# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global #=================================================================== _journal_coden_Cambridge 182 loop_ _publ_author_name 'Matthias Tamm' 'Thomas Bannenberg' 'Eberhardt Herdtweck' 'Soren Randoll' _publ_contact_author_name 'Prof Matthias Tamm' _publ_contact_author_address ; Anorganisch-Chemisches Technische Universitat Munchen Garching GERMANY ; _publ_contact_author_email MATTHIAS.TAMM@CH.TUM.DE _publ_requested_journal 'Chemical Communications' _publ_section_title ; Titanium Complexes with Imidazolin-2-iminato Ligands ; _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). SIR92, J. Appl. Cryst. 27, 435-436. Nonius (2001a). Data Collection Software for Nonius Kappa-CCD devices. Nonius BV, Delft, The Netherlands. Nonius (2001b). DENZO Processing Software for Nonius Kappa-CCD devices, Nonius BV, Delft, The Netherlands. Sheldrick, G. M. (1998). SHELXL97, University of Gottingen, Gottingen, Germany. Spek, A. L. (2001). PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. ; #=================================================================== data_RANE-4317-173 _database_code_depnum_ccdc_archive 'CCDC 229688' #=================================================================== # 0. AUDIT DETAILS _audit_creation_date 24-Oct-03 _audit_creation_method 'PLATON option' _audit_update_record ; 24-Oct-03 Updated by the Author E.H. Textwriting by E.H. Checkcif OK 14-Jan-04 Updated by the Author E.H. 20-Jan-04 Updated by the Author E.H. ; #=================================================================== # 5. CHEMICAL DATA #=================================================================== _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety 'C14 H29 N3 Si' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C14 H29 N3 Si' _chemical_formula_weight 267.49 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Si Si 0.0817 0.0704 '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' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #=================================================================== # 6. CRYSTAL DATA #=================================================================== _symmetry_cell_setting Triclinic _symmetry_space_group_name_Hall '-P 1' _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z _cell_length_a 9.0758(2) _cell_length_b 9.4187(2) _cell_length_c 11.0961(3) _cell_angle_alpha 84.7122(12) _cell_angle_beta 83.0332(13) _cell_angle_gamma 63.7546(9) _cell_volume 843.66(4) _cell_formula_units_Z 2 _cell_measurement_temperature 173(1) _cell_measurement_reflns_used 3090 _cell_measurement_theta_min 1.85 _cell_measurement_theta_max 25.40 _exptl_crystal_description fragment _exptl_crystal_colour colourless _exptl_crystal_size_max 0.53 _exptl_crystal_size_mid 0.46 _exptl_crystal_size_min 0.35 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.053 _exptl_crystal_density_method none _exptl_crystal_F_000 296 _exptl_absorpt_coefficient_mu 0.130 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.955 _exptl_absorpt_correction_T_max 0.965 _exptl_absorpt_process_details '(applied during the scaling procedure; Nonius, 