Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 186 _publ_requested_journal ' Dalton Transactions' loop_ _publ_author_name 'Hamura, Satoshi' 'Nagashima, Hideo' 'Oda, Takashi' 'Shimizu, Yasuaki' _publ_contact_author 'Hideo Nagashima' _publ_contact_author_address ; Hideo Nagashima Institute of Advanced Material Study Kyushu University, Kasuga, Hukuoka 816-8580, Japan ; _publ_contact_author_email ' nagasima@cm.kyushu-u.ac.jp ' data_1 _database_code_CSD 160977 #--------------------------------------------------------------------- #-------- _audit_creation_date 'Mar 2 19:49 1999' _audit_creation_method 'SHELXL-97' _audit_update_record ? #--------------------------------------------------------------------- #-------- _computing_data_collection 'CAD-4 softwere (Enraf-Nonius 1989)' _computing_cell_refinement 'CAD-4 softwere (Enraf-Nonius 1989)' _computing_data_reduction 'MoLEN' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' #--------------------------------------------------------------------- #-------- _chemical_compound_source ? _chemical_name_common ? _chemical_formula_weight 560.62 _chemical_formula_analytical ? _chemical_formula_sum 'C24 H40 N4 O4 S2 Ti' _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_melting_point ? #--------------------------------------------------------------------- #-------- _cell_length_a 8.708(3) _cell_length_b 16.383(4) _cell_length_c 19.432(5) _cell_angle_alpha 90 _cell_angle_beta 90.53(4) _cell_angle_gamma 90 _cell_volume 2772.1(14) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 12 _cell_measurement_theta_max 18 #--------------------------------------------------------------------- #-------- _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_Int_Tables_number 14 _symmetry_space_group_name_Hall ? 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' _exptl_crystal_description 'Block' _exptl_crystal_colour 'Red' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_diffrn 1.343 _exptl_crystal_density_meas '?' _exptl_absorpt_coefficient_mu 0.495 _exptl_absorpt_correction_type ? _exptl_special_details ; ? ; #--------------------------------------------------------------------- _diffrn_special_details ; ? ; _diffrn_ambient_temperature 296(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector '?' _diffrn_measurement_device_type '4-circle diffractometer' _diffrn_measurement_method 'scintillation counter' _diffrn_standards_number 3 _diffrn_standards_interval_count 200 _diffrn_standards_decay_% 0 _diffrn_reflns_number 13536 _reflns_number_observed 13280 _reflns_number_total 6351 _reflns_observed_criterion >2sigma(I) _diffrn_reflns_av_R_equivalents 0.2618 _diffrn_reflns_av_sigmaI/netI 0.3241 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.84 _diffrn_reflns_theta_max 27.51 #--------------------------------------------------------------------- #-------- loop_ _atom_type_symbol _atom_type_oxidation_number _atom_type_number_in_cell _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' .0033 .0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' .0000 .0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' .0061 .0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' .0106 .0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' .1246 .1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ti' 'Ti' .2776 .4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #--------------------------------------------------------------------- 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 0.94274(12) 0.11314(6) 0.74356(5) 0.0221(3) Uani 1 1 d . . . S1 S 0.92381(16) 0.23480(9) 0.64191(7) 0.0226(3) Uani 1 1 d . . . S2 S 0.68686(16) 0.14252(9) 0.82979(7) 0.0234(3) Uani 1 1 d . . . O2 O 0.9290(4) 0.2452(2) 0.71745(17) 0.0220(9) Uani 1 1 d . . . O1 O 1.0432(4) 0.2759(2) 0.60436(18) 0.0267(10) Uani 1 1 d . . . N2 N 1.1566(5) 0.1176(3) 0.7586(2) 0.0273(12) Uani 1 1 d . . . N4 N 0.8670(5) 0.1427(3) 0.8397(2) 0.0214(11) Uani 1 1 d . . . O3 O 0.6769(4) 0.1262(2) 0.75547(17) 0.0254(9) Uani 1 1 d . . . N3 N 0.9191(5) 0.1393(3) 0.6380(2) 0.0219(11) Uani 1 1 d . . . O4 O 0.6047(4) 0.0884(2) 0.87383(19) 0.0327(10) Uani 1 1 d . . . C11 C 0.7499(6) 0.2809(3) 0.6139(3) 0.0212(13) Uani 1 1 d . . . N1 N 0.9280(6) -0.0025(3) 0.7395(2) 0.0293(12) Uani 1 1 d . . . C8 C 0.9306(6) 0.1571(4) 0.9100(3) 0.0251(14) Uani 1 1 d . . . H8 H 0.8489 0.1806 0.9381 0.030 Uiso 1 1 calc . . . C16 C 0.6137(7) 0.2391(4) 0.6176(3) 0.0275(14) Uani 1 1 d . . . H16 H 0.6111 0.1859 0.6342 0.033 Uiso 1 1 calc . . . C14 C 0.4809(6) 0.3561(4) 0.5723(3) 0.0251(13) Uani 1 1 d . . . C15 C 0.4793(6) 0.2778(4) 0.5960(3) 0.0292(15) Uani 1 1 d . . . H15 H 0.3866 0.2497 0.5977 0.035 Uiso 1 1 calc . . . C18 C 0.6099(6) 0.2405(4) 0.8459(3) 0.0243(13) Uani 1 1 d . . . C10 C 1.0605(7) 0.2187(4) 0.9063(3) 0.0387(17) Uani 1 1 d . . . H10A H 1.0234 0.2683 0.8858 0.058 Uiso 1 1 calc . . . H10B H 1.1421 0.1969 0.8790 0.058 Uiso 1 1 calc . . . H10C H 1.0983 0.2299 0.9519 0.058 Uiso 1 1 calc . . . C17 C 0.3376(7) 0.3975(4) 0.5460(3) 0.0382(17) Uani 1 1 d . . . H17A H 0.3620 0.4521 0.5318 0.057 Uiso 1 1 calc . . . H17B H 0.2627 0.3993 0.5819 0.057 Uiso 1 1 calc . . . H17C H 0.2969 0.3676 0.5075 0.057 Uiso 1 1 calc . . . C5 C 0.9532(7) 0.0955(4) 0.5728(3) 0.0317(15) Uani 1 1 d . . . H5 H 0.9292 0.0378 0.5804 0.038 Uiso 1 1 calc . . . C21 C 0.4893(7) 0.3942(4) 0.8738(3) 0.0360(16) Uani 1 1 d . . . C13 C 0.6212(7) 0.3966(4) 0.5707(3) 0.0360(16) Uani 1 1 d . . . H13 H 0.6247 0.4501 0.5548 0.043 Uiso 1 1 calc . . . C12 C 0.7537(7) 0.3597(4) 0.5920(3) 0.0307(15) Uani 1 1 d . . . H12 H 0.8461 0.3882 0.5916 0.037 Uiso 1 1 calc . . . C19 C 0.6201(7) 0.3019(4) 0.7976(3) 0.0345(16) Uani 1 1 d . . . H19 H 0.6674 0.2919 0.7557 0.041 Uiso 1 1 calc . . . C20 C 0.5604(7) 0.3777(4) 0.8114(3) 0.0388(17) Uani 1 1 d . . . H20 H 0.5676 0.4188 0.7785 0.047 Uiso 1 1 calc . . . C2 C 0.8205(8) -0.0543(4) 0.7767(4) 0.0480(19) Uani 1 1 d . . . H2A H 0.7561 -0.0210 0.8050 0.072 Uiso 1 1 calc . . . H2B H 0.8767 -0.0920 0.8051 0.072 Uiso 1 1 calc . . . H2C H 0.7580 -0.0840 0.7444 0.072 Uiso 1 1 calc . . . C9 C 0.9788(7) 0.0775(4) 0.9423(3) 0.0397(17) Uani 1 1 d . . . H9A H 0.8928 0.0408 0.9430 0.060 Uiso 1 1 calc . . . H9B H 1.0142 0.0872 0.9885 0.060 Uiso 1 1 calc . . . H9C H 1.0601 0.0537 0.9160 0.060 Uiso 1 1 calc . . . C7 C 0.8547(8) 0.1239(4) 0.5123(3) 0.0405(17) Uani 