# om0008777.cif data_global #============================================================================ # 1. SUBMISSION DETAILS _publ_contact_author ; Isabel L\'opez-Solera Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Facultad de Qu\'imicas Universidad Castilla La Mancha 13071-Ciudad Real Spain ; _publ_contact_author_phone '+34 926 295300 (ext:3512)' _publ_contact_author_fax '+34 926 295318' _publ_contact_author_email milsolera@qino-cr.uclm.es _publ_requested_journal 'Organometallics' _publ_requested_coeditor_name ? _publ_contact_letter ; 10th October, 2000 Please consider this CIF submission as supplementary material of the structures containing in a paper which will be submitted to Organometallics shortly. ; #============================================================================ # 2. PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic? _journal_date_to_coeditor ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_date_printers_first ? _journal_date_printers_final ? _journal_date_proofs_out ? _journal_date_proofs_in ? _journal_coeditor_name ? _journal_coeditor_code ? _journal_coeditor_notes ? _journal_techeditor_code ? _journal_techeditor_notes ? _journal_coden_ASTM ? _journal_name_full ? _journal_year ? _journal_volume ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? #============================================================================ # 3. TITLE AND AUTHOR LIST _publ_section_title ; Polymerization of ethylene by the electrophilic heteroscorpionate- containing complexes [TiCl~3(bdmpza)] and [TiCl~2(bdmpza){O(CH~2)~4Cl}] [bdmpza=bis(3,5-dimethylpyrazol-1-yl)-acetate] ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address 'Otero, Antonio' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'Fern\'andez-Baeza, Juan' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'Anti¤olo, Antonio' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'Carrillo-Hermosilla, Fernando' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'Tejeda, Juan' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'D\'iez-Barra, Enrique' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'Lara-S\'anchez, Agust\'in' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'S\'anchez-Barba, Luis' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'L\'opez-Solera, Isabel' ; Departamento de Qu\'imica In\'organica, Org\'anica y Bioqu\'imica Universidad Castilla-La Mancha Facultad de Qu\'imicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'Ribeiro, M. R.' ; Departamento de Engenharia Quimica Instituto Superior Tecnico de Lisboa 1049-001-Lisboa Portugal ; 'Campos, J. M.' ; Departamento de Engenharia Quimica Instituto Superior Tecnico de Lisboa 1049-001-Lisboa Portugal ; #============================================================================ data_2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H23 Cl3 N4 O3 Ti' _chemical_formula_weight 473.63 