrn 1.218 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1200 _exptl_absorpt_coefficient_mu 0.525 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.823176 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details ? _diffrn_measurement_method CCD _diffrn_ambient_temperature 296(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Bruker SMART system' _diffrn_radiation_monochromator graphite _diffrn_reflns_number 28755 _diffrn_reflns_av_R_equivalents 0.0751 _diffrn_reflns_av_sigmaI/netI 0.0590 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 1.58 _diffrn_reflns_theta_max 25.00 _reflns_number_total 5420 _reflns_number_gt 3328 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _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^)+(0.1000P)^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 constr _refine_ls_extinction_method none _refine_ls_number_reflns 5420 _refine_ls_number_parameters 307 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1104 _refine_ls_R_factor_gt 0.0609 _refine_ls_wR_factor_ref 0.1816 _refine_ls_wR_factor_gt 0.1518 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _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 0.03919(7) 0.29683(6) 0.14129(3) 0.0414(3) Uani 1 1 d . . . Cl1 Cl 0.00210(16) 0.44847(11) 0.19870(5) 0.0826(5) Uani 1 1 d . . . Cl2 Cl 0.25458(12) 0.27253(13) 0.15576(5) 0.0762(4) Uani 1 1 d . . . P1 P -0.04369(11) 0.05603(9) 0.20844(4) 0.0407(3) Uani 1 1 d . . . N1 N -0.0156(3) 0.1675(3) 0.17190(11) 0.0392(8) Uani 1 1 d . . . O1 O -0.4018(3) 0.0970(3) 0.11865(13) 0.0680(9) Uani 1 1 d . . . C1 C -0.0133(5) 0.4484(4) 0.07518(16) 0.0559(13) Uani 1 1 d . . . C2 C -0.1146(4) 0.3663(4) 0.07757(16) 0.0510(11) Uani 1 1 d . . . C3 C -0.0721(4) 0.2528(4) 0.06109(14) 0.0416(10) Uani 1 1 d . . . C4 C 0.0544(4) 0.2653(4) 0.05103(15) 0.0447(10) Uani 1 1 d . . . C5 C 0.0901(5) 0.3872(4) 0.05903(15) 0.0528(12) Uani 1 1 d . . . C6 C -0.0195(6) 0.5807(4) 0.0854(2) 0.092(2) Uani 1 1 d . . . H6A H -0.0418 0.6221 0.0535 0.138 Uiso 1 1 calc R . . H6B H 0.0609 0.6083 0.0998 0.138 Uiso 1 1 calc R . . H6C H -0.0817 0.5962 0.1096 0.138 Uiso 1 1 calc R . . C7 C -0.2457(5) 0.3930(5) 0.0914(2) 0.0858(18) Uani 1 1 d . . . H7A H -0.2951 0.4200 0.0610 0.129 Uiso 1 1 calc R . . H7B H -0.2434 0.4544 0.1175 