1 1 d . . . H7A H 0.7482 0.1200 0.5241 0.061 Uiso 1 1 calc . . . H7B H 0.8746 0.0901 0.4730 0.061 Uiso 1 1 calc . . . H7C H 0.8792 0.1796 0.5016 0.061 Uiso 1 1 calc . . . C4 C 1.2499(8) 0.0554(5) 0.7918(4) 0.0493(19) Uani 1 1 d . . . H4A H 1.1873 0.0088 0.8020 0.074 Uiso 1 1 calc . . . H4B H 1.2930 0.0769 0.8337 0.074 Uiso 1 1 calc . . . H4C H 1.3312 0.0394 0.7616 0.074 Uiso 1 1 calc . . . C23 C 0.5391(7) 0.2560(4) 0.9069(3) 0.0372(17) Uani 1 1 d . . . H23 H 0.5305 0.2149 0.9396 0.045 Uiso 1 1 calc . . . C22 C 0.4802(8) 0.3324(4) 0.9200(3) 0.0429(18) Uani 1 1 d . . . H22 H 0.4327 0.3419 0.9619 0.052 Uiso 1 1 calc . . . C6 C 1.1237(7) 0.1002(4) 0.5541(3) 0.0410(17) Uani 1 1 d . . . H6A H 1.1850 0.0823 0.5925 0.061 Uiso 1 1 calc . . . H6B H 1.1499 0.1555 0.5428 0.061 Uiso 1 1 calc . . . H6C H 1.1430 0.0656 0.5152 0.061 Uiso 1 1 calc . . . C3 C 1.2559(7) 0.1877(4) 0.7431(3) 0.0450(18) Uani 1 1 d . . . H3A H 1.1962 0.2297 0.7213 0.068 Uiso 1 1 calc . . . H3B H 1.3365 0.1707 0.7129 0.068 Uiso 1 1 calc . . . H3C H 1.2999 0.2083 0.7851 0.068 Uiso 1 1 calc . . . C1 C 1.0246(8) -0.0532(4) 0.6964(3) 0.0455(18) Uani 1 1 d . . . H1A H 1.0959 -0.0193 0.6721 0.068 Uiso 1 1 calc . . . H1B H 0.9616 -0.0824 0.6639 0.068 Uiso 1 1 calc . . . H1C H 1.0801 -0.0913 0.7246 0.068 Uiso 1 1 calc . . . C24 C 0.4268(8) 0.4789(5) 0.8875(4) 0.056(2) Uani 1 1 d . . . H24A H 0.4439 0.5129 0.8482 0.084 Uiso 1 1 calc . . . H24B H 0.4782 0.5018 0.9269 0.084 Uiso 1 1 calc . . . H24C H 0.3186 0.4755 0.8962 0.084 Uiso 1 1 calc . . . 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 0.0163(5) 0.0230(6) 0.0270(6) 0.0010(5) -0.0017(4) 0.0021(5) S1 0.0175(7) 0.0231(8) 0.0271(8) 0.0011(6) -0.0015(6) -0.0009(7) S2 0.0158(7) 0.0267(8) 0.0277(8) 0.0040(7) -0.0023(6) 0.0001(7) O2 0.018(2) 0.030(2) 0.019(2) 0.0005(17) -0.0024(16) -0.0010(18) O1 0.018(2) 0.030(2) 0.031(2) 0.0083(18) 0.0035(17) -0.0033(19) N2 0.014(2) 0.031(3) 0.038(3) 0.004(2) -0.003(2) 0.004(2) N4 0.008(2) 0.025(3) 0.031(3) 0.004(2) -0.0030(19) 0.002(2) O3 0.022(2) 0.030(3) 0.024(2) 0.0003(18) -0.0080(17) 0.0005(19) N3 0.017(2) 0.022(3) 0.026(3) -0.006(2) 0.001(2) -0.001(2) O4 0.023(2) 0.038(3) 0.037(2) 0.011(2) 0.0041(19) -0.001(2) C11 0.017(3) 0.028(4) 0.019(3) 0.005(2) -0.004(2) 0.001(3) N1 0.031(3) 0.026(3) 0.031(3) 0.003(2) -0.004(2) 0.006(2) C8 0.020(3) 0.036(4) 0.019(3) 0.003(3) -0.001(2) 0.003(3) C16 0.023(3) 0.026(4) 0.034(3) 0.007(3) 0.003(3) -0.007(3) C14 0.024(3) 0.025(3) 0.027(3) 0.002(3) 0.002(3) 0.006(3) C15 0.019(3) 0.033(4) 0.035(4) 0.006(3) -0.003(3) -0.003(3) C18 0.010(3) 0.030(4) 0.032(3) -0.005(3) -0.004(2) 0.001(3) C10 0.032(4) 0.035(4) 0.049(4) -0.011(3) -0.007(3) -0.009(3) C17 0.025(3) 0.041(4) 0.049(4) 0.005(3) -0.008(3) 0.013(3) C5 0.037(4) 0.025(4) 0.033(4) -0.005(3) 0.007(3) -0.002(3) C21 0.019(3) 0.034(4) 0.055(4) -0.008(4) 0.002(3) 0.004(3) C13 0.031(4) 0.026(4) 0.051(4) 0.013(3) -0.005(3) -0.001(3) C12 0.023(3) 0.022(3) 0.047(4) 0.006(3) -0.002(3) -0.012(3) C19 0.027(4) 0.030(4) 0.047(4) 0.007(3) 0.019(3) 0.003(3) C20 0.036(4) 0.027(4) 0.054(4) 0.011(3) 0.015(3) 0.005(3) C2 0.053(5) 0.031(4) 0.059(5) 0.007(4) 0.006(4) 0.004(4) C9 0.039(4) 0.048(4) 0.032(4) 0.012(3) -0.015(3) -0.003(4) C7 0.046(4) 0.042(4) 0.034(4) -0.007(3) -0.002(3) -0.008(4) C4 0.030(4) 0.053(5) 0.065(5) 0.002(4) -0.005(4) 0.012(4) C23 0.036(4) 0.048(5) 0.028(3) 0.005(3) 0.006(3) 0.010(3) C22 0.047(4) 0.050(5) 0.032(4) -0.005(3) 0.008(3) 0.020(4) C6 0.029(4) 0.046(5) 0.048(4) -0.006(3) 0.015(3) -0.003(3) C3 0.020(3) 0.057(5) 0.058(5) 0.012(4) 0.000(3) -0.008(4) C1 0.051(5) 0.041(4) 0.045(4) -0.007(4) 0.000(4) 0.008(4) C24 0.048(5) 0.044(5) 0.075(5) -0.007(4) 0.001(4) 0.012(4) #--------------------------------------------------------------------- #-------- _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 'w=1/[\s^2^(Fo^2^)+(0.0561P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 6351 _refine_ls_number_parameters 316 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all 0.2641 _refine_ls_R_factor_obs 0.0585 _refine_ls_wR_factor_all 0.1763 _refine_ls_wR_factor_obs 0.1180 _refine_ls_goodness_of_fit_all 0.953 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_mean 0.000 _refine_diff_density_min -0.675 _refine_diff_density_max 0.495 #--------------------------------------------------------------------- #-------- _geom_special_details ; ? ; 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 Ti1 N2 1.883(5) . ? Ti1 N1 1.900(5) . ? Ti1 N4 2.045(4) . ? Ti1 N3 2.104(4) . ? Ti1 O2 2.226(4) . ? Ti1 O3 2.338(4) . ? Ti1 S1 2.8100(18) . ? Ti1 S2 2.841(2) . ? S1 O1 1.443(4) . ? S1 O2 1.478(4) . ? S1 N3 1.566(5) . ? S1 C11 1.773(5) . ? S2 O4 1.429(4) . ? S2 O3 1.470(4) . ? S2 N4 1.579(4) . ? S2 C18 1.769(6) . ? N2 C4 1.450(8) . ? N2 C3 1.470(8) . ? N4 C8 1.488(6) . ? N3 C5 1.490(7) . ? C11 C12 1.360(7) . ? C11 C16 1.372(7) . ? N1 C1 1.454(7) . ? N1 C2 1.460(8) . ? C8 C9 1.505(8) . ? C8 C10 1.519(8) . ? C16 C15 1.392(8) . ? C14 C15 1.362(8) . ? C14 C13 1.391(8) . ? C14 C17 1.506(8) . ? C18 C23 1.365(7) . ? C18 C19 1.379(8) . ? C5 C7 1.522(8) . ? C5 C6 1.534(8) . ? C21 C22 1.356(9) . ? C21 C20 1.393(8) . ? C21 C24 1.515(9) . ? C13 C12 1.364(8) . ? C19 C20 1.375(8) . ? C23 C22 1.377(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 N2 Ti1 N1 96.4(2) . . ? N2 Ti1 N4 100.14(19) . . ? N1 Ti1 N4 104.6(2) . . ? N2 Ti1 N3 103.35(19) . . ? N1 Ti1 N3 99.03(19) . . ? N4 Ti1 N3 144.38(18) . . ? N2 Ti1 O2 92.80(18) . . ? N1 Ti1 O2 163.01(17) . . ? N4 Ti1 O2 87.77(16) . . ? N3 Ti1 O2 64.84(15) . . ? N2 Ti1 O3 163.59(17) . . ? N1 Ti1 O3 91.67(19) . . ? N4 Ti1 O3 63.89(15) . . ? N3 Ti1 O3 89.40(15) . . ? O2 Ti1 O3 83.23(13) . . ? N2 Ti1 S1 97.65(15) . . ? N1 Ti1 S1 132.41(15) . . ? N4 Ti1 S1 117.20(14) . . ? N3 Ti1 S1 33.42(12) . . ? O2 Ti1 S1 31.51(9) . . ? O3 Ti1 S1 87.29(10) . . ? N2 Ti1 S2 132.97(15) . . ? N1 Ti1 S2 98.07(16) . . ? N4 Ti1 S2 32.85(12) . . ? N3 Ti1 S2 118.04(13) . . ? O2 Ti1 S2 85.92(10) . . ? O3 Ti1 S2 31.09(9) . . ? S1 Ti1 S2 104.66(6) . . ? O1 S1 O2 115.6(2) . . ? O1 S1 N3 117.4(2) . . ? O2 S1 N3 99.4(2) . . ? O1 S1 C11 105.3(2) . . ? O2 S1 C11 105.9(2) . . ? N3 S1 C11 112.8(3) . . ? O1 S1 Ti1 130.45(16) . . ? O2 S1 Ti1 51.90(15) . . ? N3 S1 Ti1 47.71(16) . . ? C11 S1 Ti1 124.19(19) . . ? O4 S2 O3 116.8(2) . . ? O4 S2 N4 115.5(2) . . ? O3 S2 N4 99.7(2) . . ? O4 S2 C18 105.3(3) . . ? O3 