# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Guo-Xin Jin' _publ_contact_author_email GXJIN@FUDAN.EDU.CN _publ_section_title ; Syntheses, Characterization, and Ethylene Polymerization of Titanium and Zirconium Complexes with [N, O] Ligands ; loop_ _publ_author_name 'Guo-Xin Jin' 'Ai-Quan Jia' # Attachment '2b.cif' data_f90316b _database_code_depnum_ccdc_archive 'CCDC 727482' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C35 H28 Cl2 N2 O2 S2 Ti' _chemical_formula_weight 691.51 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' S S 0.1246 0.1234 '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 16.734(5) _cell_length_b 12.974(4) _cell_length_c 15.553(5) _cell_angle_alpha 90.00 _cell_angle_beta 106.260(5) _cell_angle_gamma 90.00 _cell_volume 3241.5(18) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 632 _cell_measurement_theta_min 2.536 _cell_measurement_theta_max 18.882 _exptl_crystal_description block _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.417 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1424 _exptl_absorpt_coefficient_mu 0.593 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8906 _exptl_absorpt_correction_T_max 0.9541 _exptl_absorpt_process_details sadabs _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 6.58 _diffrn_reflns_number 13151 _diffrn_reflns_av_R_equivalents 0.1176 _diffrn_reflns_av_sigmaI/netI 0.2372 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.02 _diffrn_reflns_theta_max 25.01 _reflns_number_total 5706 _reflns_number_gt 1970 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0193P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5706 _refine_ls_number_parameters 400 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1720 _refine_ls_R_factor_gt 0.0501 _refine_ls_wR_factor_ref 0.0871 _refine_ls_wR_factor_gt 0.0687 _refine_ls_goodness_of_fit_ref 0.696 _refine_ls_restrained_S_all 0.696 _refine_ls_shift/su_max 0.006 _refine_ls_shift/su_mean 0.001 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 0.26873(5) 0.85549(6) 0.46668(6) 0.0451(3) Uani 1 1 d . . . Cl1 Cl 0.13588(7) 0.89956(9) 0.38106(8) 0.0562(4) Uani 1 1 d . . . Cl2 Cl 0.29729(9) 1.00319(10) 0.54696(9) 0.0741(5) Uani 1 1 d . . . N1 N 0.2419(2) 0.7070(3) 0.3854(2) 0.0399(10) Uani 1 1 d . . . N2 N 0.2143(2) 0.7853(3) 0.5677(2) 0.0423(11) Uani 1 1 d . . . O1 O 0.32113(17) 0.8883(2) 0.3832(2) 