0.129 Uiso 1 1 calc R . . H7C H -0.2825 0.3218 0.1045 0.129 Uiso 1 1 calc R . . C8 C -0.1513(4) 0.1437(4) 0.05157(18) 0.0621(13) Uani 1 1 d . . . H8A H -0.1874 0.1443 0.0164 0.093 Uiso 1 1 calc R . . H8B H -0.2172 0.1432 0.0749 0.093 Uiso 1 1 calc R . . H8C H -0.1002 0.0735 0.0573 0.093 Uiso 1 1 calc R . . C9 C 0.1354(5) 0.1690(4) 0.03036(18) 0.0657(14) Uani 1 1 d . . . H9A H 0.1283 0.1712 -0.0069 0.099 Uiso 1 1 calc R . . H9B H 0.1084 0.0922 0.0420 0.099 Uiso 1 1 calc R . . H9C H 0.2214 0.1821 0.0428 0.099 Uiso 1 1 calc R . . C10 C 0.2152(6) 0.4418(5) 0.0495(2) 0.0902(19) Uani 1 1 d . . . H10A H 0.2130 0.4715 0.0145 0.135 Uiso 1 1 calc R . . H10B H 0.2798 0.3822 0.0545 0.135 Uiso 1 1 calc R . . H10C H 0.2327 0.5067 0.0734 0.135 Uiso 1 1 calc R . . C11 C 0.0445(5) -0.0775(4) 0.18798(17) 0.0527(12) Uani 1 1 d . . . C12 C 0.1869(5) -0.0572(5) 0.1973(3) 0.0916(19) Uani 1 1 d . . . H12A H 0.2308 -0.1268 0.1865 0.137 Uiso 1 1 calc R . . H12B H 0.2080 -0.0430 0.2335 0.137 Uiso 1 1 calc R . . H12C H 0.2109 0.0109 0.1776 0.137 Uiso 1 1 calc R . . C13 C 0.0133(5) -0.0937(4) 0.12946(17) 0.0656(14) Uani 1 1 d . . . H13A H 0.0575 -0.1621 0.1176 0.098 Uiso 1 1 calc R . . H13B H 0.0384 -0.0235 0.1114 0.098 Uiso 1 1 calc R . . H13C H -0.0755 -0.1056 0.1227 0.098 Uiso 1 1 calc R . . C14 C 0.0097(6) -0.1926(4) 0.2148(2) 0.0847(18) Uani 1 1 d . . . H14A H 0.0583 -0.2576 0.2026 0.127 Uiso 1 1 calc R . . H14B H -0.0781 -0.2087 0.2072 0.127 Uiso 1 1 calc R . . H14C H 0.0270 -0.1840 0.2517 0.127 Uiso 1 1 calc R . . C15 C -0.0076(4) 0.0974(4) 0.27778(15) 0.0482(11) Uani 1 1 d . . . C16 C 0.1283(5) 0.1382(6) 0.2874(2) 0.098(2) Uani 1 1 d . . . H16A H 0.1448 0.1590 0.3234 0.147 Uiso 1 1 calc R . . H16B H 0.1424 0.2068 0.2662 0.147 Uiso 1 1 calc R . . H16C H 0.1835 0.0745 0.2788 0.147 Uiso 1 1 calc R . . C17 C -0.0308(6) -0.0057(5) 0.31457(19) 0.0889(19) Uani 1 1 d . . . H17A H -0.0110 0.0196 0.3498 0.133 Uiso 1 1 calc R . . H17B H 0.0215 -0.0724 0.3069 0.133 Uiso 1 1 calc R . . H17C H -0.1175 -0.0292 0.3102 0.133 Uiso 1 1 calc R . . C18 C -0.0898(6) 0.2028(5) 0.28930(19) 0.0852(18) Uani 1 1 d . . . H18A H -0.0733 0.2263 0.3249 0.128 Uiso 1 1 calc R . . H18B H -0.1766 0.1806 0.2832 0.128 Uiso 1 1 calc R . . H18C H -0.0718 0.2686 0.2671 0.128 Uiso 1 1 calc