S2 C18 108.6(2) . . ? N4 S2 C18 110.8(3) . . ? O4 S2 Ti1 130.37(18) . . ? O3 S2 Ti1 55.21(15) . . ? N4 S2 Ti1 44.62(16) . . ? C18 S2 Ti1 124.0(2) . . ? S1 O2 Ti1 96.60(19) . . ? C4 N2 C3 108.1(5) . . ? C4 N2 Ti1 126.2(4) . . ? C3 N2 Ti1 125.5(4) . . ? C8 N4 S2 118.2(3) . . ? C8 N4 Ti1 139.1(3) . . ? S2 N4 Ti1 102.5(2) . . ? S2 O3 Ti1 93.70(18) . . ? C5 N3 S1 121.2(4) . . ? C5 N3 Ti1 135.5(4) . . ? S1 N3 Ti1 98.9(2) . . ? C12 C11 C16 120.9(5) . . ? C12 C11 S1 118.5(4) . . ? C16 C11 S1 120.6(4) . . ? C1 N1 C2 109.3(5) . . ? C1 N1 Ti1 123.7(4) . . ? C2 N1 Ti1 127.1(4) . . ? N4 C8 C9 110.2(5) . . ? N4 C8 C10 109.5(4) . . ? C9 C8 C10 112.9(5) . . ? C11 C16 C15 118.8(5) . . ? C15 C14 C13 117.9(5) . . ? C15 C14 C17 121.9(5) . . ? C13 C14 C17 120.1(5) . . ? C14 C15 C16 121.3(5) . . ? C23 C18 C19 119.2(6) . . ? C23 C18 S2 119.9(5) . . ? C19 C18 S2 121.0(5) . . ? N3 C5 C7 113.2(5) . . ? N3 C5 C6 112.2(5) . . ? C7 C5 C6 110.0(5) . . ? C22 C21 C20 117.5(6) . . ? C22 C21 C24 123.0(6) . . ? C20 C21 C24 119.6(6) . . ? C12 C13 C14 121.5(5) . . ? C11 C12 C13 119.5(5) . . ? C20 C19 C18 120.0(6) . . ? C19 C20 C21 121.1(6) . . ? C18 C23 C22 120.2(6) . . ? C21 C22 C23 122.1(6) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N2 Ti1 S1 O1 10.3(3) . . . . ? N1 Ti1 S1 O1 -95.7(3) . . . . ? N4 Ti1 S1 O1 115.8(3) . . . . ? N3 Ti1 S1 O1 -92.4(3) . . . . ? O2 Ti1 S1 O1 93.1(3) . . . . ? O3 Ti1 S1 O1 174.5(2) . . . . ? S2 Ti1 S1 O1 148.5(2) . . . . ? N2 Ti1 S1 O2 -82.8(2) . . . . ? N1 Ti1 S1 O2 171.2(3) . . . . ? N4 Ti1 S1 O2 22.8(2) . . . . ? N3 Ti1 S1 O2 174.5(3) . . . . ? O3 Ti1 S1 O2 81.4(2) . . . . ? S2 Ti1 S1 O2 55.42(19) . . . . ? N2 Ti1 S1 N3 102.7(3) . . . . ? N1 Ti1 S1 N3 -3.3(3) . . . . ? N4 Ti1 S1 N3 -151.7(3) . . . . ? O2 Ti1 S1 N3 -174.5(3) . . . . ? O3 Ti1 S1 N3 -93.0(2) . . . . ? S2 Ti1 S1 N3 -119.1(2) . . . . ? N2 Ti1 S1 C11 -166.4(3) . . . . ? N1 Ti1 S1 C11 87.7(3) . . . . ? N4 Ti1 S1 C11 -60.8(3) . . . . ? N3 Ti1 S1 C11 90.9(3) . . . . ? O2 Ti1 S1 C11 -83.6(3) . . . . ? O3 Ti1 S1 C11 -2.1(2) . . . . ? S2 Ti1 S1 C11 -28.1(2) . . . . ? N2 Ti1 S2 O4 -88.9(3) . . . . ? N1 Ti1 S2 O4 17.7(3) . . . . ? N4 Ti1 S2 O4 -86.7(3) . . . . ? N3 Ti1 S2 O4 122.5(3) . . . . ? O2 Ti1 S2 O4 -178.9(2) . . . . ? O3 Ti1 S2 O4 97.4(3) . . . . ? S1 Ti1 S2 O4 155.5(2) . . . . ? N2 Ti1 S2 O3 173.7(3) . . . . ? N1 Ti1 S2 O3 -79.7(2) . . . . ? N4 Ti1 S2 O3 175.9(3) . . . . ? N3 Ti1 S2 O3 25.0(2) . . . . ? O2 Ti1 S2 O3 83.6(2) . . . . ? S1 Ti1 S2 O3 58.09(19) . . . . ? N2 Ti1 S2 N4 -2.2(3) . . . . ? N1 Ti1 S2 N4 104.4(3) . . . . ? N3 Ti1 S2 N4 -150.8(3) . . . . ? O2 Ti1 S2 N4 -92.2(3) . . . . ? O3 Ti1 S2 N4 -175.9(3) . . . . ? S1 Ti1 S2 N4 -117.8(3) . . . . ? N2 Ti1 S2 C18 83.6(3) . . . . ? N1 Ti1 S2 C18 -169.8(3) . . . . ? N4 Ti1 S2 C18 85.8(3) . . . . ? N3 Ti1 S2 C18 -65.0(3) . . . . ? O2 Ti1 S2 C18 -6.4(2) . . . . ? O3 Ti1 S2 C18 -90.1(3) . . . . ? S1 Ti1 S2 C18 -32.0(2) . . . . ? O1 S1 O2 Ti1 -122.6(2) . . . . ? N3 S1 O2 Ti1 4.1(2) . . . . ? C11 S1 O2 Ti1 121.3(2) . . . . ? N2 Ti1 O2 S1 100.1(2) . . . . ? N1 Ti1 O2 S1 -22.7(7) . . . . ? N4 Ti1 O2 S1 -159.9(2) . . . . ? N3 Ti1 O2 S1 -3.35(18) . . . . ? O3 Ti1 O2 S1 -95.89(19) . . . . ? S2 Ti1 O2 S1 -127.01(17) . . . . ? N1 Ti1 N2 C4 -27.7(5) . . . . ? N4 Ti1 N2 C4 78.4(5) . . . . ? N3 Ti1 N2 C4 -128.6(5) . . . . ? O2 Ti1 N2 C4 166.6(5) . . . . ? O3 Ti1 N2 C4 91.2(8) . . . . ? S1 Ti1 N2 C4 -162.1(5) . . . . ? S2 Ti1 N2 C4 79.6(5) . . . . ? N1 Ti1 N2 C3 157.1(5) . . . . ? N4 Ti1 N2 C3 -96.8(5) . . . . ? N3 Ti1 N2 C3 56.2(5) . . . . ? O2 Ti1 N2 C3 -8.6(5) . . . . ? O3 Ti1 N2 C3 -84.0(8) . . . . ? S1 Ti1 N2 C3 22.7(5) . . . . ? S2 Ti1 N2 C3 -95.6(5) . . . . ? O4 S2 N4 C8 -53.7(5) . . . . ? O3 S2 N4 C8 -179.7(4) . . . . ? C18 S2 N4 C8 65.9(5) . . . . ? Ti1 S2 N4 C8 -176.3(5) . . . . ? O4 S2 N4 Ti1 122.6(2) . . . . ? O3 S2 N4 Ti1 -3.5(3) . . . . ? C18 S2 N4 Ti1 -117.8(3) . . . . ? N2 Ti1 N4 C8 -6.6(6) . . . . ? N1 Ti1 N4 C8 92.8(6) . . . . ? N3 Ti1 N4 C8 -137.4(5) . . . . ? O2 Ti1 N4 C8 -99.1(6) . . . . ? O3 Ti1 N4 C8 177.4(6) . . . . ? S1 Ti1 N4 C8 -110.8(5) . . . . ? S2 Ti1 N4 C8 175.0(7) . . . . ? N2 Ti1 N4 S2 178.4(2) . . . . ? N1 Ti1 N4 S2 -82.2(3) . . . . ? N3 Ti1 N4 S2 47.6(4) . . . . ? O2 Ti1 N4 S2 85.9(2) . . . . ? O3 Ti1 N4 S2 2.38(19) . . . . ? S1 Ti1 N4 S2 74.3(2) . . . . ? O4 S2 O3 Ti1 -122.2(2) . . . . ? N4 S2 O3 Ti1 3.0(2) . . . . ? C18 S2 O3 Ti1 118.9(2) . . . . ? N2 Ti1 O3 S2 -16.6(7) . . . . ? N1 Ti1 O3 S2 102.9(2) . . . . ? N4 Ti1 O3 S2 -2.5(2) . . . . ? N3 Ti1 O3 S2 -158.1(2) . . . . ? O2 Ti1 O3 S2 -93.34(18) . . . . ? S1 Ti1 O3 S2 -124.70(17) . . . . ? O1 S1 N3 C5 -38.6(5) . . . . ? O2 S1 N3 C5 -164.0(4) . . . . ? C11 S1 N3 C5 84.2(5) . . . . ? Ti1 S1 N3 C5 -159.6(5) . . . . ? O1 S1 N3 Ti1 121.1(2) . . . . ? O2 S1 N3 Ti1 -4.4(2) . . . . ? C11 S1 N3 Ti1 -116.2(2) . . . . ? N2 Ti1 N3 C5 71.3(5) . . . . ? N1 Ti1 N3 C5 -27.5(5) . . . . ? N4 Ti1 N3 C5 -158.8(5) . . . . ? O2 Ti1 N3 C5 158.1(5) . . . . ? O3 Ti1 N3 C5 -119.1(5) . . . . ? S1 Ti1 N3 C5 154.9(6) . . . . ? S2 Ti1 N3 C5 -131.8(5) . . . . ? N2 Ti1 N3 S1 -83.6(3) . . . . ? N1 Ti1 N3 S1 177.6(2) . . . . ? N4 Ti1 N3 S1 46.3(4) . . . . ? O2 Ti1 N3 S1 3.18(17) . . . . ? O3 Ti1 N3 S1 86.0(2) . . . . ? S2 Ti1 N3 S1 73.4(2) . . . . ? O1 S1 C11 C12 -28.2(5) . . . . ? O2 S1 C11 C12 94.7(5) . . . . ? N3 S1 C11 C12 -157.5(5) . . . . ? Ti1 S1 C11 C12 149.1(4) . . . . ? O1 S1 C11 C16 155.0(5) . . . . ? O2 S1 C11 C16 -82.1(5) . . . . ? N3 S1 C11 C16 25.7(5) . . . . ? Ti1 S1 C11 C16 -27.7(6) . . . . ? N2 Ti1 N1 C1 -50.4(5) . . . . ? N4 Ti1 N1 C1 -152.7(4) . . . . ? N3 Ti1 N1 C1 54.2(5) . . . . ? O2 Ti1 N1 C1 71.9(8) . . . . ? O3 Ti1 N1 C1 143.9(4) . . . . ? S1 Ti1 N1 C1 56.0(5) . . . . ? S2 Ti1 N1 C1 174.4(4) . . . . ? N2 Ti1 N1 C2 130.6(5) . . . . ? N4 Ti1 N1 C2 28.3(5) . . . . ? N3 Ti1 N1 C2 -124.7(5) . . . . ? O2 Ti1 N1 C2 -107.1(7) . . . . ? O3 Ti1 N1 C2 -35.1(5) . . . . ? S1 Ti1 N1 C2 -122.9(5) . . . . ? S2 Ti1 N1 C2 -4.5(5) . . . . ? S2 N4 C8 C9 101.1(5) . . . . ? Ti1 N4 C8 C9 -73.3(7) . . . . ? S2 N4 C8 C10 -134.1(4) . . . . ? Ti1 N4 C8 C10 51.5(7) . . . . ? C12 C11 C16 C15 2.4(9) . . . . ? S1 C11 C16 C15 179.1(4) . . . . ? C13 C14 C15 C16 -0.4(9) . . . . ? C17 C14 C15 C16 177.4(5) . . . . ? C11 C16 C15 C14 -0.8(9) . . . . ? O4 S2 C18 C23 23.2(5) . . . . ? O3 S2 C18 C23 149.0(5) . . . . ? N4 S2 C18 C23 -102.4(5) . . . . ? Ti1 S2 C18 C23 -150.9(4) . . . . ? O4 S2 C18 C19 -156.8(5) . . . . ? O3 S2 C18 C19 -30.9(5) . . . . ? N4 S2 C18 C19 77.7(5) . . . . ? Ti1 S2 C18 C19 29.2(6) . . . . ? S1 N3 C5 C7 -54.4(6) . . . . ? Ti1 N3 C5 C7 154.9(4) . . . . ? S1 N3 C5 C6 70.9(6) . . . . ? Ti1 N3 C5 C6 -79.8(7) . . . . ? C15 C14 C13 C12 0.1(9) . . . . ? C17 C14 C13 C12 -177.8(6) . . . . ? C16 C11 C12 C13 -2.7(9) . . . . ? S1 C11 C12 C13 -179.5(5) . . . . ? C14 C13 C12 C11 1.5(10) . . . . ? C23 C18 C19 C20 0.5(9) . . . . ? S2 C18 C19 C20 -179.6(5) . . . . ? C18 C19 C20 C21 0.1(10) . . . . ? C22 C21 C20 C19 -0.5(10) . . . . ? C24 C21 C20 C19 179.1(6) . . . . ? C19 C18 C23 C22 -0.7(9) . . . . ? S2 C18 C23 C22 179.4(5) . . . . ? C20 C21 C22 C23 0.3(10) . . . . ? C24 C21 C22 C23 -179.3(6) . . . . ? C18 C23 C22 C21 0.3(11) . . . . ? #===END data_2 _database_code_CSD 160978 #--------------------------------------------------------------------- #-------- _audit_creation_date 'Jun 14 17:11 2000' _audit_creation_method 'SHELXL-97' _audit_update_record ? #--------------------------------------------------------------------- #-------- _computing_data_collection 'MSC/AFC Diffractometer Control' _computing_cell_refinement 'MSC/AFC Diffractometer Control' _computing_data_reduction 'teXsan for Windows version 1.06 (MSC, 1997-1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' #--------------------------------------------------------------------- #-------- _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H34 N4 O5 S2 Ti' _chemical_formula_weight 546.55 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' 'S' 'S' 0.1246 0.1234 '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 'P 21/n ' _symmetry_Int_Tables_number 14 _symmetry_space_group_name_Hall ? loop_ _symmetry_equiv_pos_as_xyz ' +x, +y, +z' '1/2-x,1/2+y,1/2-z' ' -x, -y, -z' '1/2+x,1/2-y,1/2+z' _cell_length_a 14.0471(9) _cell_length_b 11.8424(6) _cell_length_c 15.7599(9) _cell_angle_alpha 90 _cell_angle_beta 100.603(4) _cell_angle_gamma 90 _cell_volume 2576.9(2) _cell_formula_units_Z 4 _cell_measurement_temperature 223.2 _cell_measurement_reflns_used 16604 _cell_measurement_theta_min 2.1 _cell_measurement_theta_max 27.5 _publ_section_exptl_prep ; ENTER EXPERIMENTAL SECTION ; _exptl_crystal_description 'platelet' _exptl_crystal_colour 'yellow' _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.10 _exptl_crystal_density_diffrn 1.409 _exptl_crystal_density_meas 'not measured' _chemical_formula_weight 546.55 _chemical_formula_analytical ? _chemical_formula_sum 'C22 H34 N4 O5 S2 Ti ' _chemical_formula_moiety 'C22 H34 N4 O5 S2 Ti ' _chemical_formula_structural ? _chemical_compound_source ? _exptl_crystal_F_000 1152.00 _exptl_absorpt_coefficient_mu 0.534 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_max 1.215 _exptl_absorpt_correction_T_min 0.821 _exptl_special_details ; ? ; _diffrn_ambient_temperature 223.2 _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Rigaku rotating anode' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'Imaging Plate' _diffrn_measurement_device 'Rigaku RAXIS-RAPID' _diffrn_detector_area_resol_mean ? _diffrn_measurement_method ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_decay_% 0.00 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ? _diffrn_reflns_number 6171 _reflns_number_total 5886 _reflns_number_gt 4027 _reflns_threshold_expression >2sigma(I) _diffrn_reflns_av_R_equivalents 0.04244 _diffrn_reflns_av_sigmaI/netI 0.067 _diffrn_reflns_theta_full ? _diffrn_measured_fraction_theta_max ? _diffrn_measured_fraction_theta_full ? _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.48 _diffrn_reflns_theta_max 27.48 _diffrn_reflns_reduction_process 'Lp corrections applied' _diffrn_orient_matrix_UB_11 -0.04092 _diffrn_orient_matrix_UB_12 -0.00636 _diffrn_orient_matrix_UB_13 -0.05885 _diffrn_orient_matrix_UB_21 0.05703 _diffrn_orient_matrix_UB_22 -0.02927 _diffrn_orient_matrix_UB_23 -0.02298 _diffrn_orient_matrix_UB_31 -0.01785 _diffrn_orient_matrix_UB_32 -0.07895 _diffrn_orient_matrix_UB_33 0.01326 _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^)+(0.0681P)^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 5886 _refine_ls_number_parameters 307 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0736 _refine_ls_R_factor_gt 0.0414 _refine_ls_wR_factor_ref 0.1227 _refine_ls_wR_factor_gt 0.1053 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _refine_ls_shift/su_max 0.001 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 1.08026(3) 0.25795(4) 0.59251(3) 0.02304(12) Uani 1 1 d . . . S1 S 0.86557(5) 0.12783(6) 0.57945(5) 0.03064(16) Uani 1 1 d . . . S2 S 1.32165(5) 0.28754(6) 0.65326(5) 0.03552(18) Uani 1 1 d . . . O1 O 1.08264(13) 0.24922(15) 0.45578(11) 0.0296(4) Uani 1 1 d . . . O2 O 0.90616(14) 0.08785(18) 0.66425(13) 0.0409(5) Uani 1 1 d . . . O3 O 0.81073(15) 0.04759(17) 0.52086(15) 0.0428(5) Uani 1 1 d . . . O4 O 1.29760(15) 0.2703(2) 0.73715(13) 0.0455(5) Uani 1 1 d . . . O5 O 1.37323(16) 0.38944(18) 0.64052(17) 0.0514(6) Uani 1 1 d . . . N1 N 1.04470(16) 0.40311(18) 0.61967(14) 0.0308(5) Uani 1 1 d . . . N2 N 1.10001(16) 0.18194(18) 0.69595(14) 0.0286(5) Uani 1 1 d . . . N3 N 1.22549(16) 0.27529(19) 0.58113(14) 0.0300(5) Uani 1 1 d . . . N4 N 0.94927(15) 0.18440(18) 0.53603(14) 0.0264(4) Uani 1 1 d . . . C1 C 1.1152(3) 0.4776(3) 0.6721(2) 0.0505(8) Uani 1 1 d . . . H1A H 1.1759 0.4387 0.6877 0.076 Uiso 1 1 calc R . . H1B H 1.0920 0.4987 0.7235 0.076 Uiso 1 1 calc R . . H1C H 1.1241 0.5441 0.6396 0.076 Uiso 1 1 calc R . . C2 C 0.9517(2) 0.4596(3) 0.5940(2) 0.0442(8) Uani 1 1 d . . . H2A H 0.9069 0.4093 0.5593 0.066 Uiso 1 1 calc R . . H2B H 0.9600 0.5260 0.5613 0.066 Uiso 1 1 calc R . . H2C H 0.9268 0.4805 0.6446 0.066 Uiso 1 1 calc R . . C3 C 1.1311(2) 0.0660(2) 0.6875(2) 0.0398(7) Uani 1 1 d . . . H3A H 1.1336 0.0507 0.6281 0.060 Uiso 1 1 calc R . . H3B H 1.0860 0.0155 0.7066 0.060 Uiso 1 1 calc R . . H3C H 1.1942 0.0554 0.7221 0.060 Uiso 1 1 calc R . . C4 C 1.0939(3) 0.2115(3) 0.7834(2) 0.0498(8) Uani 1 1 d . . . H4A H 1.0730 0.2886 0.7852 0.075 Uiso 1 1 calc R . . H4B H 1.1563 0.2029 0.8195 0.075 Uiso 1 1 calc R . . H4C H 1.0481 0.1629 0.8036 0.075 Uiso 1 1 calc R . . C5 C 1.2429(2) 0.3082(2) 0.49445(19) 0.0363(6) Uani 1 1 d . . . H5A H 1.2309 0.3883 0.4849 0.044 Uiso 1 1 calc R . . H5B H 1.3094 0.2924 0.4896 0.044 Uiso 1 1 calc R . . C6 C 1.1755(2) 