0.0467(9) Uani 1 1 d . . . O2 O 0.35927(18) 0.7801(2) 0.53189(19) 0.0482(9) Uani 1 1 d . . . S1 S 0.27797(9) 0.55284(11) 0.29913(10) 0.0669(5) Uani 1 1 d . . . S2 S 0.18097(8) 0.64490(11) 0.67084(9) 0.0576(4) Uani 1 1 d . . . C1 C 0.3757(3) 0.8411(4) 0.3488(3) 0.0440(14) Uani 1 1 d . . . C2 C 0.4426(3) 0.8949(4) 0.3371(3) 0.0450(14) Uani 1 1 d . . . C3 C 0.4975(3) 0.8465(4) 0.3010(3) 0.0582(15) Uani 1 1 d . . . H3 H 0.5435 0.8820 0.2938 0.070 Uiso 1 1 calc R . . C4 C 0.4849(3) 0.7427(5) 0.2744(3) 0.0602(16) Uani 1 1 d . . . H4 H 0.5219 0.7104 0.2484 0.072 Uiso 1 1 calc R . . C5 C 0.4194(3) 0.6898(4) 0.2866(3) 0.0520(15) Uani 1 1 d . . . H5 H 0.4121 0.6213 0.2684 0.062 Uiso 1 1 calc R . . C6 C 0.3626(3) 0.7346(4) 0.3254(3) 0.0416(13) Uani 1 1 d . . . C7 C 0.2953(3) 0.6774(3) 0.3413(3) 0.0426(14) Uani 1 1 d . . . C8 C 0.1822(3) 0.6319(4) 0.3834(3) 0.0440(14) Uani 1 1 d . . . C9 C 0.1141(3) 0.6408(4) 0.4175(3) 0.0545(15) Uani 1 1 d . . . H9 H 0.1038 0.7021 0.4434 0.065 Uiso 1 1 calc R . . C10 C 0.0619(4) 0.5570(5) 0.4124(4) 0.0746(18) Uani 1 1 d . . . H10 H 0.0161 0.5623 0.4349 0.090 Uiso 1 1 calc R . . C11 C 0.0769(4) 0.4651(5) 0.3739(4) 0.082(2) Uani 1 1 d . . . H11 H 0.0423 0.4088 0.3727 0.098 Uiso 1 1 calc R . . C12 C 0.1416(4) 0.4567(4) 0.3381(4) 0.0750(19) Uani 1 1 d . . . H12 H 0.1508 0.3953 0.3115 0.090 Uiso 1 1 calc R . . C13 C 0.1943(3) 0.5404(4) 0.3411(3) 0.0539(15) Uani 1 1 d . . . C14 C 0.4532(3) 1.0065(4) 0.3635(3) 0.0703(17) Uani 1 1 d . . . H14A H 0.4140 1.0473 0.3199 0.105 Uiso 1 1 calc R . . H14B H 0.5088 1.0281 0.3663 0.105 Uiso 1 1 calc R . . H14C H 0.4437 1.0154 0.4211 0.105 Uiso 1 1 calc R . . C15 C 0.3707(3) 0.6832(4) 0.5619(3) 0.0456(14) Uani 1 1 d . . . C16 C 0.4448(3) 0.6333(5) 0.5640(3) 0.0582(16) Uani 1 1 d . . . C17 C 0.4523(4) 0.5307(5) 0.5896(3) 0.0723(19) Uani 1 1 d . . . H17 H 0.5010 0.4956 0.5908 0.087 Uiso 1 1 calc R . . C18 C 0.3899(4) 0.4793(4) 0.6134(4) 0.078(2) Uani 1 1 d . . . H18 H 0.3960 0.4096 0.6278 0.094 Uiso 1 1 calc R . . C19 C 0.3193(4) 0.5292(4) 0.6162(3) 0.0639(17) Uani 1 1 d . . . H19 H 0.2782 0.4943 0.6342 0.077 Uiso 1 1 calc R . . C20 C 0.3083(3) 0.6348(4) 0.5914(3) 0.0437(13) Uani 1 1 d . . . C21 C 0.2377(3) 0.6924(4) 0.6030(3) 0.0439(14) Uani 1 1 d . . . C22 C 0.1483(3) 0.8213(4) 0.5983(3) 0.0437(14) Uani 1 1 d . . . C23 C 0.1105(3) 0.9184(4) 0.5797(3) 0.0533(15) Uani 1 1 d . . . H23 H 0.1290 