2001b)' _exptl_special_details ; Diffractometer operator E. Herdtweck scanspeed 2 x 25 s per film repetition 1 dx 40 516 films measured in 9 data sets set 1: phi-scan with delta_phi = 2.0 set 2 to 9 omega-scans with delta_omega = 2.0 ; _publ_section_exptl_prep ; The crystal was fixed in a capillary with perfluorinated ether and transferred to the diffractometer. ; _publ_section_exptl_refinement ; Straight forward after integration with the program NPROCESS, source: Nonius (2001b). Hydrogen atoms could be located in the difference Fourier maps and refined freely. ; #=================================================================== # 7. EXPERIMENTAL DATA #=================================================================== _diffrn_ambient_temperature 173(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'NONIUS FR 591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device ' \k-geometry diffractometer ' _diffrn_measurement_device_type ' Nonius \k-CCD diffractometer' _diffrn_measurement_method ' phi- and omega-rotation ' _diffrn_detector ' CCD plate ' _diffrn_detector_area_resol_mean 18 # 9 for binned mode _diffrn_standards_decay_% 0 # number of measured reflections (redundant set) _diffrn_reflns_number 18531 _diffrn_reflns_av_R_equivalents 0.042 _diffrn_reflns_av_sigmaI/netI 0.0257 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.85 _diffrn_reflns_theta_max 25.40 _reflns_number_total 3097 _reflns_number_gt 2758 # number of observed reflections (> n sig(I)) _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Kappa-CCD Control Software (Nonius, 2001a)' _computing_cell_refinement 'DENZO (Nonius, 2001b)' _computing_data_reduction 'DENZO (Nonius, 2001b)' _computing_structure_solution 'SIR92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1998)' _computing_molecular_graphics 'PLATON (Spek, 2001)' _computing_publication_material 'PLATON (Spek, 2001)' #=================================================================== # 8. REFINEMENT DATA #=================================================================== _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 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 sigma _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(Fo^2^)+(0.0549P)^2^+0.5892P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_number_reflns 3097 _refine_ls_number_parameters 279 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0524 _refine_ls_R_factor_gt 0.0465 _refine_ls_wR_factor_ref 0.1367 _refine_ls_wR_factor_gt 0.1333 _refine_ls_goodness_of_fit_ref 1.149 _refine_ls_restrained_S_all 1.149 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.40 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.481 _refine_diff_density_min -0.241 _refine_diff_density_rms 0.048 #=================================================================== # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS #=================================================================== loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Si Si Uani 0.12347(7) 0.84057(7) 0.25932(6) 1.000 0.0344(2) . . N1 N Uani 0.3060(2) 0.6861(2) 0.26453(17) 1.000 0.0341(5) . . N2 N Uani 