0.2413(3) 0.43004(18) 0.0358(6) Uani 1 1 d . . . H6A H 1.1725 0.2721 0.3726 0.043 Uiso 1 1 calc R . . H6B H 1.1965 0.1633 0.4302 0.043 Uiso 1 1 calc R . . C7 C 1.0059(2) 0.1887(3) 0.40161(18) 0.0361(6) Uani 1 1 d . . . H7A H 1.0214 0.1090 0.3998 0.043 Uiso 1 1 calc R . . H7B H 0.9948 0.2184 0.3433 0.043 Uiso 1 1 calc R . . C8 C 0.9190(2) 0.2064(2) 0.44234(17) 0.0330(6) Uani 1 1 d . . . H8A H 0.8955 0.2832 0.4328 0.040 Uiso 1 1 calc R . . H8B H 0.8676 0.1550 0.4176 0.040 Uiso 1 1 calc R . . C9 C 0.78375(18) 0.2380(2) 0.59184(17) 0.0298(5) Uani 1 1 d . . . C10 C 0.7823(2) 0.2833(3) 0.67269(19) 0.0396(7) Uani 1 1 d . . . H10 H 0.8223 0.2538 0.7212 0.047 Uiso 1 1 calc R . . C11 C 0.7213(2) 0.3722(3) 0.6809(2) 0.0441(7) Uani 1 1 d . . . H11 H 0.7200 0.4014 0.7355 0.053 Uiso 1 1 calc R . . C12 C 0.6623(2) 0.4188(3) 0.6103(2) 0.0390(7) Uani 1 1 d . . . C13 C 0.6644(2) 0.3736(3) 0.5298(2) 0.0410(7) Uani 1 1 d . . . H13 H 0.6256 0.4048 0.4813 0.049 Uiso 1 1 calc R . . C14 C 0.7236(2) 0.2826(3) 0.52035(19) 0.0371(6) Uani 1 1 d . . . H14 H 0.7228 0.2516 0.4660 0.045 Uiso 1 1 calc R . . C15 C 0.5944(3) 0.5155(3) 0.6199(3) 0.0552(9) Uani 1 1 d . . . H15A H 0.5592 0.5367 0.5640 0.083 Uiso 1 1 calc R . . H15B H 0.6312 0.5789 0.6459 0.083 Uiso 1 1 calc R . . H15C H 0.5496 0.4922 0.6557 0.083 Uiso 1 1 calc R . . C16 C 1.39888(18) 0.1752(2) 0.63520(17) 0.0306(6) Uani 1 1 d . . . C17 C 1.4987(2) 0.1881(3) 0.6580(2) 0.0428(7) Uani 1 1 d . . . H17 H 1.5250 0.2571 0.6788 0.051 Uiso 1 1 calc R . . C18 C 1.5590(2) 0.0977(3) 0.6496(2) 0.0474(8) Uani 1 1 d . . . H18 H 1.6257 0.1063 0.6661 0.057 Uiso 1 1 calc R . . C19 C 1.5220(2) -0.0049(3) 0.61734(19) 0.0387(7) Uani 1 1 d . . . C20 C 1.4223(2) -0.0155(3) 0.59301(19) 0.0384(7) Uani 1 1 d . . . H20 H 1.3962 -0.0835 0.5702 0.046 Uiso 1 1 calc R . . C21 C 1.36081(19) 0.0739(2) 0.60211(18) 0.0350(6) Uani 1 1 d . . . H21 H 1.2941 0.0652 0.5859 0.042 Uiso 1 1 calc R . . C22 C 1.5873(3) -0.1024(3) 0.6075(2) 0.0573(10) Uani 1 1 d . . . H22A H 1.5489 -0.1662 0.5842 0.086 Uiso 1 1 calc R . . H22B H 1.6247 -0.1219 0.6629 0.086 Uiso 1 1 calc R . . H22C H 1.6301 -0.0816 0.5692 0.086 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 0.0273(2) 0.0186(2) 0.0222(2) -0.00091(18) 0.00209(16) 0.00014(17) S1 0.0286(3) 0.0264(3) 0.0343(4) 0.0027(3) -0.0014(3) -0.0037(3) S2 0.0293(3) 0.0381(4) 0.0380(4) -0.0113(3) 0.0033(3) -0.0063(3) O1 0.0331(9) 0.0296(9) 0.0255(9) -0.0034(8) 0.0044(7) 0.0002(8) O2 0.0356(10) 0.0442(12) 0.0403(12) 0.0162(10) 0.0002(9) -0.0019(9) O3 0.0395(11) 0.0301(10) 0.0544(13) -0.0068(10) -0.0025(10) -0.0099(9) O4 0.0347(11) 0.0680(15) 0.0321(11) -0.0150(11) 0.0016(9) -0.0030(10) O5 0.0434(12) 0.0373(12) 0.0732(16) -0.0162(12) 0.0098(11) -0.0135(10) N1 0.0401(12) 0.0210(10) 0.0309(12) -0.0019(9) 0.0055(10) 0.0024(9) N2 0.0307(11) 0.0275(11) 0.0260(11) 0.0011(9) 0.0012(9) -0.0031(9) N3 0.0293(11) 0.0306(12) 0.0301(12) -0.0006(9) 0.0060(9) -0.0028(9) N4 0.0262(10) 0.0261(11) 0.0255(11) 0.0004(9) 0.0011(8) -0.0018(9) C1 0.059(2) 0.0337(17) 0.053(2) -0.0149(15) -0.0038(16) -0.0002(15) C2 0.0433(17) 0.0278(15) 0.064(2) -0.0034(14) 0.0154(16) 0.0045(13) C3 0.0400(15) 0.0306(15) 0.0456(18) 0.0079(13) -0.0007(13) 0.0044(12) C4 0.063(2) 0.059(2) 0.0282(15) -0.0044(15) 0.0092(15) -0.0112(17) C5 0.0382(15) 0.0342(14) 0.0379(16) 0.0052(13) 0.0108(13) -0.0016(12) C6 0.0388(15) 0.0412(16) 0.0295(14) 0.0013(13) 0.0118(12) 0.0018(13) C7 0.0384(15) 0.0407(16) 0.0268(14) -0.0045(12) 0.0000(12) 0.0002(13) C8 0.0331(14) 0.0350(14) 0.0270(13) -0.0010(12) -0.0053(11) 0.0038(11) C9 0.0252(12) 0.0315(14) 0.0310(13) 0.0002(11) 0.0009(10) -0.0037(10) C10 0.0388(15) 0.0467(17) 0.0312(15) 0.0012(13) 0.0013(12) -0.0049(13) C11 0.0476(17) 0.0474(18) 0.0394(17) -0.0107(14) 0.0132(14) -0.0023(14) C12 0.0310(14) 0.0384(16) 0.0499(18) -0.0053(14) 0.0137(13) -0.0030(12) C13 0.0331(15) 0.0461(18) 0.0416(17) 0.0020(14) 0.0009(13) 0.0074(13) C14 0.0331(14) 0.0436(16) 0.0321(15) -0.0037(13) -0.0006(12) 0.0032(12) C15 0.051(2) 0.050(2) 0.069(2) -0.0039(18) 0.0226(18) 0.0082(16) C16 0.0262(12) 0.0383(15) 0.0262(13) -0.0013(11) 0.0018(10) -0.0028(11) C17 0.0304(14) 0.0509(18) 0.0458(18) -0.0022(15) 0.0037(13) -0.0081(13) C18 0.0260(14) 0.068(2) 0.0480(19) 0.0117(17) 0.0051(13) 0.0006(14) C19 0.0350(14) 0.0508(18) 0.0316(15) 0.0143(14) 0.0094(12) 0.0093(13) C20 0.0406(16) 0.0401(16) 0.0340(15) 0.0016(13) 0.0056(13) 0.0059(13) C21 0.0267(13) 0.0415(16) 0.0350(15) -0.0021(13) 0.0008(11) -0.0021(12) C22 0.052(2) 0.069(2) 0.053(2) 0.0198(19) 0.0159(17) 0.0266(18) _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 N2 1.838(2) . ? Ti1 N1 1.862(2) . ? Ti1 N4 2.082(2) . ? Ti1 N3 2.091(2) . ? Ti1 O1 2.1637(18) . ? S1 O2 1.434(2) . ? S1 O3 1.445(2) . ? S1 N4 1.611(2) . ? S1 C9 1.773(3) . ? S2 O4 1.438(2) . ? S2 O5 1.440(2) . ? S2 N3 1.604(2) . ? S2 C16 1.772(3) . ? O1 C7 1.437(3) . ? O1 C6 1.439(3) . ? N1 C2 1.457(4) . ? N1 C1 1.463(4) . ? N2 C4 1.439(4) . ? N2 C3 1.454(4) . ? N3 C5 1.483(3) . ? N4 C8 1.482(3) . ? C5 C6 1.483(4) . ? C7 C8 1.494(4) . ? C9 C14 1.383(4) . ? C9 C10 1.386(4) . ? C10 C11 1.378(4) . ? C11 C12 1.374(5) . ? C12 C13 1.382(4) . ? C12 C15 1.517(4) . ? C13 C14 1.385(4) . ? C16 C21 1.377(4) . ? C16 C17 1.391(4) . ? C17 C18 1.386(5) . ? C18 C19 1.382(5) . ? C19 C20 1.387(4) . ? C19 C22 1.501(4) . ? C20 C21 1.390(4) . ? 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 N2 Ti1 N1 104.56(10) . . ? N2 Ti1 N4 98.72(9) . . ? N1 Ti1 N4 103.36(9) . . ? N2 Ti1 N3 97.69(9) . . ? N1 Ti1 N3 103.67(10) . . ? N4 Ti1 N3 143.52(9) . . ? N2 Ti1 O1 146.35(9) . . ? N1 Ti1 O1 109.09(9) . . ? N4 Ti1 O1 74.25(8) . . ? N3 Ti1 O1 74.05(8) . . ? O2 S1 O3 116.90(13) . . ? O2 S1 N4 109.71(12) . . ? O3 S1 N4 110.31(12) . . ? O2 S1 C9 107.16(13) . . ? O3 S1 C9 105.91(13) . . ? N4 S1 C9 106.22(12) . . ? O4 S2 O5 117.14(14) . . ? O4 S2 N3 109.21(12) . . ? O5 S2 N3 110.89(14) . . ? O4 S2 C16 107.19(14) . . ? O5 S2 C16 105.54(13) . . ? N3 S2 C16 106.19(12) . . ? C7 O1 C6 114.8(2) . . ? C7 O1 Ti1 117.91(15) . . ? C6 O1 Ti1 117.70(16) . . ? C2 N1 C1 111.1(2) . . ? C2 N1 Ti1 128.7(2) . . ? C1 N1 Ti1 120.25(19) . . ? C4 N2 C3 112.9(2) . . ? C4 N2 Ti1 134.7(2) . . ? C3 N2 Ti1 112.33(18) . . ? C5 N3 S2 111.66(18) . . ? C5 N3 Ti1 115.67(18) . . ? S2 N3 Ti1 130.99(13) . . ? C8 N4 S1 113.46(17) . . ? C8 N4 Ti1 114.92(16) . . ? S1 N4 Ti1 130.47(12) . . ? C6 C5 N3 