0.9658 0.5447 0.064 Uiso 1 1 calc R . . C24 C 0.0458(3) 0.9420(4) 0.6143(3) 0.0641(17) Uani 1 1 d . . . H24 H 0.0199 1.0058 0.6016 0.077 Uiso 1 1 calc R . . C25 C 0.0183(3) 0.8730(5) 0.6677(4) 0.0671(18) Uani 1 1 d . . . H25 H -0.0261 0.8908 0.6897 0.080 Uiso 1 1 calc R . . C26 C 0.0561(3) 0.7780(4) 0.6886(3) 0.0576(16) Uani 1 1 d . . . H26 H 0.0388 0.7315 0.7252 0.069 Uiso 1 1 calc R . . C27 C 0.1204(3) 0.7553(4) 0.6526(3) 0.0474(14) Uani 1 1 d . . . C28 C 0.5134(3) 0.6896(4) 0.5399(3) 0.0728(18) Uani 1 1 d . . . H28A H 0.4964 0.7062 0.4772 0.109 Uiso 1 1 calc R . . H28B H 0.5621 0.6468 0.5526 0.109 Uiso 1 1 calc R . . H28C H 0.5259 0.7519 0.5743 0.109 Uiso 1 1 calc R . . C29 C 0.1779(8) 0.2671(7) 0.6481(8) 0.154(4) Uani 1 1 d . . . C30 C 0.2491(6) 0.2160(6) 0.6809(8) 0.131(3) Uani 1 1 d . . . H30 H 0.2674 0.1696 0.6450 0.157 Uiso 1 1 calc R . . C31 C 0.2946(5) 0.2317(7) 0.7663(9) 0.142(3) Uani 1 1 d . . . H31 H 0.3438 0.1951 0.7885 0.171 Uiso 1 1 calc R . . C32 C 0.2704(6) 0.2998(8) 0.8211(6) 0.129(3) Uani 1 1 d . . . H32 H 0.3015 0.3102 0.8802 0.155 Uiso 1 1 calc R . . C33 C 0.2026(6) 0.3485(6) 0.7867(9) 0.137(4) Uani 1 1 d . . . H33 H 0.1847 0.3954 0.8225 0.164 Uiso 1 1 calc R . . C34 C 0.1542(6) 0.3356(9) 0.6990(8) 0.165(4) Uani 1 1 d . . . H34 H 0.1061 0.3742 0.6765 0.198 Uiso 1 1 calc R . . C35 C 0.1279(6) 0.2445(6) 0.5554(6) 0.244(6) Uani 1 1 d . . . H35A H 0.1635 0.2172 0.5220 0.366 Uiso 1 1 calc R . . H35B H 0.1022 0.3068 0.5275 0.366 Uiso 1 1 calc R . . H35C H 0.0856 0.1949 0.5565 0.366 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 0.0465(6) 0.0419(6) 0.0482(6) -0.0022(5) 0.0156(5) 0.0056(5) Cl1 0.0519(9) 0.0625(9) 0.0552(9) 0.0092(7) 0.0167(7) 0.0146(7) Cl2 0.0799(11) 0.0554(9) 0.0936(12) -0.0260(9) 0.0348(9) -0.0019(8) N1 0.041(3) 0.041(3) 0.038(3) 0.006(2) 0.012(2) 0.006(2) N2 0.043(3) 0.045(3) 0.041(3) -0.003(2) 0.016(2) 0.009(2) O1 0.043(2) 0.041(2) 0.065(2) -0.0051(17) 0.0300(19) 0.0009(17) O2 0.048(2) 0.046(2) 0.047(2) -0.0035(19) 0.0080(17) 0.0102(19) S1 0.0783(11) 0.0463(9) 0.0758(12) -0.0132(9) 0.0212(9) 0.0014(8) S2 0.0689(10) 0.0585(10) 0.0468(9) 0.0056(8) 0.0186(8) 0.0028(8) C1 0.031(3) 0.063(4) 0.040(3) 0.008(3) 0.014(3) 0.007(3) C2 0.038(3) 0.052(4) 0.051(4) 0.008(3) 0.022(3) 0.009(3) C3 0.050(4) 0.070(4) 0.060(4) 0.011(4) 0.023(3) 0.002(3) C4 0.061(4) 0.074(5) 0.053(4) 0.009(4) 0.028(3) 0.020(4) C5 