0.4735(2) 0.4093(2) 0.30412(16) 1.000 0.0308(5) . . N3 N Uani 0.5867(2) 0.5414(2) 0.18475(15) 1.000 0.0307(5) . . C1 C Uani 0.4396(3) 0.5593(2) 0.25118(18) 1.000 0.0290(6) . . C2 C Uani 0.6367(3) 0.3071(3) 0.2718(2) 1.000 0.0378(7) . . C3 C Uani 0.7050(3) 0.3865(3) 0.2000(2) 1.000 0.0376(7) . . C4 C Uani 0.3536(3) 0.3675(3) 0.38516(19) 1.000 0.0342(7) . . C5 C Uani 0.4370(4) 0.1922(3) 0.4246(3) 1.000 0.0506(9) . . C6 C Uani 0.2067(3) 0.3973(3) 0.3156(2) 1.000 0.0412(8) . . C7 C Uani 0.3005(3) 0.4656(3) 0.4987(2) 1.000 0.0418(8) . . C8 C Uani 0.6141(3) 0.6707(3) 0.11252(19) 1.000 0.0348(7) . . C9 C Uani 0.4925(3) 0.7392(3) 0.0152(2) 1.000 0.0442(8) . . C10 C Uani 0.5959(3) 0.7962(3) 0.1986(2) 1.000 0.0420(8) . . C11 C Uani 0.7889(3) 0.6015(4) 0.0491(3) 1.000 0.0478(9) . . C12 C Uani 0.0214(4) 0.8369(4) 0.1237(3) 1.000 0.0546(10) . . C13 C Uani 0.1384(4) 1.0337(3) 0.2517(3) 1.000 0.0531(9) . . C14 C Uani -0.0233(4) 0.8463(4) 0.3959(3) 1.000 0.0580(10) . . H21 H Uiso 0.685(3) 0.197(4) 0.296(2) 1.000 0.053(7) . . H31 H Uiso 0.814(4) 0.351(3) 0.164(3) 1.000 0.056(8) . . H51 H Uiso 0.475(4) 0.127(4) 0.353(3) 1.000 0.058(8) . . H52 H Uiso 0.357(3) 0.164(3) 0.476(2) 1.000 0.044(7) . . H53 H Uiso 0.530(4) 0.174(4) 0.474(3) 1.000 0.063(9) . . H61 H Uiso 0.240(3) 0.335(4) 0.246(3) 1.000 0.057(8) . . H62 H Uiso 0.152(3) 0.508(3) 0.285(2) 1.000 0.045(7) . . H63 H Uiso 0.127(3) 0.370(3) 0.369(2) 1.000 0.050(7) . . H71 H Uiso 0.256(3) 0.579(4) 0.477(2) 1.000 0.049(7) . . H72 H Uiso 0.391(4) 0.438(3) 0.546(3) 1.000 0.053(8) . . H73 H Uiso 0.215(3) 0.443(3) 0.549(2) 1.000 0.043(7) . . H91 H Uiso 0.379(4) 0.783(3) 0.046(2) 1.000 0.046(7) . . H92 H Uiso 0.504(4) 0.652(4) -0.042(3) 1.000 0.067(9) . . H93 H Uiso 0.511(3) 0.821(3) -0.035(3) 1.000 0.057(8) . . H101 H Uiso 0.683(4) 0.752(3) 0.254(3) 1.000 0.053(8) . . H102 H Uiso 0.483(4) 0.841(3) 0.246(3) 1.000 0.053(8) . . H103 H Uiso 0.610(3) 0.880(4) 0.151(3) 1.000 0.058(8) . . H111 H Uiso 0.869(4) 0.556(3) 0.109(3) 1.000 0.052(8) . . H112 H Uiso 0.804(4) 0.686(4) -0.002(3) 1.000 0.059(8) . . H113 H Uiso 0.800(3) 0.517(4) -0.010(3) 1.000 0.058(8) . . H121 H Uiso -0.002(4) 0.747(4) 0.131(3) 1.000 0.073(10) . . H122 H Uiso 0.078(4) 0.846(4) 0.046(3) 1.000 0.077(10) . . H123 H Uiso -0.086(5) 0.927(5) 0.121(3) 1.000 0.088(11) . . H131 H Uiso 0.208(5) 1.025(5) 0.168(4) 1.000 0.098(12) . . H132 H Uiso 0.204(4) 1.033(4) 0.321(3) 1.000 0.065(9) . . H133 H Uiso 0.032(4) 1.122(4) 0.258(3) 1.000 0.070(9) . . H141 H Uiso -0.042(3) 0.741(4) 0.396(2) 1.000 0.054(8) . . H142 H Uiso -0.127(5) 0.952(5) 0.400(3) 1.000 0.086(11) . . H143 H Uiso 0.027(4) 0.847(4) 0.474(3) 1.000 0.086(11) . . 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 Si 0.0291(3) 0.0261(3) 0.0446(4) 0.0002(2) -0.0018(2) -0.0097(3) N1 0.0305(9) 0.0274(9) 0.0403(10) 0.0004(7) 0.0000(8) -0.0101(8) N2 0.0312(9) 0.0261(9) 0.0329(9) 0.0001(7) -0.0030(7) -0.0108(7) N3 0.0279(9) 0.0308(9) 0.0321(9) -0.0016(7) -0.0017(7) -0.0117(7) C1 0.0317(10) 0.0308(10) 0.0269(10) -0.0014(8) -0.0046(8) -0.0154(9) C2 0.0329(12) 0.0278(11) 0.0429(12) 0.0003(9) -0.0062(9) -0.0041(9) C3 0.0278(11) 0.0348(12) 