107.3(2) . . ? O1 C6 C5 105.6(2) . . ? O1 C7 C8 104.9(2) . . ? N4 C8 C7 107.2(2) . . ? C14 C9 C10 119.4(3) . . ? C14 C9 S1 120.2(2) . . ? C10 C9 S1 120.4(2) . . ? C11 C10 C9 119.8(3) . . ? C12 C11 C10 121.5(3) . . ? C11 C12 C13 118.5(3) . . ? C11 C12 C15 121.3(3) . . ? C13 C12 C15 120.2(3) . . ? C12 C13 C14 120.9(3) . . ? C9 C14 C13 119.9(3) . . ? C21 C16 C17 119.8(3) . . ? C21 C16 S2 120.6(2) . . ? C17 C16 S2 119.6(2) . . ? C18 C17 C16 119.7(3) . . ? C19 C18 C17 121.3(3) . . ? C18 C19 C20 118.3(3) . . ? C18 C19 C22 121.2(3) . . ? C20 C19 C22 120.5(3) . . ? C19 C20 C21 121.2(3) . . ? C16 C21 C20 119.8(3) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N2 Ti1 O1 C7 74.3(2) . . . . ? N1 Ti1 O1 C7 -106.71(19) . . . . ? N4 Ti1 O1 C7 -7.70(18) . . . . ? N3 Ti1 O1 C7 154.01(19) . . . . ? N2 Ti1 O1 C6 -70.3(2) . . . . ? N1 Ti1 O1 C6 108.72(19) . . . . ? N4 Ti1 O1 C6 -152.28(19) . . . . ? N3 Ti1 O1 C6 9.43(18) . . . . ? N2 Ti1 N1 C2 -112.9(2) . . . . ? N4 Ti1 N1 C2 -10.1(3) . . . . ? N3 Ti1 N1 C2 145.2(2) . . . . ? O1 Ti1 N1 C2 67.6(2) . . . . ? N2 Ti1 N1 C1 68.3(2) . . . . ? N4 Ti1 N1 C1 171.2(2) . . . . ? N3 Ti1 N1 C1 -33.5(2) . . . . ? O1 Ti1 N1 C1 -111.1(2) . . . . ? N1 Ti1 N2 C4 -0.2(3) . . . . ? N4 Ti1 N2 C4 -106.6(3) . . . . ? N3 Ti1 N2 C4 106.1(3) . . . . ? O1 Ti1 N2 C4 178.8(2) . . . . ? N1 Ti1 N2 C3 -178.55(18) . . . . ? N4 Ti1 N2 C3 75.11(19) . . . . ? N3 Ti1 N2 C3 -72.19(19) . . . . ? O1 Ti1 N2 C3 0.5(3) . . . . ? O4 S2 N3 C5 171.86(19) . . . . ? O5 S2 N3 C5 41.3(2) . . . . ? C16 S2 N3 C5 -72.9(2) . . . . ? O4 S2 N3 Ti1 7.5(2) . . . . ? O5 S2 N3 Ti1 -123.00(17) . . . . ? C16 S2 N3 Ti1 122.83(17) . . . . ? N2 Ti1 N3 C5 165.30(19) . . . . ? N1 Ti1 N3 C5 -87.61(19) . . . . ? N4 Ti1 N3 C5 49.2(3) . . . . ? O1 Ti1 N3 C5 18.68(17) . . . . ? N2 Ti1 N3 S2 -30.89(18) . . . . ? N1 Ti1 N3 S2 76.20(18) . . . . ? N4 Ti1 N3 S2 -146.98(15) . . . . ? O1 Ti1 N3 S2 -177.51(19) . . . . ? O2 S1 N4 C8 167.85(18) . . . . ? O3 S1 N4 C8 37.7(2) . . . . ? C9 S1 N4 C8 -76.6(2) . . . . ? O2 S1 N4 Ti1 -25.2(2) . . . . ? O3 S1 N4 Ti1 -155.38(15) . . . . ? C9 S1 N4 Ti1 90.29(17) . . . . ? N2 Ti1 N4 C8 -167.24(17) . . . . ? N1 Ti1 N4 C8 85.43(18) . . . . ? N3 Ti1 N4 C8 -51.5(2) . . . . ? O1 Ti1 N4 C8 -20.96(16) . . . . ? N2 Ti1 N4 S1 25.98(18) . . . . ? N1 Ti1 N4 S1 -81.35(17) . . . . ? N3 Ti1 N4 S1 141.77(15) . . . . ? O1 Ti1 N4 S1 172.26(17) . . . . ? S2 N3 C5 C6 150.4(2) . . . . ? Ti1 N3 C5 C6 -42.7(3) . . . . ? C7 O1 C6 C5 -179.5(2) . . . . ? Ti1 O1 C6 C5 -33.9(3) . . . . ? N3 C5 C6 O1 46.4(3) . . . . ? C6 O1 C7 C8 178.3(2) . . . . ? Ti1 O1 C7 C8 32.7(3) . . . . ? S1 N4 C8 C7 -145.70(19) . . . . ? Ti1 N4 C8 C7 45.2(3) . . . . ? O1 C7 C8 N4 -47.2(3) . . . . ? O2 S1 C9 C14 -171.1(2) . . . . ? O3 S1 C9 C14 -45.6(3) . . . . ? N4 S1 C9 C14 71.7(2) . . . . ? O2 S1 C9 C10 11.5(3) . . . . ? O3 S1 C9 C10 137.0(2) . . . . ? N4 S1 C9 C10 -105.7(2) . . . . ? C14 C9 C10 C11 -0.2(4) . . . . ? S1 C9 C10 C11 177.2(2) . . . . ? C9 C10 C11 C12 -1.0(5) . . . . ? C10 C11 C12 C13 0.6(5) . . . . ? C10 C11 C12 C15 179.1(3) . . . . ? C11 C12 C13 C14 0.8(4) . . . . ? C15 C12 C13 C14 -177.6(3) . . . . ? C10 C9 C14 C13 1.6(4) . . . . ? S1 C9 C14 C13 -175.7(2) . . . . ? C12 C13 C14 C9 -2.0(5) . . . . ? O4 S2 C16 C21 85.4(3) . . . . ? O5 S2 C16 C21 -149.1(2) . . . . ? N3 S2 C16 C21 -31.3(3) . . . . ? O4 S2 C16 C17 -92.0(3) . . . . ? O5 S2 C16 C17 33.6(3) . . . . ? N3 S2 C16 C17 151.4(2) . . . . ? C21 C16 C17 C18 -1.9(5) . . . . ? S2 C16 C17 C18 175.4(2) . . . . ? C16 C17 C18 C19 1.3(5) . . . . ? C17 C18 C19 C20 0.2(5) . . . . ? C17 C18 C19 C22 179.4(3) . . . . ? C18 C19 C20 C21 -1.1(4) . . . . ? C22 C19 C20 C21 179.7(3) . . . . ? C17 C16 C21 C20 1.0(4) . . . . ? S2 C16 C21 C20 -176.3(2) . . . . ? C19 C20 C21 C16 0.5(4) . . . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 0.50 _diffrn_measured_fraction_theta_full 0.000 _refine_diff_density_max 0.450 _refine_diff_density_min -0.475 _refine_diff_density_rms 0.120 #===END data_4 _database_code_CSD 160979 _journal_coden_Cambridge 186 _publ_requested_journal ' Dalton Transactions' loop_ _publ_author_name 'Nagashima, Hideo' 'Hamura, Satoshi' 'Matsubara, Kouki' 'Oda, Takashi' 'Shimizu, Yasuaki' _publ_contact_author 'Prof Hideo Nagashima' _publ_contact_author_address ; Institute of Advanced Material Study Kyushu University Kasuga Fukuoka 816-8580 JAPAN ; _publ_contact_author_email ' nagasima@cm.kyushu-u.ac.jp ' _audit_creation_method 'SHELXL-97' _audit_update_record ? _chemical_formula_weight 1245.70 _chemical_formula_analytical ? _chemical_formula_sum 'C42 H60 Cl6 N6 O10 S4 Ti2' _chemical_formula_moiety 'C40 H56 Cl2 N6 O10 S4 Ti2, 2(C H2 Cl2)' _chemical_formula_structural ? _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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 '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 'P 21/c' _symmetry_Int_Tables_number 14 _symmetry_space_group_name_Hall ? loop_ _symmetry_equiv_pos_as_xyz ' +x, +y, +z' ' -x,1/2+y,1/2-z' ' -x, -y, -z' ' +x,1/2-y,1/2+z' _cell_length_a 11.1393(5) _cell_length_b 17.965(1) _cell_length_c 13.887(1) _cell_angle_alpha 90 _cell_angle_beta 91.168(3) _cell_angle_gamma 90 _cell_volume 2778.5(3) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 20149 _cell_measurement_theta_min 2.6 _cell_measurement_theta_max 27.5 _publ_section_exptl_prep ; ENTER EXPERIMENTAL SECTION ; _exptl_crystal_description 'prism' _exptl_crystal_colour 'red' _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.60 _exptl_crystal_size_min 0.40 _exptl_crystal_density_diffrn 1.489 _exptl_crystal_density_meas 'not measured' _exptl_crystal_F_000 1288.00 _exptl_absorpt_coefficient_mu 0.783 _exptl_absorpt_correction_type 'empirical' _exptl_absorpt_correction_T_max 0.731 _exptl_absorpt_correction_T_min 0.332 _exptl_special_details ; ? ; _diffrn_special_details ; ? ; _diffrn_ambient_temperature 223(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Rigaku rotating anode' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'Imaging Plate' _diffrn_measurement_device 'Rigaku RAXIS-RAPID' _diffrn_detector_area_resol_mean ? _diffrn_measurement_method 'oscillation' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 6531 _diffrn_reflns_av_R_equivalents 0.11879 _diffrn_reflns_av_sigmaI/netI 0.211 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.63 _diffrn_reflns_theta_max 27.48 _reflns_number_total 6149 _reflns_number_gt 2796 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'MSC/AFC Diffractometer Control' _computing_cell_refinement 'MSC/AFC Diffractometer Control' _computing_data_reduction 'teXsan for Windows version 1.06 (MSC, 1997-1999)' _computing_structure_solution 'DIRDIF94 PATTY (Beurskens, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _computing_molecular_graphics 'ORTEP III (Farrujia, 1998)' _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^)+(0.0594P)^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 6149 _refine_ls_number_parameters 320 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1714 _refine_ls_R_factor_gt 0.0744 _refine_ls_wR_factor_ref 0.1757 _refine_ls_wR_factor_gt 0.1401 _refine_ls_goodness_of_fit_ref 0.938 _refine_ls_restrained_S_all 0.938 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.19186(8) 0.09613(5) 0.01070(7) 0.0317(2) Uani 1 1 d . . . Cl1 Cl 0.38221(12) 0.08728(9) 0.08306(12) 0.0516(4) Uani 1 1 d . . . Cl2 Cl -0.0953(6) 0.3997(4) 0.0993(4) 0.319(4) Uani 1 1 d . . . Cl3 Cl -0.1451(4) 0.4392(2) -0.0999(4) 0.1819(17) Uani 1 1 d . . . S1 S 0.11435(11) -0.08345(7) 0.01991(10) 0.0334(3) Uani 1 1 d . . . S2 S 0.24075(12) 0.27214(8) -0.05575(10) 0.0377(3) Uani 1 1 d . . . O1 O 0.1213(3) 0.12188(19) 0.1504(3) 0.0360(8) Uani 1 1 d . . . O2 O 0.1517(3) -0.0816(2) -0.0790(3) 0.0411(9) Uani 1 1 d . . . O3 O -0.0106(3) -0.10725(18) 0.0356(3) 0.0359(8) Uani 1 1 d . . . O4 O 0.3105(4) 0.2361(2) -0.1280(3) 0.0454(10) Uani 1 1 d . . . O5 O 0.1457(3) 0.3210(2) -0.0872(3) 0.0468(10) Uani 1 1 d . . . N1 N 0.2423(4) 0.0759(2) -0.1143(3) 0.0419(11) Uani 1 1 d . . . N2 N 0.1401(4) -0.0069(2) 0.0715(3) 0.0338(10) Uani 1 1 d . . . N3 N 0.1906(4) 0.2105(2) 0.0160(3) 0.0333(9) Uani 1 1 d . . . C1 C 0.0965(6) -0.0050(3) 0.1718(4) 0.0435(14) Uani 1 1 d . . . H1A H 0.1266 -0.0486 0.2073 0.052 Uiso 1 1 calc R . . H1B H 0.0085 -0.0066 0.1713 0.052 Uiso 1 1 calc R . . C2 C 0.1394(6) 0.0650(3) 0.2210(4) 0.0468(14) Uani 1 1 d . . . H2A H 0.0927 0.0751 0.2785 0.056 Uiso 1 1 calc R . . H2B H 0.2245 0.0610 0.2396 0.056 Uiso 1 1 calc R . . C3 C 0.1402(6) 0.1983(3) 0.1828(4) 0.0435(14) Uani 1 1 d . . . H3A H 0.2223 0.2054 0.2077 0.052 Uiso 1 1 calc R . . H3B H 0.0836 0.2116 0.2331 0.052 Uiso 1 1 calc R . . C4 C 0.1185(6) 0.2426(3) 0.0956(4) 0.0457(14) Uani 1 1 d . . . H4A H 0.1422 0.2945 0.1072 0.055 Uiso 1 1 calc R . . H4B H 0.0329 0.2417 0.0779 0.055 Uiso 1 1 calc R . . C5 C 0.1989(5) -0.1525(3) 0.0825(4) 0.0404(13) Uani 1 1 d . . . C6 C 0.1441(6) -0.2052(3) 0.1367(6) 0.0605(19) Uani 1 1 d . . . H6 H 0.0601 -0.2053 0.1419 0.073 Uiso 1 1 calc R . . C7 C 0.2126(7) -0.2587(4) 0.1839(6) 0.073(2) Uani 1 1 d . . . H7 H 0.1746 -0.2946 0.2218 0.087 Uiso 1 1 calc R . . C8 C 0.3359(7) -0.2599(3) 0.1760(6) 0.064(2) Uani 1 1 d . . . C9 C 0.3906(6) -0.2050(4) 0.1228(6) 0.0604(19) Uani 1 1 d . . . H9 H 0.4748 -0.2038 0.1194 0.073 Uiso 1 1 calc R . . C10 C 0.3225(5) -0.1513(3) 0.0740(5) 0.0528(16) Uani 1 1 d . . . H10 H 0.3597 -0.1151 0.0360 0.063 Uiso 1 1 calc R . . C11 C 0.4144(8) -0.3191(4) 0.2260(8) 0.098(3) Uani 1 1 d . . . H11A H 0.4922 -0.2978 0.2425 0.147 Uiso 1 1 calc R . . H11B H 0.4248 -0.3609 0.1829 0.147 Uiso 1 1 calc R . . H11C H 0.3758 -0.3358 0.2841 0.147 Uiso 1 1 calc R . . C12 C 0.3412(5) 0.3284(3) 0.0161(4) 0.0460(15) Uani 1 1 d . . . C13 C 0.3228(6) 0.4028(3) 0.0226(5) 0.0537(16) Uani 1 1 d . . . H13 H 0.2551 0.4248 -0.0073 0.064 Uiso 1 1 calc R . . C14 C 0.4050(6) 0.4461(4) 0.0740(5) 0.0608(18) Uani 1 1 d . . . H14 H 0.3931 0.4978 0.0769 0.073 Uiso 1 1 calc R . . C15 C 0.5038(6) 0.4154(4) 0.1211(4) 0.0583(18) Uani 1 1 d . . . C16 C 0.5184(6) 0.3397(4) 0.1139(5) 0.069(2) Uani 1 1 d . . . H16 H 0.5847 0.3173 0.1452 0.083 Uiso 1 1 calc R . . C17 C 0.4376(7) 0.2950(4) 0.0614(5) 0.066(2) Uani 1 1 d . . . H17 H 0.4492 0.2433 0.0572 0.079 Uiso 1 1 calc R . . C18 C 0.5939(7) 0.4627(4) 0.1770(6) 0.079(2) Uani 1 1 d . . . H18A H 0.5651 0.5136 0.1799 0.119 Uiso 1 1 calc R . . H18B H 0.6705 0.4616 0.1450 0.119 Uiso 1 1 calc R . . H18C H 0.6038 0.4432 0.2418 0.119 Uiso 1 1 calc R . . C19 C 0.1837(6) 0.1011(4) -0.2043(4) 0.0552(16) Uani 1 1 d . . . H19A H 0.1130 0.1301 -0.1895 0.083 Uiso 1 1 calc R . . H19B H 0.1604 0.0582 -0.2428 0.083 Uiso 1 1 calc R . . H19C H 0.2391 0.1317 -0.2400 0.083 Uiso 1 1 calc R . . C20 C 0.3540(5) 0.0345(4) -0.1390(5) 0.0595(18) Uani 1 1 d . . . H20A H 0.3895 0.0130 -0.0809 0.089 Uiso 1 1 calc R . . H20B H 0.4108 0.0684 -0.1677 0.089 Uiso 1 1 calc R . . H20C H 0.3343 -0.0050 -0.1844 0.089 Uiso 1 1 calc R . . C21 C -0.1111(17) 0.3766(10) -0.0097(12) 0.227(9) Uani 1 1 d . . . H21A H -0.1739 0.3384 -0.0122 0.273 Uiso 1 1 calc R . . H21B H -0.0364 0.3520 -0.0277 0.273 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 0.0320(5) 0.0359(5) 0.0269(5) -0.0015(4) -0.0070(4) 0.0015(4) Cl1 0.0350(7) 0.0586(9) 0.0604(10) 0.0030(8) -0.0170(6) 0.0010(7) Cl2 0.347(7) 0.477(10) 0.131(4) -0.139(5) -0.051(4) 0.276(7) Cl3 0.203(4) 0.135(3) 0.206(5) 0.005(3) -0.048(3) 0.061(2) S1 0.0330(6) 0.0341(7) 0.0328(7) -0.0003(6) -0.0096(5) 0.0021(5) S2 0.0462(8) 0.0382(7) 0.0283(7) 0.0023(6) -0.0088(6) -0.0023(6) O1 0.047(2) 0.0362(19) 0.0243(19) 0.0000(15) -0.0068(16) 0.0014(16) O2 0.047(2) 0.047(2) 0.029(2) -0.0073(17) -0.0010(16) 0.0006(17) O3 0.0363(19) 0.038(2) 0.033(2) 0.0015(17) -0.0071(16) -0.0024(15) O4 0.058(2) 0.045(2) 0.033(2) 0.0008(18) 0.0019(19) -0.0035(19) O5 0.054(2) 0.056(2) 0.030(2) 0.0010(19) -0.0116(19) 0.0084(19) N1 0.047(3) 0.035(2) 0.044(3) -0.002(2) 0.002(2) 0.003(2) N2 0.041(2) 0.030(2) 0.030(2) 0.0013(19) -0.008(2) 0.0007(18) N3 0.035(2) 0.039(2) 0.026(2) -0.0009(19) -0.0068(18) -0.0008(19) C1 0.063(4) 0.033(3) 0.034(3) 0.002(2) -0.001(3) 0.001(3) C2 0.061(4) 0.043(3) 0.036(3) 0.006(3) -0.001(3) 0.001(3) C3 0.058(4) 0.039(3) 0.034(3) 0.000(3) 0.003(3) 0.002(3) C4 0.060(4) 0.034(3) 0.043(4) -0.001(3) 0.007(3) 0.005(3) C5 0.040(3) 0.035(3) 0.046(3) -0.002(3) -0.009(3) 0.006(2) C6 0.051(4) 0.047(4) 0.083(5) 0.012(4) -0.011(4) 0.003(3) C7 0.066(5) 0.051(4) 0.101(7) 0.026(4) -0.010(4) 0.009(3) C8 0.076(5) 0.041(4) 0.074(5) -0.005(4) -0.035(4) 0.021(3) C9 0.046(4) 0.055(4) 0.080(5) -0.003(4) -0.019(4) 0.018(3) C10 0.038(3) 0.050(4) 0.070(5) 0.003(3) 0.003(3) 0.010(3) C11 0.098(6) 0.055(5) 0.137(9) 0.015(5) -0.062(6) 0.020(4) C12 0.055(4) 0.043(3) 0.039(3) 