0.062(4) 0.043(4) 0.053(4) 0.006(3) 0.020(3) 0.006(3) C6 0.043(3) 0.046(4) 0.040(3) 0.008(3) 0.017(3) 0.007(3) C7 0.044(3) 0.041(4) 0.040(3) 0.010(3) 0.006(3) 0.010(3) C8 0.044(3) 0.049(4) 0.036(3) 0.015(3) 0.007(3) -0.002(3) C9 0.060(4) 0.057(4) 0.040(3) 0.002(3) 0.004(3) -0.014(3) C10 0.071(5) 0.092(5) 0.058(4) 0.010(4) 0.014(3) -0.017(4) C11 0.076(5) 0.085(6) 0.087(5) 0.005(4) 0.029(4) -0.021(4) C12 0.095(5) 0.039(4) 0.084(5) -0.017(4) 0.013(4) -0.015(4) C13 0.065(4) 0.035(4) 0.056(4) -0.002(3) 0.008(3) 0.000(3) C14 0.061(4) 0.067(4) 0.088(5) -0.001(4) 0.029(3) -0.008(3) C15 0.047(4) 0.054(4) 0.032(3) -0.012(3) 0.004(3) 0.012(3) C16 0.056(4) 0.077(5) 0.038(3) -0.005(3) 0.005(3) 0.036(4) C17 0.085(5) 0.090(6) 0.042(4) 0.001(4) 0.016(4) 0.054(4) C18 0.109(6) 0.058(5) 0.072(5) 0.012(4) 0.032(4) 0.043(4) C19 0.084(5) 0.056(4) 0.050(4) 0.002(3) 0.018(3) 0.013(4) C20 0.052(4) 0.046(4) 0.029(3) 0.000(3) 0.005(3) 0.017(3) C21 0.043(3) 0.052(4) 0.035(3) -0.009(3) 0.009(3) 0.001(3) C22 0.039(3) 0.056(4) 0.031(3) -0.004(3) 0.000(3) 0.001(3) C23 0.051(4) 0.067(4) 0.044(4) 0.004(3) 0.018(3) 0.015(3) C24 0.056(4) 0.087(5) 0.050(4) -0.011(4) 0.015(3) 0.025(4) C25 0.050(4) 0.104(6) 0.053(4) -0.005(4) 0.024(3) 0.008(4) C26 0.052(4) 0.082(5) 0.042(4) -0.004(3) 0.018(3) -0.006(3) C27 0.045(4) 0.060(4) 0.036(4) -0.001(3) 0.010(3) -0.001(3) C28 0.048(4) 0.101(5) 0.065(4) -0.016(4) 0.010(3) 0.028(3) C29 0.220(13) 0.099(7) 0.149(11) 0.023(7) 0.063(10) 0.086(8) C30 0.133(8) 0.112(7) 0.145(9) -0.059(7) 0.036(7) 0.021(6) C31 0.115(8) 0.123(8) 0.187(11) -0.061(8) 0.038(8) -0.001(6) C32 0.114(8) 0.129(9) 0.141(9) -0.048(7) 0.030(7) -0.036(6) C33 0.086(7) 0.110(7) 0.219(13) -0.032(8) 0.052(7) 0.021(6) C34 0.120(8) 0.200(12) 0.151(10) -0.001(9) -0.001(7) 0.076(8) C35 0.409(16) 0.156(9) 0.091(7) 0.010(7) -0.054(9) 0.032(9) _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 O1 1.809(3) . ? Ti1 O2 1.850(3) . ? Ti1 N2 2.220(4) . ? Ti1 Cl2 2.2640(16) . ? Ti1 N1 2.279(4) . ? Ti1 Cl1 2.3204(15) . ? N1 C7 1.326(5) . ? N1 C8 1.391(5) . ? N2 C21 1.338(5) . ? N2 C22 1.399(5) . ? O1 C1 1.330(5) . ? O2 C15 1.336(5) . ? S1 C13 1.709(5) . ? S1 C7 1.738(5) . ? S2 C21 1.719(5) . ? S2 C27 1.731(5) . ? C1 C2 1.373(6) . ? C1 C6 1.431(6) . ? C2 C3 1.358(6) . ? C2 C14 1.501(6) . ? C3 C4 1.407(6) . ? C4 C5 1.352(6) . ? C5 C6 1.387(6) . ? C6 C7 1.427(6) . ? C8 C9 1.390(6) . ? C8 C13 