0.0421(12) -0.0032(9) -0.0026(9) -0.0061(9) C4 0.0408(12) 0.0308(11) 0.0331(11) 0.0026(9) -0.0026(9) -0.0184(10) C5 0.0568(17) 0.0351(13) 0.0562(16) 0.0104(12) -0.0020(14) -0.0199(12) C6 0.0452(14) 0.0417(14) 0.0440(13) 0.0005(11) -0.0040(11) -0.0261(12) C7 0.0496(14) 0.0473(15) 0.0325(12) 0.0010(10) -0.0009(11) -0.0260(12) C8 0.0356(11) 0.0404(12) 0.0328(11) 0.0011(9) -0.0013(9) -0.0216(10) C9 0.0456(15) 0.0563(16) 0.0354(12) 0.0098(11) -0.0063(11) -0.0279(13) C10 0.0467(14) 0.0428(13) 0.0445(13) -0.0011(11) -0.0025(12) -0.0273(12) C11 0.0408(14) 0.0566(16) 0.0485(15) -0.0030(13) 0.0055(12) -0.0257(13) C12 0.0465(16) 0.0562(17) 0.0654(19) 0.0096(14) -0.0183(14) -0.0252(14) C13 0.0473(15) 0.0291(13) 0.079(2) -0.0037(12) -0.0033(15) -0.0136(12) C14 0.0441(15) 0.0455(16) 0.0674(19) -0.0014(13) 0.0141(14) -0.0092(13) #================================================================== # 10. MOLECULAR GEOMETRY #=================================================================== loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Si N1 1.6554(19) . . yes Si C12 1.871(4) . . yes Si C13 1.877(3) . . yes Si C14 1.880(4) . . yes N1 C1 1.275(3) . . yes N2 C1 1.394(2) . . yes N2 C2 1.387(3) . . yes N2 C4 1.491(3) . . yes N3 C1 1.393(3) . . yes N3 C3 1.387(3) . . yes N3 C8 1.492(3) . . yes C2 C3 1.326(4) . . no C4 C5 1.527(4) . . no C4 C6 1.527(4) . . no C4 C7 1.532(3) . . no C8 C9 1.527(4) . . no C8 C10 1.528(3) . . no C8 C11 1.528(4) . . no C2 H21 0.96(3) . . no C3 H31 0.94(4) . . no C5 H51 0.98(3) . . no C5 H52 0.98(3) . . no C5 H53 1.00(4) . . no C6 H61 0.95(3) . . no C6 H62 0.98(3) . . no C6 H63 0.99(3) . . no C7 H71 0.98(3) . . no C7 H72 0.95(4) . . no C7 H73 0.99(3) . . no C9 H91 0.96(3) . . no C9 H92 1.05(3) . . no C9 H93 0.97(3) . . no C10 H101 0.98(4) . . no C10 H102 1.02(4) . . no C10 H103 0.96(3) . . no C11 H111 0.97(4) . . no C11 H112 0.98(4) . . no C11 H113 1.04(3) . . no C12 H121 0.95(4) . . no C12 H122 0.97(4) . . no C12 H123 0.97(5) . . no C13 H131 1.05(5) . . no C13 H132 1.03(4) . . no C13 H133 0.96(4) . . no C14 H141 1.08(3) . . no C14 H142 1.02(4) . . no C14 H143 1.03(4) . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Si C12 110.96(13) . . . yes N1 Si C13 112.26(13) . . . yes N1 Si C14 112.85(13) . . . yes C12 Si C13 107.84(15) . . . yes C12 Si C14 106.34(17) . . . yes C13 Si C14 106.24(15) . . . yes Si N1 C1 169.33(18) . . . yes C1 N2 C2 109.2(2) . . . yes C1 N2 C4 125.05(19) . . . yes C2 N2 C4 125.74(19) . . . yes C1 N3 C3 109.39(18) . . . yes C1 N3 C8 125.12(18) . . . yes C3 N3 C8 125.4(2) . . . yes N1 C1 N2 127.8(2) . . . yes N1 C1 N3 127.65(19) . . . yes N2 C1 N3 104.52(17) . . . yes N2 C2 C3 108.6(2) . . . yes N3 C3 C2 108.3(2) . . . yes N2 C4 C5 109.4(2) . . . yes N2 C4 C6 109.26(18) . . . yes N2 C4 C7 109.0(2) . . . yes C5 C4 C6 108.9(2) . . . no C5 C4 C7 108.5(2) . . . no C6 C4 C7 111.8(2) . . . no N3 C8 C9 109.5(2) . . . yes N3 C8 C10 108.91(17) . . . yes N3 C8 C11 109.0(2) . . . yes C9 C8 C10 112.1(2) . . . no C9 C8 C11 108.3(2) . . . no C10 C8 C11 109.1(2) . . . no N2 C2 H21 123.1(18) . . . no C3 C2 H21 128.2(18) . . . no N3 C3 H31 122.5(17) . . . no C2 C3 H31 