R . . C19 C -0.2087(4) 0.0121(4) 0.19966(17) 0.0537(12) Uani 1 1 d . . . H19A H -0.2223 -0.0248 0.1657 0.064 Uiso 1 1 calc R . . H19B H -0.2230 -0.0491 0.2252 0.064 Uiso 1 1 calc R . . C20 C -0.3080(4) 0.1080(4) 0.20372(18) 0.0597(13) Uani 1 1 d . . . H20A H -0.3265 0.1166 0.2398 0.072 Uiso 1 1 calc R . . H20B H -0.2754 0.1840 0.1924 0.072 Uiso 1 1 calc R . . C21 C -0.4276(4) 0.0786(5) 0.17127(19) 0.0652(14) Uani 1 1 d . . . H21A H -0.4519 -0.0038 0.1768 0.078 Uiso 1 1 calc R . . H21B H -0.4954 0.1305 0.1805 0.078 Uiso 1 1 calc R . . C22 C -0.5031(5) 0.0630(5) 0.0828(2) 0.0802(16) Uani 1 1 d . . . H22A H -0.4943 0.1035 0.0501 0.096 Uiso 1 1 calc R . . H22B H -0.5814 0.0894 0.0960 0.096 Uiso 1 1 calc R . . C23 C -0.5100(5) -0.0693(5) 0.07333(17) 0.0622(13) Uani 1 1 d . . . C24 C -0.4025(5) -0.1323(6) 0.0659(2) 0.0781(16) Uani 1 1 d . . . H24A H -0.3249 -0.0940 0.0679 0.094 Uiso 1 1 calc R . . C25 C -0.4110(8) -0.2550(6) 0.0552(2) 0.095(2) Uani 1 1 d . . . H25A H -0.3383 -0.2978 0.0498 0.114 Uiso 1 1 calc R . . C26 C -0.5230(9) -0.3127(6) 0.0525(2) 0.102(2) Uani 1 1 d . . . H26A H -0.5279 -0.3945 0.0460 0.123 Uiso 1 1 calc R . . C27 C -0.6273(8) -0.2482(7) 0.0596(3) 0.108(2) Uani 1 1 d . . . H27A H -0.7050 -0.2863 0.0567 0.129 Uiso 1 1 calc R . . C28 C -0.6224(5) -0.1280(6) 0.0709(2) 0.0806(16) Uani 1 1 d . . . H28A H -0.6956 -0.0867 0.0769 0.097 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 0.0618(5) 0.0286(4) 0.0337(4) -0.0023(3) 0.0024(3) -0.0025(4) Cl1 0.1594(15) 0.0408(7) 0.0485(7) -0.0121(5) 0.0132(8) 0.0064(8) Cl2 0.0581(8) 0.0914(11) 0.0772(9) 0.0106(7) -0.0087(7) -0.0103(7) P1 0.0532(7) 0.0310(6) 0.0372(6) 0.0014(4) -0.0001(5) -0.0011(5) N1 0.053(2) 0.0311(18) 0.0335(17) 0.0014(14) 0.0007(15) 0.0015(15) O1 0.061(2) 0.082(2) 0.060(2) 0.0018(18) -0.0025(17) -0.0048(18) C1 0.096(4) 0.029(2) 0.041(2) 0.0008(19) 0.001(2) 0.002(3) C2 0.064(3) 0.048(3) 0.041(2) 0.003(2) 0.005(2) 0.016(2) C3 0.055(3) 0.040(2) 0.029(2) 0.0016(17) -0.0028(19) 0.001(2) C4 0.058(3) 0.043(3) 0.033(2) 0.0018(18) 0.0015(19) 0.000(2) C5 0.080(3) 0.040(3) 0.039(2) -0.001(2) 0.010(2) -0.014(2) C6 0.178(7) 0.030(3) 0.068(4) 0.005(2) 0.005(4) 0.005(3) C7 0.086(4) 0.098(5) 0.074(4) 0.012(3) 0.009(3) 0.033(4) C8 0.061(3) 0.063(3) 0.060(3) -0.002(2) -0.012(2) -0.015(3) C9 