0.002(3) -0.004(3) -0.016(3) C13 0.058(4) 0.044(3) 0.059(4) -0.007(3) 0.002(3) -0.010(3) C14 0.076(5) 0.046(4) 0.061(5) -0.009(3) 0.004(4) -0.021(3) C15 0.068(4) 0.073(5) 0.034(3) -0.004(3) 0.005(3) -0.038(4) C16 0.061(4) 0.082(5) 0.062(5) 0.007(4) -0.032(4) -0.016(4) C17 0.085(5) 0.050(4) 0.061(5) 0.009(3) -0.035(4) -0.009(3) C18 0.083(5) 0.091(6) 0.063(5) -0.010(4) -0.010(4) -0.047(4) C19 0.066(4) 0.070(4) 0.029(3) -0.010(3) 0.003(3) -0.009(3) C20 0.054(4) 0.072(4) 0.054(4) -0.016(4) 0.015(3) 0.011(3) C21 0.29(2) 0.238(18) 0.151(15) 0.001(14) -0.076(14) 0.160(16) _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 1.871(5) . ? Ti1 N3 2.057(4) . ? Ti1 O3 2.116(3) 3 ? Ti1 N2 2.119(4) . ? Ti1 O1 2.158(4) . ? Ti1 Cl1 2.3332(15) . ? Cl2 C21 1.575(16) . ? Cl3 C21 1.721(15) . ? S1 O2 1.443(4) . ? S1 O3 1.476(3) . ? S1 N2 1.574(4) . ? S1 C5 1.774(5) . ? S2 O4 1.436(4) . ? S2 O5 1.437(4) . ? S2 N3 1.598(4) . ? S2 C12 1.795(6) . ? O1 C2 1.428(6) . ? O1 C3 1.459(6) . ? O3 Ti1 2.116(3) 3 ? N1 C19 1.469(7) . ? N1 C20 1.496(7) . ? N2 C1 1.486(7) . ? N3 C4 1.495(7) . ? C1 C2 1.503(8) . ? C3 C4 1.464(8) . ? C5 C6 1.362(9) . ? C5 C10 1.384(7) . ? C6 C7 1.383(9) . ? C7 C8 1.381(9) . ? C8 C9 1.382(10) . ? C8 C11 1.533(9) . ? C9 C10 1.394(8) . ? C12 C13 1.355(8) . ? C12 C17 1.372(9) . ? C13 C14 1.388(9) . ? C14 C15 1.384(10) . ? C15 C16 1.372(10) . ? C15 C18 1.517(8) . ? C16 C17 1.401(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 N3 103.27(19) . . ? N1 Ti1 O3 92.26(17) . 3 ? N3 Ti1 O3 84.79(15) . 3 ? N1 Ti1 N2 106.82(18) . . ? N3 Ti1 N2 148.92(18) . . ? O3 Ti1 N2 86.43(15) 3 . ? N1 Ti1 O1 175.85(17) . . ? N3 Ti1 O1 75.57(16) . . ? O3 Ti1 O1 83.68(13) 3 . ? N2 Ti1 O1 73.86(15) . . ? N1 Ti1 Cl1 95.67(15) . . ? N3 Ti1 Cl1 93.42(13) . . ? O3 Ti1 Cl1 172.07(11) 3 . ? N2 Ti1 Cl1 91.21(12) . . ? O1 Ti1 Cl1 88.39(10) . . ? O2 S1 O3 116.0(2) . . ? O2 S1 N2 111.0(2) . . ? O3 S1 N2 110.5(2) . . ? O2 S1 C5 108.8(3) . . ? O3 S1 C5 102.6(2) . . ? N2 S1 C5 107.3(2) . . ? O4 S2 O5 118.0(2) . . ? O4 S2 N3 109.0(2) . . ? O5 S2 N3 110.4(2) . . ? O4 S2 C12 107.6(3) . . ? O5 S2 C12 105.8(3) . . ? N3 S2 C12 105.4(2) . . ? C2 O1 C3 116.4(4) . . ? C2 O1 Ti1 114.5(3) . . ? C3 O1 Ti1 115.2(3) . . ? S1 O3 Ti1 145.6(2) . 3 ? C19 N1 C20 108.4(5) . . ? C19 N1 Ti1 126.3(4) . . ? C20 N1 Ti1 125.2(4) . . ? C1 N2 S1 112.7(3) . . ? C1 N2 Ti1 116.8(3) . . ? S1 N2 Ti1 129.1(3) . . ? C4 N3 S2 113.2(3) . . ? C4 N3 Ti1 114.6(3) . . ? S2 N3 Ti1 131.9(3) . . ? N2 C1 C2 109.7(5) . . ? O1 C2 C1 104.4(5) . . ? O1 C3 C4 103.7(5) . . ? C3 C4 N3 108.6(4) . . ? C6 C5 C10 121.0(6) . . ? C6 C5 S1 121.2(4) . . ? C10 C5 S1 117.8(5) . . ? C5 C6 C7 119.7(6) . . ? C8 C7 C6 120.9(7) . . ? C7 C8 C9 118.8(6) . . ? C7 C8 C11 122.3(7) . . ? C9 C8 C11 118.9(7) . . ? C8 C9 C10 120.8(6) . . ? C5 C10 C9 118.7(6) . . ? C13 C12 C17 121.2(6) . . ? C13 C12 S2 119.9(5) . . ? C17 C12 S2 118.8(5) . . ? C12 C13 C14 119.2(7) . . ? C15 C14 C13 122.0(6) . . ? C16 C15 C14 117.0(6) . . ? C16 C15 C18 121.0(7) . . ? C14 C15 C18 122.0(7) . . ? C15 C16 C17 122.0(7) . . ? C12 C17 C16 118.5(6) . . ? Cl2 C21 Cl3 123.1(11) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N3 Ti1 O1 C2 -154.5(4) . . . . ? O3 Ti1 O1 C2 119.3(3) 3 . . . ? N2 Ti1 O1 C2 31.2(3) . . . . ? Cl1 Ti1 O1 C2 -60.5(3) . . . . ? N3 Ti1 O1 C3 -15.5(3) . . . . ? O3 Ti1 O1 C3 -101.7(3) 3 . . . ? N2 Ti1 O1 C3 170.2(4) . . . . ? Cl1 Ti1 O1 C3 78.5(3) . . . . ? O2 S1 O3 Ti1 -44.9(4) . . . 3 ? N2 S1 O3 Ti1 82.5(4) . . . 3 ? C5 S1 O3 Ti1 -163.3(4) . . . 3 ? N3 Ti1 N1 C19 -57.9(5) . . . . ? O3 Ti1 N1 C19 27.3(5) 3 . . . ? N2 Ti1 N1 C19 114.3(5) . . . . ? Cl1 Ti1 N1 C19 -152.8(4) . . . . ? N3 Ti1 N1 C20 118.5(5) . . . . ? O3 Ti1 N1 C20 -156.3(5) 3 . . . ? N2 Ti1 N1 C20 -69.4(5) . . . . ? Cl1 Ti1 N1 C20 23.6(5) . . . . ? O2 S1 N2 C1 176.7(4) . . . . ? O3 S1 N2 C1 46.6(4) . . . . ? C5 S1 N2 C1 -64.6(4) . . . . ? O2 S1 N2 Ti1 10.8(4) . . . . ? O3 S1 N2 Ti1 -119.3(3) . . . . ? C5 S1 N2 Ti1 129.6(3) . . . . ? N1 Ti1 N2 C1 179.8(4) . . . . ? N3 Ti1 N2 C1 -15.1(5) . . . . ? O3 Ti1 N2 C1 -88.9(4) 3 . . . ? O1 Ti1 N2 C1 -4.4(4) . . . . ? Cl1 Ti1 N2 C1 83.6(4) . . . . ? N1 Ti1 N2 S1 -14.7(4) . . . . ? N3 Ti1 N2 S1 150.3(3) . . . . ? O3 Ti1 N2 S1 76.5(3) 3 . . . ? O1 Ti1 N2 S1 161.0(3) . . . . ? Cl1 Ti1 N2 S1 -111.0(3) . . . . ? O4 S2 N3 C4 178.8(4) . . . . ? O5 S2 N3 C4 -50.2(4) . . . . ? C12 S2 N3 C4 63.5(4) . . . . ? O4 S2 N3 Ti1 -8.7(4) . . . . ? O5 S2 N3 Ti1 122.3(3) . . . . ? C12 S2 N3 Ti1 -123.9(3) . . . . ? N1 Ti1 N3 C4 161.9(4) . . . . ? O3 Ti1 N3 C4 70.8(4) 3 . . . ? N2 Ti1 N3 C4 -3.4(6) . . . . ? O1 Ti1 N3 C4 -14.0(4) . . . . ? Cl1 Ti1 N3 C4 -101.4(4) . . . . ? N1 Ti1 N3 S2 -10.5(4) . . . . ? O3 Ti1 N3 S2 -101.6(3) 3 . . . ? N2 Ti1 N3 S2 -175.8(3) . . . . ? O1 Ti1 N3 S2 173.6(3) . . . . ? Cl1 Ti1 N3 S2 86.1(3) . . . . ? S1 N2 C1 C2 171.9(4) . . . . ? Ti1 N2 C1 C2 -20.3(6) . . . . ? C3 O1 C2 C1 171.9(5) . . . . ? Ti1 O1 C2 C1 -49.6(5) . . . . ? N2 C1 C2 O1 43.0(6) . . . . ? C2 O1 C3 C4 178.5(5) . . . . ? Ti1 O1 C3 C4 40.3(5) . . . . ? O1 C3 C4 N3 -50.1(6) . . . . ? S2 N3 C4 C3 -144.9(4) . . . . ? Ti1 N3 C4 C3 41.3(6) . . . . ? O2 S1 C5 C6 -129.6(6) . . . . ? O3 S1 C5 C6 -6.2(6) . . . . ? N2 S1 C5 C6 110.2(6) . . . . ? O2 S1 C5 C10 50.0(5) . . . . ? O3 S1 C5 C10 173.3(5) . . . . ? N2 S1 C5 C10 -70.3(5) . . . . ? C10 C5 C6 C7 -0.1(11) . . . . ? S1 C5 C6 C7 179.4(6) . . . . ? C5 C6 C7 C8 -0.8(12) . . . . ? C6 C7 C8 C9 2.3(12) . . . . ? C6 C7 C8 C11 -179.0(7) . . . . ? C7 C8 C9 C10 -3.0(11) . . . . ? C11 C8 C9 C10 178.2(7) . . . . ? C6 C5 C10 C9 -0.6(10) . . . . ? S1 C5 C10 C9 179.9(5) . . . . ? C8 C9 C10 C5 2.2(10) . . . . ? O4 S2 C12 C13 121.0(5) . . . . ? O5 S2 C12 C13 -5.9(6) . . . . ? N3 S2 C12 C13 -122.9(5) . . . . ? O4 S2 C12 C17 -57.2(6) . . . . ? O5 S2 C12 C17 175.8(5) . . . . ? N3 S2 C12 C17 58.9(6) . . . . ? C17 C12 C13 C14 1.8(10) . . . . ? S2 C12 C13 C14 -176.4(5) . . . . ? C12 C13 C14 C15 -1.8(10) . . . . ? C13 C14 C15 C16 0.8(10) . . . . ? C13 C14 C15 C18 179.8(6) . . . . ? C14 C15 C16 C17 0.1(11) . . . . ? C18 C15 C16 C17 -178.9(7) . . . . ? C13 C12 C17 C16 -0.9(11) . . . . ? S2 C12 C17 C16 177.3(6) . . . . ? C15 C16 C17 C12 -0.1(12) . . . . ? _diffrn_measured_fraction_theta_max 0.965 _diffrn_reflns_theta_full 0.50 _diffrn_measured_fraction_theta_full 0.000 _refine_diff_density_max 0.458 _refine_diff_density_min -0.676 _refine_diff_density_rms 0.090