1.399(6) . ? C9 C10 1.382(6) . ? C10 C11 1.389(7) . ? C11 C12 1.353(6) . ? C12 C13 1.392(6) . ? C15 C16 1.390(6) . ? C15 C20 1.401(6) . ? C16 C17 1.385(7) . ? C16 C28 1.496(6) . ? C17 C18 1.375(7) . ? C18 C19 1.358(6) . ? C19 C20 1.422(6) . ? C20 C21 1.451(6) . ? C22 C27 1.374(6) . ? C22 C23 1.402(6) . ? C23 C24 1.372(6) . ? C24 C25 1.384(6) . ? C25 C26 1.382(6) . ? C26 C27 1.377(6) . ? C29 C34 1.323(10) . ? C29 C30 1.333(9) . ? C29 C35 1.480(10) . ? C30 C31 1.348(9) . ? C31 C32 1.365(9) . ? C32 C33 1.277(8) . ? C33 C34 1.387(10) . ? 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 O1 Ti1 O2 91.76(14) . . ? O1 Ti1 N2 169.03(14) . . ? O2 Ti1 N2 80.25(14) . . ? O1 Ti1 Cl2 97.27(11) . . ? O2 Ti1 Cl2 97.54(11) . . ? N2 Ti1 Cl2 91.26(11) . . ? O1 Ti1 N1 81.97(14) . . ? O2 Ti1 N1 81.99(13) . . ? N2 Ti1 N1 89.44(15) . . ? Cl2 Ti1 N1 179.09(12) . . ? O1 Ti1 Cl1 96.27(10) . . ? O2 Ti1 Cl1 162.01(11) . . ? N2 Ti1 Cl1 89.43(11) . . ? Cl2 Ti1 Cl1 97.37(6) . . ? N1 Ti1 Cl1 83.22(10) . . ? C7 N1 C8 111.8(4) . . ? C7 N1 Ti1 118.4(3) . . ? C8 N1 Ti1 129.3(3) . . ? C21 N2 C22 109.3(4) . . ? C21 N2 Ti1 121.9(3) . . ? C22 N2 Ti1 128.5(3) . . ? C1 O1 Ti1 134.9(3) . . ? C15 O2 Ti1 134.8(3) . . ? C13 S1 C7 90.7(3) . . ? C21 S2 C27 90.1(3) . . ? O1 C1 C2 119.7(5) . . ? O1 C1 C6 118.3(5) . . ? C2 C1 C6 122.0(5) . . ? C3 C2 C1 119.4(5) . . ? C3 C2 C14 121.1(5) . . ? C1 C2 C14 119.5(5) . . ? C2 C3 C4 120.1(5) . . ? C5 C4 C3 120.4(5) . . ? C4 C5 C6 121.9(5) . . ? C5 C6 C7 121.9(5) . . ? C5 C6 C1 116.1(5) . . ? C7 C6 C1 122.0(5) . . ? N1 C7 C6 128.2(5) . . ? N1 C7 S1 113.5(4) . . ? C6 C7 S1 118.3(4) . . ? C9 C8 N1 126.5(5) . . ? C9 C8 C13 119.5(5) . . ? N1 C8 C13 113.9(5) . . ? C10 C9 C8 119.0(5) . . ? C9 C10 C11 120.8(6) . . ? C12 C11 C10 120.6(6) . . ? C11 C12 C13 119.7(6) . . ? C12 C13 C8 120.2(5) . . ? C12 C13 S1 129.8(5) . . ? C8 C13 S1 110.0(4) . . ? O2 C15 C16 119.1(5) . . ? O2 C15 C20 119.2(5) . . ? C16 C15 C20 121.7(5) . . ? C17 C16 C15 117.6(6) . . ? C17 C16 C28 121.8(5) . . ? C15 C16 C28 120.6(6) . . ? C18 C17 C16 122.0(6) . . ? C19 C18 C17 120.7(6) . . ? C18 C19 C20 119.9(6) . . ? C15 C20 C19 117.9(5) . . ? C15 C20 C21 121.2(5) . . ? C19 C20 C21 120.6(5) . . ? N2 C21 C20 124.6(5) . . ? N2 C21 S2 115.2(4) . . ? C20 C21 S2 120.1(4) . . ? C27 C22 N2 116.0(5) . . ? C27 C22 C23 118.4(5) . . ? N2 C22 C23 125.7(5) . . ? C24 C23 C22 118.7(5) . . ? C23 C24 C25 