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' '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)/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 7.9870(10) _cell_length_b 16.2090(10) _cell_length_c 16.9960(10) _cell_angle_alpha 90.00 _cell_angle_beta 100.47 _cell_angle_gamma 90.00 _cell_volume 2163.7(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Prismatic _exptl_crystal_colour Colorless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.454 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 976 _exptl_absorpt_coefficient_mu 0.789 _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 293(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_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 ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5376 _diffrn_reflns_av_R_equivalents 0.1131 _diffrn_reflns_av_sigmaI/netI 0.2881 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.44 _diffrn_reflns_theta_max 28.03 _reflns_number_total 5208 _reflns_number_gt 1761 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius (control program)' _computing_cell_refinement 'Npnius (control program)' _computing_data_reduction 'XCAD4 (Harms, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _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^)+(0.0807P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5208 _refine_ls_number_parameters 259 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.2943 _refine_ls_R_factor_gt 0.0861 _refine_ls_wR_factor_ref 0.2225 _refine_ls_wR_factor_gt 0.1600 _refine_ls_goodness_of_fit_ref 0.961 _refine_ls_restrained_S_all 0.961 _refine_ls_shift/su_max 0.184 _refine_ls_shift/su_mean 0.014 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 0.33617(18) 0.29983(7) 0.42133(8) 0.0462(4) Uani 1 1 d . . . Cl1 Cl 0.4547(3) 0.40991(11) 0.36647(12) 0.0630(6) Uani 1 1 d . . . Cl2 Cl 0.2682(3) 0.37068(12) 0.52807(12) 0.0653(6) Uani 1 1 d . . . Cl3 Cl -0.136(4) 0.5557(19) 0.207(3) 0.151(9) Uani 0.65(8) 1 d P A 1 Cl3A Cl -0.094(3) 0.5773(19) 0.254(5) 0.137(12) Uani 0.35(8) 1 d P A 2 O1 O 0.2900(6) 0.1916(3) 0.4676(3) 0.0511(13) Uani 1 1 d . . . O2 O 0.3439(7) 0.0649(3) 0.5107(4) 0.0734(18) Uani 1 1 d . . . O3 O 0.1372(7) 0.3023(3) 0.3606(3) 0.0606(14) Uani 1 1 d . . . N1 N 0.5984(7) 0.2731(3) 0.4947(3) 0.0421(15) Uani 1 1 d . . . N2 N 0.6601(7) 0.1933(3) 0.4964(3) 0.0419(14) Uani 1 1 d . . . N3 N 0.4409(7) 0.2195(3) 0.3375(3) 0.0438(15) Uani 1 1 d . . . N4 N 0.5292(7) 0.1492(3) 0.3664(3) 0.0430(14) Uani 1 1 d . . . C1 C 0.5537(8) 0.1308(4) 0.4508(4) 0.0409(17) Uani 1 1 d . . . H1 H 0.6103 0.0771 0.4604 0.049 Uiso 1 1 calc R . . C2 C 0.3814(9) 0.1270(4) 0.4797(4) 0.0458(19) Uani 1 1 d . . . C3 C 0.7284(10) 0.3167(4) 0.5350(4) 0.050(2) Uani 1 1 d . . . C4 C 0.8660(11) 0.2656(5) 0.5622(5) 0.062(2) Uani 1 1 d . . . H4 H 0.9691 0.2818 0.5930 0.074 Uiso 1 1 calc R . . C5 C 0.8242(9) 0.1879(4) 0.5359(4) 0.0482(19) Uani 1 1 d . . . C6 C 0.7190(10) 