129.2(17) . . . no C4 C5 H51 110(2) . . . no C4 C5 H52 109.3(15) . . . no C4 C5 H53 109(2) . . . no H51 C5 H52 108(3) . . . no H51 C5 H53 112(3) . . . no H52 C5 H53 108(2) . . . no C4 C6 H61 111(2) . . . no C4 C6 H62 111.9(17) . . . no C4 C6 H63 109.5(15) . . . no H61 C6 H62 106(2) . . . no H61 C6 H63 108(2) . . . no H62 C6 H63 110(2) . . . no C4 C7 H71 111.2(14) . . . no C4 C7 H72 111.1(18) . . . no C4 C7 H73 108.5(14) . . . no H71 C7 H72 108(2) . . . no H71 C7 H73 109(2) . . . no H72 C7 H73 108(3) . . . no C8 C9 H91 114.6(15) . . . no C8 C9 H92 112(2) . . . no C8 C9 H93 110.8(18) . . . no H91 C9 H92 104(3) . . . no H91 C9 H93 108(2) . . . no H92 C9 H93 108(3) . . . no C8 C10 H101 110.3(16) . . . no C8 C10 H102 111.5(19) . . . no C8 C10 H103 108(2) . . . no H101 C10 H102 111(3) . . . no H101 C10 H103 107(3) . . . no H102 C10 H103 109(2) . . . no C8 C11 H111 110(2) . . . no C8 C11 H112 109(2) . . . no C8 C11 H113 108.7(18) . . . no H111 C11 H112 112(3) . . . no H111 C11 H113 111(2) . . . no H112 C11 H113 106(3) . . . no Si C12 H121 110(2) . . . no Si C12 H122 115(2) . . . no Si C12 H123 111(2) . . . no H121 C12 H122 113(3) . . . no H121 C12 H123 104(4) . . . no H122 C12 H123 103(3) . . . no Si C13 H131 100(2) . . . no Si C13 H132 108.7(19) . . . no Si C13 H133 112(2) . . . no H131 C13 H132 110(3) . . . no H131 C13 H133 116(3) . . . no H132 C13 H133 110(3) . . . no Si C14 H141 106.8(14) . . . no Si C14 H142 112(2) . . . no Si C14 H143 110(2) . . . no H141 C14 H142 117(3) . . . no H141 C14 H143 110(2) . . . no H142 C14 H143 101(3) . . . no # CIF-file generated for RANF 4332-173 # Compound 5 #=================================================================== data_RANF-4332-173 _database_code_depnum_ccdc_archive 'CCDC 229689' #=================================================================== _audit_creation_date 13-Jan-04 _audit_creation_method 'PLATON
option' _audit_update_record ; 13-Jan-04 Updated by the Author E.H. Textwriting by E.H. Checkcif OK 14-Jan-04 Updated by the Author E.H. 20-Jan-04 Updated by the Author E.H. ; #=================================================================== # 5. CHEMICAL DATA #=================================================================== _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety 'C16 H25 Cl2 N3 Ti' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16 H25 Cl2 N3 Ti' _chemical_formula_weight 378.16 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Ti Ti 0.2776 0.4457 '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' Cl Cl 0.1484 0.1585 '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' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #=================================================================== # 6. CRYSTAL DATA #=================================================================== _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_Hall '-P 2ac 2n' _symmetry_space_group_name_H-M 'P n m a' loop_ _symmetry_equiv_pos_as_xyz x,y,z 1/2-x,-y,1/2+z 1/2+x,1/2-y,1/2-z -x,1/2+y,-z -x,-y,-z 1/2+x,y,1/2-z 1/2-x,1/2+y,1/2+z x,1/2-y,z _cell_length_a 12.8780(2) _cell_length_b 17.5935(2) _cell_length_c 