0.076(4) 0.064(3) 0.059(3) -0.010(2) 0.016(3) 0.006(3) C10 0.109(5) 0.085(4) 0.078(4) 0.011(3) 0.018(3) -0.044(4) C11 0.073(3) 0.030(2) 0.054(3) 0.004(2) 0.003(2) 0.008(2) C12 0.067(4) 0.078(4) 0.128(5) -0.017(4) -0.005(3) 0.027(3) C13 0.093(4) 0.050(3) 0.054(3) -0.005(2) 0.009(3) 0.021(3) C14 0.141(6) 0.035(3) 0.080(4) 0.017(3) 0.020(4) 0.013(3) C15 0.063(3) 0.050(3) 0.031(2) -0.0004(19) 0.000(2) -0.003(2) C16 0.085(4) 0.151(6) 0.057(3) -0.030(4) -0.002(3) -0.035(4) C17 0.151(6) 0.074(4) 0.043(3) 0.016(3) 0.018(3) -0.009(4) C18 0.125(5) 0.077(4) 0.050(3) -0.022(3) -0.017(3) 0.029(4) C19 0.057(3) 0.045(3) 0.058(3) 0.002(2) -0.001(2) -0.014(2) C20 0.058(3) 0.066(3) 0.055(3) -0.014(2) 0.003(2) -0.005(3) C21 0.048(3) 0.076(4) 0.072(3) -0.003(3) 0.010(2) 0.003(3) C22 0.073(4) 0.091(4) 0.074(4) 0.001(3) -0.015(3) 0.006(3) C23 0.059(3) 0.080(4) 0.046(3) 0.005(2) -0.007(2) -0.002(3) C24 0.067(4) 0.087(5) 0.082(4) -0.002(3) 0.017(3) -0.005(3) C25 0.123(6) 0.091(5) 0.075(4) 0.000(4) 0.024(4) 0.017(4) C26 0.156(8) 0.070(5) 0.078(4) 0.006(3) -0.009(5) -0.020(5) C27 0.100(6) 0.101(6) 0.118(6) 0.029(5) -0.023(5) -0.040(5) C28 0.057(4) 0.102(5) 0.081(4) 0.013(4) -0.003(3) -0.004(3) _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 N1 1.767(3) . ? Ti1 Cl1 2.3040(14) . ? Ti1 Cl2 2.3169(15) . ? Ti1 C3 2.361(4) . ? Ti1 C2 2.367(4) . ? Ti1 C4 2.374(4) . ? Ti1 C1 2.439(4) . ? Ti1 C5 2.449(4) . ? P1 N1 1.603(3) . ? P1 C19 1.825(4) . ? P1 C11 1.861(4) . ? P1 C15 1.861(4) . ? O1 C21 1.421(5) . ? O1 C22 1.421(5) . ? C1 C5 1.388(6) . ? C1 C2 1.422(6) . ? C1 C6 1.503(6) . ? C2 C3 1.422(6) . ? C2 C7 1.499(6) . ? C3 C4 1.400(6) . ? C3 C8 1.492(6) . ? C4 C5 1.425(6) . ? C4 C9 1.502(6) . ? C5 C10 1.505(7) . ? C11 C14 1.519(6) . ? C11 C13 1.533(6) . ? C11 C12 1.537(7) . ? C15 C18 1.511(6) . ? C15 C16 1.524(6) . ? C15 C17 1.524(6) . ? C19 C20 1.516(6) . ? C20 C21 1.510(6) . ? C22 C23 1.499(7) . ? C23 C28 1.364(7) . ? C23 C24 1.372(7) . ? C24 C25 1.399(8) . ? C25 C26 1.356(9) . ? C26 C27 1.349(9) . ? C27 C28 1.374(9) . ? 