0.4083(4) 0.5487(5) 0.062(2) Uani 1 1 d . . . H6A H 0.7677 0.4371 0.5089 0.074 Uiso 1 1 calc R . . H6B H 0.7810 0.4217 0.6009 0.074 Uiso 1 1 calc R . . H6C H 0.6021 0.4245 0.5448 0.074 Uiso 1 1 calc R . . C7 C 0.9241(10) 0.1105(5) 0.5420(5) 0.072(3) Uani 1 1 d . . . H7A H 0.8628 0.0678 0.5637 0.087 Uiso 1 1 calc R . . H7B H 1.0319 0.1191 0.5765 0.087 Uiso 1 1 calc R . . H7C H 0.9423 0.0946 0.4898 0.087 Uiso 1 1 calc R . . C8 C 0.4438(10) 0.2195(4) 0.2592(4) 0.052(2) Uani 1 1 d . . . C9 C 0.5321(10) 0.1528(5) 0.2383(5) 0.063(2) Uani 1 1 d . . . H9 H 0.5508 0.1400 0.1873 0.076 Uiso 1 1 calc R . . C10 C 0.5876(9) 0.1086(4) 0.3070(5) 0.0493(19) Uani 1 1 d . . . C11 C 0.3529(12) 0.2849(5) 0.2041(5) 0.077(3) Uani 1 1 d . . . H11A H 0.2345 0.2855 0.2079 0.092 Uiso 1 1 calc R . . H11B H 0.3644 0.2729 0.1500 0.092 Uiso 1 1 calc R . . H11C H 0.4022 0.3379 0.2193 0.092 Uiso 1 1 calc R . . C12 C 0.6910(11) 0.0297(5) 0.3220(5) 0.077(3) Uani 1 1 d . . . H12A H 0.7975 0.0412 0.3565 0.092 Uiso 1 1 calc R . . H12B H 0.7120 0.0083 0.2720 0.092 Uiso 1 1 calc R . . H12C H 0.6289 -0.0103 0.3469 0.092 Uiso 1 1 calc R . . C13 C -0.0366(15) 0.2852(7) 0.3356(8) 0.115(4) Uani 1 1 d . . . H13A H -0.0841 0.2662 0.3810 0.138 Uiso 1 1 calc R . . H13B H -0.0494 0.2411 0.2962 0.138 Uiso 1 1 calc R . . C14 C -0.1293(16) 0.3562(9) 0.3013(13) 0.207(10) Uani 1 1 d . . . H14A H -0.1506 0.3462 0.2441 0.248 Uiso 1 1 calc R . . H14B H -0.2392 0.3520 0.3176 0.248 Uiso 1 1 calc R . . C15 C -0.092(2) 0.4311(11) 0.3085(15) 0.244(13) Uani 1 1 d . A . H15A H 0.0036 0.4360 0.2805 0.293 Uiso 1 1 calc R . . H15B H -0.0422 0.4364 0.3648 0.293 Uiso 1 1 calc R . . C16 C -0.1754(19) 0.5032(10) 0.2917(9) 0.174(6) Uani 1 1 d . . . H16A H -0.1459 0.5393 0.3377 0.209 Uiso 1 1 calc R A 1 H16B H -0.2966 0.4923 0.2848 0.209 Uiso 1 1 calc R A 1 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 0.0568(9) 0.0322(7) 0.0498(8) 0.0051(6) 0.0103(7) 0.0113(7) Cl1 0.0946(17) 0.0368(10) 0.0612(13) 0.0101(9) 0.0235(12) 0.0052(11) Cl2 0.0880(16) 0.0507(12) 0.0637(13) -0.0012(10) 0.0306(12) 0.0137(11) Cl3 0.150(10) 0.177(10) 0.141(18) 0.081(12) 0.066(12) 0.070(7) Cl3A 0.134(11) 0.149(13) 0.14(3) 0.061(15) 0.040(13) 0.014(12) O1 0.053(3) 0.032(3) 0.070(3) 0.008(3) 0.014(3) 0.010(3) O2 0.073(4) 0.041(3) 0.118(5) 0.029(3) 0.046(4) 0.012(3) O3 0.060(4) 0.052(3) 0.066(3) 0.007(3) 0.003(3) 0.013(3) N1 0.052(4) 0.030(3) 0.043(3) 0.008(3) 0.006(3) -0.002(3) N2 0.052(4) 0.027(3) 0.046(4) -0.003(3) 0.007(3) -0.004(3) N3 0.060(4) 0.029(3) 0.042(4) 0.000(3) 0.006(3) 0.003(3) N4 0.056(4) 0.036(3) 0.036(3) -0.007(3) 0.008(3) 0.000(3) C1 0.050(5) 0.028(3) 0.047(4) 0.003(3) 0.013(4) 0.010(3) C2 0.060(5) 0.025(4) 0.052(5) -0.002(3) 0.008(4) 0.008(4) C3 0.067(6) 0.043(4) 0.042(4) 0.000(4) 0.014(4) -0.011(4) C4 0.054(5) 0.058(5) 0.066(6) -0.004(5) -0.007(4) 0.000(5) C5 0.046(5) 0.043(5) 0.055(5) 0.002(4) 0.006(4) 0.001(4) C6 0.082(6) 0.046(5) 0.057(5) -0.008(4) 