8.5676(1) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1941.15(4) _cell_formula_units_Z 4 _cell_measurement_temperature 173(1) _cell_measurement_reflns_used 2077 _cell_measurement_theta_min 2.64 _cell_measurement_theta_max 25.36 _exptl_crystal_description fragment _exptl_crystal_colour red _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.294 _exptl_crystal_density_method none _exptl_crystal_F_000 792 _exptl_absorpt_coefficient_mu 0.716 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.870 _exptl_absorpt_correction_T_max 0.945 _exptl_absorpt_process_details '(applied during the scaling procedure; Nonius, 2001b)' _exptl_special_details ; Diffractometer operator E. Herdtweck scanspeed 2 x 120 s per film repetition 1 dx 40 467 films measured in 8 data sets set 1: phi-scan with delta_phi = 2.0 set 2 to 8 omega-scans with delta_omega = 2.0 ; _publ_section_exptl_prep ; The crystal was fixed in a capillary with perfluorinated ether and transferred to the diffractometer. ; _publ_section_exptl_refinement ; Straight forward after integration with the program NPROCESS, source: Nonius (2001b). Hydrogen atoms could be located in the difference Fourier maps and refined freely. ; #=================================================================== # 7. EXPERIMENTAL DATA #=================================================================== _diffrn_ambient_temperature 173(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'NONIUS FR 591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device ' \k-geometry diffractometer ' _diffrn_measurement_device_type ' Nonius \k-CCD diffractometer' _diffrn_measurement_method ' phi- and omega-rotation ' _diffrn_detector ' CCD plate ' _diffrn_detector_area_resol_mean 18 # 9 for binned mode _diffrn_standards_decay_% 0 # number of measured reflections (redundant set) _diffrn_reflns_number 40109 _diffrn_reflns_av_R_equivalents 0.050 _diffrn_reflns_av_sigmaI/netI 0.0190 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.64 _diffrn_reflns_theta_max 25.36 _reflns_number_total 1848 _reflns_number_gt 1665 # number of observed reflections (> n sig(I)) _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Kappa-CCD Control Software (Nonius, 2001a)' _computing_cell_refinement 'DENZO (Nonius, 2001b)' _computing_data_reduction 'DENZO (Nonius, 2001b)' _computing_structure_solution 'SIR92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1998)' _computing_molecular_graphics 'PLATON (Spek, 2001)' _computing_publication_material 'PLATON (Spek, 2001)' #=================================================================== # 8. REFINEMENT DATA #=================================================================== _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 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 sigma _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(Fo^2^)+(0.0303P)^2^+1.9495P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_number_reflns 1848 _refine_ls_number_parameters 157 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0403 _refine_ls_R_factor_gt 0.0347 _refine_ls_wR_factor_ref 0.0901 _refine_ls_wR_factor_gt 0.0877 _refine_ls_goodness_of_fit_ref 