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 N1 Ti1 Cl1 103.58(11) . . ? N1 Ti1 Cl2 100.92(11) . . ? Cl1 Ti1 Cl2 101.43(6) . . ? N1 Ti1 C3 93.47(14) . . ? Cl1 Ti1 C3 128.16(11) . . ? Cl2 Ti1 C3 123.05(12) . . ? N1 Ti1 C2 110.09(16) . . ? Cl1 Ti1 C2 93.59(11) . . ? Cl2 Ti1 C2 141.16(12) . . ? C3 Ti1 C2 35.01(14) . . ? N1 Ti1 C4 111.51(14) . . ? Cl1 Ti1 C4 140.18(11) . . ? Cl2 Ti1 C4 90.09(12) . . ? C3 Ti1 C4 34.40(15) . . ? C2 Ti1 C4 57.37(15) . . ? N1 Ti1 C1 144.48(16) . . ? Cl1 Ti1 C1 84.18(11) . . ? Cl2 Ti1 C1 111.56(14) . . ? C3 Ti1 C1 57.07(14) . . ? C2 Ti1 C1 34.39(15) . . ? C4 Ti1 C1 56.29(14) . . ? N1 Ti1 C5 145.80(14) . . ? Cl1 Ti1 C5 108.34(11) . . ? Cl2 Ti1 C5 84.65(13) . . ? C3 Ti1 C5 56.96(14) . . ? C2 Ti1 C5 56.57(16) . . ? C4 Ti1 C5 34.33(13) . . ? C1 Ti1 C5 32.98(15) . . ? N1 P1 C19 110.88(19) . . ? N1 P1 C11 109.53(19) . . ? C19 P1 C11 104.7(2) . . ? N1 P1 C15 109.82(18) . . ? C19 P1 C15 108.3(2) . . ? C11 P1 C15 113.5(2) . . ? P1 N1 Ti1 168.6(2) . . ? C21 O1 C22 113.0(4) . . ? C5 C1 C2 108.7(4) . . ? C5 C1 C6 125.7(5) . . ? C2 C1 C6 125.6(5) . . ? C5 C1 Ti1 73.9(2) . . ? C2 C1 Ti1 70.0(2) . . ? C6 C1 Ti1 124.7(3) . . ? C3 C2 C1 107.5(4) . . ? C3 C2 C7 124.9(5) . . ? C1 C2 C7 127.5(4) . . ? C3 C2 Ti1 72.3(2) . . ? C1 C2 Ti1 75.6(3) . . ? C7 C2 Ti1 120.7(3) . . ? C4 C3 C2 107.5(4) . . ? C4 C3 C8 126.3(4) . . ? C2 C3 C8 126.0(4) . . ? C4 C3 Ti1 73.3(2) . . ? C2 C3 Ti1 72.7(2) . . ? C8 C3 Ti1 123.8(3) . . ? C3 C4 C5 108.6(4) . . ? C3 C4 C9 125.7(4) . . ? C5 C4 C9 125.5(4) . . ? C3 C4 Ti1 72.3(2) . . ? C5 C4 Ti1 75.7(2) . . ? C9 C4 Ti1 122.5(3) . . ? C1 C5 C4 107.7(4) . . ? C1 C5 C10 125.8(4) . . ? C4 C5 C10 126.5(5) . . ? C1 C5 Ti1 73.1(2) . . ? C4 C5 Ti1 70.0(2) . . ? C10 C5 Ti1 124.4(3) . . ? C14 C11 C13 107.9(4) . . ? C14 C11 C12 109.0(4) . . ? C13 C11 C12 108.1(4) . . ? C14 C11 P1 113.7(3) . . ? C13 C11 P1 107.3(3) . . ? C12 C11 P1 110.6(3) . . ? C18 C15 C16 107.1(4) . . ? C18 C15 C17 110.0(4) . . ? C16 C15 C17 108.7(4) . . ? C18 C15 P1 107.5(3) . . ? C16 C15 P1 111.0(3) . . ? C17 C15 P1 112.4(3) . . ? C20 C19 P1 118.3(3) . . ? C21 C20 C19 112.0(4) . . ? O1 C21 C20 106.4(4) . . ? O1 C22 C23 113.3(4) . . ? C28 C23 C24 119.3(6) . . ? C28 C23 C22 120.9(5) . . ? C24 C23 C22 119.8(5) . . ? C23 C24 C25 119.2(6) . . ? C26 C25 C24 121.3(7) . . ? C27 C26 C25 118.2(7) . . ? C26 C27 C28 122.1(7) . . ? C23 C28 C27 119.9(6) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.729 _refine_diff_density_min -0.303 _refine_diff_density_rms 0.071 #===end