121.5(5) . . ? C26 C25 C24 120.7(5) . . ? C27 C26 C25 117.0(5) . . ? C22 C27 C26 123.7(5) . . ? C22 C27 S2 109.4(4) . . ? C26 C27 S2 126.8(5) . . ? C34 C29 C30 119.4(11) . . ? C34 C29 C35 122.3(12) . . ? C30 C29 C35 118.4(12) . . ? C29 C30 C31 120.0(10) . . ? C30 C31 C32 121.9(10) . . ? C33 C32 C31 116.2(10) . . ? C32 C33 C34 123.9(10) . . ? C29 C34 C33 118.6(10) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.365 _refine_diff_density_min -0.315 _refine_diff_density_rms 0.054 # Attachment '2c.cif' data_f90325a _database_code_depnum_ccdc_archive 'CCDC 727483' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C36 H36 Cl2 N2 O2 S2 Ti' _chemical_formula_weight 711.59 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' 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' Cl Cl 0.1484 0.1585 '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 15.359(6) _cell_length_b 16.453(7) _cell_length_c 16.708(7) _cell_angle_alpha 90.00 _cell_angle_beta 93.492(6) _cell_angle_gamma 90.00 _cell_volume 4215(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 859 _cell_measurement_theta_min 2.442 _cell_measurement_theta_max 20.036 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.121 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1480 _exptl_absorpt_coefficient_mu 0.458 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9141 _exptl_absorpt_correction_T_max 0.9775 _exptl_absorpt_process_details sadabs _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 6.64 _diffrn_reflns_number 17129 _diffrn_reflns_av_R_equivalents 0.1048 _diffrn_reflns_av_sigmaI/netI 0.1449 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.74 _diffrn_reflns_theta_max 25.01 _reflns_number_total 7405 _reflns_number_gt 3373 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0762P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 7405 _refine_ls_number_parameters 414 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1393 _refine_ls_R_factor_gt 0.0698 _refine_ls_wR_factor_ref 0.1879 _refine_ls_wR_factor_gt 0.1613 _refine_ls_goodness_of_fit_ref 0.879 _refine_ls_restrained_S_all 0.879 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.74457(6) 0.91177(6) 0.90397(6) 0.0396(3) Uani 1 1 d . . . Cl1 Cl 0.67043(9) 0.82588(9) 0.98875(9) 0.0527(4) Uani 1 1 d . . . Cl2 Cl 0.81910(9) 1.01041(9) 0.83325(9) 0.0556(4) Uani 1 1 d . . . N1 N 0.8454(3) 0.9434(3) 1.0011(2) 