1.212 _refine_ls_restrained_S_all 1.212 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.36 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.450 _refine_diff_density_min -0.278 _refine_diff_density_rms 0.053 #=================================================================== # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS #=================================================================== loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Ti Ti Uani 0.53120(4) 0.25000 -0.17713(6) 1.000 0.0225(2) . . Cl Cl Uani 0.64044(4) 0.14721(3) -0.13078(7) 1.000 0.0328(2) . . N1 N Uani 0.44773(19) 0.25000 -0.0137(3) 1.000 0.0220(8) . . N2 N Uani 0.32700(14) 0.18761(10) 0.1607(2) 1.000 0.0240(6) . . C1 C Uani 0.3723(2) 0.25000 0.0927(3) 1.000 0.0209(9) . . C2 C Uani 0.25495(18) 0.21216(14) 0.2691(3) 1.000 0.0293(7) . . C3 C Uani 0.35598(18) 0.10603(13) 0.1363(3) 1.000 0.0285(7) . . C4 C Uani 0.2832(3) 0.05691(17) 0.2335(5) 1.000 0.0539(13) . . C5 C Uani 0.4669(2) 0.09464(16) 0.1924(3) 1.000 0.0375(9) . . C6 C Uani 0.3449(2) 0.08519(16) -0.0351(3) 1.000 0.0386(9) . . C7 C Uani 0.3905(4) 0.25000 -0.3495(5) 1.000 0.0633(19) . . C8 C Uani 0.4470(3) 0.1871(2) -0.3831(4) 1.000 0.0625(15) . . C9 C Uani 0.5414(3) 0.2110(2) -0.4468(3) 1.000 0.0613(13) . . H21 H Uiso 0.216(2) 0.1799(15) 0.327(3) 1.000 0.032(7) . . H41 H Uiso 0.293(3) 0.0694(19) 0.348(4) 1.000 0.061(10) . . H42 H Uiso 0.212(3) 0.0619(18) 0.200(4) 1.000 0.057(10) . . H43 H Uiso 0.301(2) 0.009(2) 0.218(4) 1.000 0.053(9) . . H51 H Uiso 0.471(2) 0.1063(18) 0.301(4) 1.000 0.054(9) . . H52 H Uiso 0.488(2) 0.0438(19) 0.184(3) 1.000 0.053(9) . . H53 H Uiso 0.515(2) 0.1280(18) 0.134(3) 1.000 0.045(8) . . H61 H Uiso 0.393(2) 0.1105(17) -0.100(3) 1.000 0.043(8) . . H62 H Uiso 0.355(2) 0.0309(18) -0.047(4) 1.000 0.050(8) . . H63 H Uiso 0.276(3) 0.0975(19) -0.071(4) 1.000 0.067(10) . . H71 H Uiso 0.309(5) 0.25000 -0.305(7) 1.000 0.10(2) . . H81 H Uiso 0.431(3) 0.133(2) -0.367(4) 1.000 0.080(12) . . H91 H Uiso 0.594(3) 0.181(2) -0.470(5) 1.000 0.088(13) . . 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 0.0175(3) 0.0325(3) 0.0175(3) 0.0000 0.0015(2) 0.0000 Cl 0.0284(3) 0.0336(3) 0.0365(3) -0.0056(3) 0.0023(2) 0.0073(2) N1 0.0216(13) 0.0225(13) 0.0220(13) 0.0000 0.0035(11) 0.0000 N2 0.0261(10) 0.0204(9) 0.0256(10) -0.0010(8) 0.0073(8) -0.0013(8) C1 0.0220(15) 0.0222(15) 0.0186(15) 0.0000 0.0011(12) 0.0000 C2 0.0296(12) 0.0292(12) 0.0292(12) 0.0021(10) 0.0109(10) -0.0024(10) C3 0.0323(13) 0.0176(11) 0.0355(13) -0.0016(10) 0.0077(10) -0.0004(10) C4 0.062(2) 0.0218(15) 0.078(3) 0.0008(15) 0.034(2) -0.0046(14) C5 0.0462(16) 0.0301(15) 0.0362(15) 0.0006(12) -0.0028(13) 0.0082(13) C6 0.0422(16) 0.0302(15) 0.0435(16) -0.0125(12) -0.0030(13) -0.0041(12) C7 0.033(2) 0.126(5) 0.031(2) 0.0000 -0.0088(18) 0.0000 C8 0.082(3) 0.077(3) 0.0285(15) -0.0069(16) -0.0198(17) -0.026(2) C9 0.0557(19) 0.107(3) 0.0212(13) -0.0197(15) -0.0048(13) 0.0243(18) #================================================================== # 10. MOLECULAR GEOMETRY #=================================================================== loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti Cl 2.3253(6) . . yes Ti N1 1.765(3) . . yes Ti C7 2.338(5) . . yes Ti C8 2.348(4) . . yes Ti C9 2.414(3) . . yes N1 C1 1.332(4) . . yes N2 C1 1.373(2) . . yes N2 C2 1.382(3) . . yes N2 C3 1.498(3) . . yes C2 C2 1.331(3) . 