0.011(5) -0.013(4) C7 0.050(5) 0.062(6) 0.096(7) 0.007(5) -0.007(5) 0.012(4) C8 0.071(6) 0.052(5) 0.033(4) -0.006(4) 0.005(4) 0.006(4) C9 0.086(6) 0.062(5) 0.046(5) -0.018(4) 0.024(5) 0.000(5) C10 0.054(5) 0.050(5) 0.046(5) -0.010(4) 0.016(4) 0.004(4) C11 0.108(8) 0.067(6) 0.048(5) 0.004(5) -0.004(5) 0.013(5) C12 0.096(7) 0.066(6) 0.073(6) -0.019(5) 0.028(5) 0.033(5) C13 0.094(9) 0.094(9) 0.146(10) 0.030(7) -0.007(8) -0.026(7) C14 0.089(10) 0.108(11) 0.39(3) -0.077(15) -0.055(13) 0.058(10) C15 0.157(16) 0.142(15) 0.43(3) 0.15(2) 0.041(18) 0.099(14) C16 0.160(14) 0.171(15) 0.205(17) 0.044(13) 0.068(12) -0.014(13) _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 O3 1.731(5) . ? Ti1 O1 1.984(4) . ? Ti1 N3 2.204(6) . ? Ti1 N1 2.276(6) . ? Ti1 Cl2 2.294(2) . ? Ti1 Cl1 2.296(2) . ? Cl3 C16 1.75(2) . ? Cl3A C16 1.56(3) . ? O1 C2 1.272(7) . ? O2 C2 1.200(8) . ? O3 C13 1.403(11) . ? N1 C3 1.337(8) . ? N1 N2 1.382(7) . ? N2 C5 1.362(8) . ? N2 C1 1.453(8) . ? N3 C8 1.335(8) . ? N3 N4 1.382(7) . ? N4 C10 1.356(8) . ? N4 C1 1.444(8) . ? C1 C2 1.544(9) . ? C3 C4 1.385(10) . ? C3 C6 1.508(10) . ? C4 C5 1.358(10) . ? C5 C7 1.479(10) . ? C8 C9 1.372(10) . ? C8 C11 1.511(10) . ? C9 C10 1.373(10) . ? C10 C12 1.518(10) . ? C13 C14 1.434(16) . ? C14 C15 1.252(18) . ? C15 C16 1.351(17) . ? 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 O3 Ti1 O1 92.3(2) . . ? O3 Ti1 N3 92.5(2) . . ? O1 Ti1 N3 81.6(2) . . ? O3 Ti1 N1 170.0(2) . . ? O1 Ti1 N1 80.41(19) . . ? N3 Ti1 N1 79.8(2) . . ? O3 Ti1 Cl2 97.84(18) . . ? O1 Ti1 Cl2 92.35(15) . . ? N3 Ti1 Cl2 168.25(17) . . ? N1 Ti1 Cl2 89.34(16) . . ? O3 Ti1 Cl1 98.16(19) . . ? O1 Ti1 Cl1 165.52(15) . . ? N3 Ti1 Cl1 87.93(16) . . ? N1 Ti1 Cl1 87.94(15) . . ? Cl2 Ti1 Cl1 96.11(8) . . ? C2 O1 Ti1 130.5(5) . . ? C13 O3 Ti1 157.9(6) . . ? C3 N1 N2 104.0(5) . . ? C3 N1 Ti1 137.1(5) . . ? N2 N1 Ti1 118.6(4) . . ? C5 N2 N1 112.2(5) . . ? C5 N2 C1 129.4(6) . . ? N1 N2 C1 118.0(5) . . ? C8 N3 N4 104.7(5) . . ? C8 N3 Ti1 136.2(5) . . ? N4 N3 Ti1 119.1(4) . . ? C10 N4 N3 111.0(6) . . ? C10 N4 C1 129.5(6) . . ? N3 N4 C1 119.4(5) . . ? N4 C1 N2 110.3(5) . . ? N4 C1 C2 110.9(6) . . ? N2 C1 C2 109.1(5) . . ? O2 C2 O1 125.5(7) . . ? O2 C2 C1 118.7(6) . . ? O1 C2 C1 115.8(6) . . ? N1 C3 C4 110.5(6) . . ? N1 C3 C6 122.9(7) . . ? C4 C3 C6 126.6(7) . . ? C5 C4 C3 108.2(7) . . ? C4 C5 N2 105.0(6) . . ? C4 C5 C7 131.7(7) . . ? N2 C5 C7 123.2(7) . . ? N3 C8 C9 111.2(7) . . ? N3 C8 C11 121.7(7) . . ? C9 C8 C11 127.1(7) . . ? C8 C9 C10 107.0(6) . . ? N4 C10 C9 106.1(6) . . ? N4 C10 C12 122.3(7) . . ? C9 C10 C12 131.6(7) . . ? O3 C13 C14 112.0(9) . . ? C15 C14 C13 130.0(15) . . ? C14 C15 C16 135.8(19) . . ? C15 C16 Cl3A 121.7(16) . . ? C15 C16 Cl3 116.0(15) . . ? Cl3A C16 Cl3 30.3(14) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 28.03 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.372 _refine_diff_density_min -0.376 _refine_diff_density_rms 0.085 #===END