0.0407(11) Uani 1 1 d . . . N2 N 0.6565(3) 1.0052(2) 0.9505(3) 0.0378(11) Uani 1 1 d . . . O1 O 0.8167(2) 0.8258(2) 0.88709(19) 0.0415(9) Uani 1 1 d . . . O2 O 0.6639(2) 0.9100(2) 0.81726(19) 0.0412(9) Uani 1 1 d . . . S1 S 0.97482(10) 0.91584(10) 1.10235(9) 0.0522(4) Uani 1 1 d . . . S2 S 0.53463(10) 1.11352(9) 0.94079(9) 0.0494(4) Uani 1 1 d . . . C1 C 0.8577(3) 0.7704(3) 0.9358(3) 0.0398(13) Uani 1 1 d . . . C2 C 0.8660(4) 0.6898(3) 0.9119(3) 0.0474(14) Uani 1 1 d . . . C3 C 0.9080(4) 0.6369(4) 0.9665(4) 0.0639(18) Uani 1 1 d . . . H3 H 0.9128 0.5824 0.9527 0.077 Uiso 1 1 calc R . . C4 C 0.9434(4) 0.6628(4) 1.0413(4) 0.0626(18) Uani 1 1 d . . . C5 C 0.9361(4) 0.7411(4) 1.0607(3) 0.0534(16) Uani 1 1 d . . . H5 H 0.9599 0.7584 1.1103 0.064 Uiso 1 1 calc R . . C6 C 0.8945(3) 0.7975(3) 1.0102(3) 0.0425(14) Uani 1 1 d . . . C7 C 0.8947(3) 0.8821(3) 1.0317(3) 0.0404(13) Uani 1 1 d . . . C8 C 0.8700(3) 1.0193(3) 1.0330(3) 0.0433(14) Uani 1 1 d . . . C9 C 0.8339(4) 1.0936(4) 1.0129(4) 0.0563(16) Uani 1 1 d . . . H9 H 0.7883 1.0970 0.9738 0.068 Uiso 1 1 calc R . . C10 C 0.8655(4) 1.1637(4) 1.0511(4) 0.0622(18) Uani 1 1 d . . . H10 H 0.8415 1.2141 1.0374 0.075 Uiso 1 1 calc R . . C11 C 0.9314(5) 1.1583(4) 1.1085(4) 0.074(2) Uani 1 1 d . . . H11 H 0.9514 1.2053 1.1344 0.089 Uiso 1 1 calc R . . C12 C 0.9707(4) 1.0832(4) 1.1300(4) 0.0631(18) Uani 1 1 d . . . H12 H 1.0172 1.0801 1.1683 0.076 Uiso 1 1 calc R . . C13 C 0.9369(3) 1.0143(3) 1.0917(3) 0.0438(14) Uani 1 1 d . . . C14 C 0.8304(4) 0.6597(4) 0.8295(4) 0.0572(17) Uani 1 1 d . . . C15 C 0.8731(5) 0.7097(4) 0.7632(4) 0.082(2) Uani 1 1 d . . . H15A H 0.8731 0.7663 0.7771 0.123 Uiso 1 1 calc R . . H15B H 0.8405 0.7020 0.7129 0.123 Uiso 1 1 calc R . . H15C H 0.9320 0.6917 0.7586 0.123 Uiso 1 1 calc R . . C16 C 0.7303(4) 0.6692(4) 0.8229(4) 0.083(2) Uani 1 1 d . . . H16A H 0.7050 0.6339 0.8609 0.124 Uiso 1 1 calc R . . H16B H 0.7085 0.6549 0.7697 0.124 Uiso 1 1 calc R . . H16C H 0.7152 0.7245 0.8339 0.124 Uiso 1 1 calc R . . C17 C 0.8518(5) 0.5686(4) 0.8145(4) 0.091(3) Uani 1 1 d . . . H17A H 0.9139 0.5614 0.8160 0.137 Uiso 1 1 calc R . . H17B H 0.8268 0.5525 0.7629 0.137 Uiso 1 1 calc R . . H17C H 0.8280 0.5358 0.8553 0.137 Uiso 1 1 calc R . . C18 C 0.9878(6) 0.5984(5) 1.0970(5) 0.114(3) Uani 1 1 d . . . H18A H 1.0367 0.6225 1.1267 0.171 Uiso 1 1 calc R . . H18B H 1.0077 0.5541 1.0654 0.171 