8_555 no C3 C4 1.523(4) . . no C3 C5 1.520(3) . . no C3 C6 1.520(4) . . no C7 C8 1.355(5) . . no C8 C9 1.397(5) . . no C9 C9 1.372(5) . 8_555 no C2 H21 0.91(3) . . no C4 H41 1.01(3) . . no C4 H42 0.96(4) . . no C4 H43 0.88(3) . . no C5 H51 0.95(3) . . no C5 H52 0.94(3) . . no C5 H53 0.99(3) . . no C6 H61 0.94(3) . . no C6 H62 0.97(3) . . no C6 H63 0.96(4) . . no C7 H71 1.12(6) . . no C8 H81 0.98(4) . . no C9 H91 0.88(4) . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl Ti N1 103.47(5) . . . yes Cl Ti C7 125.23(4) . . . yes Cl Ti C8 92.36(9) . . . yes Cl Ti C9 84.81(9) . . . yes Cl Ti Cl 102.10(3) . . 8_555 yes Cl Ti C8 140.73(9) . . 8_555 yes Cl Ti C9 110.59(9) . . 8_555 yes N1 Ti C7 91.67(14) . . . yes N1 Ti C8 108.35(12) . . . yes N1 Ti C9 142.41(12) . . . yes Cl Ti N1 103.47(5) 8_555 . . yes N1 Ti C8 108.35(12) . . 8_555 yes N1 Ti C9 142.41(12) . . 8_555 yes C7 Ti C8 33.62(11) . . . yes C7 Ti C9 55.77(14) . . . yes Cl Ti C7 125.23(4) 8_555 . . yes C7 Ti C8 33.62(11) . . 8_555 yes C7 Ti C9 55.77(14) . . 8_555 yes C8 Ti C9 34.09(13) . . . yes Cl Ti C8 140.73(9) 8_555 . . yes C8 Ti C8 56.23(12) . . 8_555 yes C8 Ti C9 55.93(12) . . 8_555 yes Cl Ti C9 110.59(9) 8_555 . . yes C8 Ti C9 55.93(12) 8_555 . . yes C9 Ti C9 33.03(12) . . 8_555 yes Cl Ti C8 92.36(9) 8_555 . 8_555 yes Cl Ti C9 84.81(9) 8_555 . 8_555 yes C8 Ti C9 34.09(13) 8_555 . 8_555 yes Ti N1 C1 170.7(2) . . . yes C1 N2 C2 108.70(18) . . . yes C1 N2 C3 126.95(18) . . . yes C2 N2 C3 124.10(19) . . . yes N1 C1 N2 126.89(11) . . . yes N1 C1 N2 126.89(11) . . 8_555 yes N2 C1 N2 106.2(2) . . 8_555 yes N2 C2 C2 108.2(2) . . 8_555 yes N2 C3 C4 108.3(2) . . . yes N2 C3 C5 108.44(19) . . . yes N2 C3 C6 110.0(2) . . . yes C4 C3 C5 109.3(2) . . . no C4 C3 C6 109.5(2) . . . no C5 C3 C6 111.2(2) . . . no Ti C7 C8 73.6(3) . . . yes Ti C7 C8 73.6(3) . . 8_555 yes C8 C7 C8 109.5(4) . . 8_555 no Ti C8 C7 72.8(2) . . . yes Ti C8 C9 75.52(19) . . . yes C7 C8 C9 107.7(3) . . . no Ti C9 C8 70.39(18) . . . yes Ti C9 C9 73.48(16) . . 8_555 yes C8 C9 C9 107.5(3) . . 8_555 no N2 C2 H21 123.0(17) . . . no C2 C2 H21 128.8(17) 8_555 . . no C3 C4 H41 109(2) . . . no C3 C4 H42 112(2) . . . no C3 C4 H43 107(2) . . . no H41 C4 H42 113(3) . . . no H41 C4 H43 109(3) . . . no H42 C4 H43 107(3) . . . no C3 C5 H51 109.4(16) . . . no C3 C5 H52 111.9(16) . . . no C3 C5 H53 110.5(15) . . . no H51 C5 H52 105(2) . . . no H51 C5 H53 109(2) . . . no H52 C5 H53 110(2) . . . no C3 C6 H61 113.2(16) . . . no C3 C6 H62 109(2) . . . no C3 C6 H63 110(2) . . . no H61 C6 H62 108(2) . . . no H61 C6 H63 108(3) . . . no H62 C6 H63 108(3) . . . no Ti C7 H71 121(3) . . . no C8 C7 H71 125.2(2) . . . no C8 C7 H71 125.2(2) 8_555 . . no Ti C8 H81 117(2) . . . no C7 C8 H81 130(2) . . . no C9 C8 H81 122(2) . . . no Ti C9 H91 115(3) . . . no C8 C9 H91 125(2) . . . no C9 C9 H91 127(2) 8_555 . . no # End of Crystallographic Information File