Uiso 1 1 calc R . . H18C H 0.9468 0.5786 1.1334 0.171 Uiso 1 1 calc R . . C19 C 0.6260(3) 0.9705(3) 0.7725(3) 0.0410(13) Uani 1 1 d . . . C20 C 0.6098(4) 0.9597(4) 0.6893(3) 0.0498(15) Uani 1 1 d . . . C21 C 0.5742(4) 1.0266(4) 0.6490(3) 0.0580(17) Uani 1 1 d . . . H21 H 0.5646 1.0224 0.5937 0.070 Uiso 1 1 calc R . . C22 C 0.5521(4) 1.0982(4) 0.6840(4) 0.0611(18) Uani 1 1 d . . . C23 C 0.5651(4) 1.1042(3) 0.7653(3) 0.0519(16) Uani 1 1 d . . . H23 H 0.5492 1.1518 0.7908 0.062 Uiso 1 1 calc R . . C24 C 0.6017(3) 1.0406(3) 0.8110(3) 0.0401(13) Uani 1 1 d . . . C25 C 0.6063(3) 1.0472(3) 0.8982(3) 0.0419(14) Uani 1 1 d . . . C26 C 0.6378(3) 1.0242(3) 1.0297(3) 0.0408(13) Uani 1 1 d . . . C27 C 0.6763(3) 0.9917(3) 1.1001(3) 0.0474(15) Uani 1 1 d . . . H27 H 0.7205 0.9532 1.0982 0.057 Uiso 1 1 calc R . . C28 C 0.6482(4) 1.0173(4) 1.1725(3) 0.0529(16) Uani 1 1 d . . . H28 H 0.6737 0.9957 1.2197 0.064 Uiso 1 1 calc R . . C29 C 0.5840(4) 1.0734(4) 1.1762(3) 0.0528(16) Uani 1 1 d . . . H29 H 0.5661 1.0889 1.2261 0.063 Uiso 1 1 calc R . . C30 C 0.5439(4) 1.1087(3) 1.1075(3) 0.0518(15) Uani 1 1 d . . . H30 H 0.5004 1.1476 1.1101 0.062 Uiso 1 1 calc R . . C31 C 0.5733(3) 1.0818(3) 1.0351(3) 0.0407(13) Uani 1 1 d . . . C32 C 0.6319(5) 0.8823(4) 0.6466(4) 0.0650(19) Uani 1 1 d . . . C33 C 0.6056(6) 0.8852(5) 0.5558(4) 0.117(3) Uani 1 1 d . . . H33A H 0.5458 0.9019 0.5479 0.176 Uiso 1 1 calc R . . H33B H 0.6124 0.8321 0.5330 0.176 Uiso 1 1 calc R . . H33C H 0.6422 0.9232 0.5301 0.176 Uiso 1 1 calc R . . C34 C 0.5866(5) 0.8091(4) 0.6813(4) 0.083(2) Uani 1 1 d . . . H34A H 0.6049 0.8033 0.7370 0.125 Uiso 1 1 calc R . . H34B H 0.6018 0.7610 0.6528 0.125 Uiso 1 1 calc R . . H34C H 0.5246 0.8169 0.6760 0.125 Uiso 1 1 calc R . . C35 C 0.7318(5) 0.8680(5) 0.6531(4) 0.089(2) Uani 1 1 d . . . H35A H 0.7611 0.9169 0.6384 0.133 Uiso 1 1 calc R . . H35B H 0.7462 0.8248 0.6177 0.133 Uiso 1 1 calc R . . H35C H 0.7500 0.8536 0.7072 0.133 Uiso 1 1 calc R . . C36 C 0.5143(5) 1.1708(4) 0.6359(4) 0.085(2) Uani 1 1 d . . . H36A H 0.5162 1.2183 0.6692 0.127 Uiso 1 1 calc R . . H36B H 0.4550 1.1594 0.6181 0.127 Uiso 1 1 calc R . . H36C H 0.5481 1.1800 0.5903 0.127 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 0.0362(6) 0.0386(6) 0.0433(6) -0.0002(5) -0.0024(4) 0.0048(5) Cl1 0.0479(9) 0.0488(9) 0.0619(10) 0.0109(8) 0.0081(7) 0.0031(7) Cl2 0.0479(9) 0.0570(10) 0.0611(10) 0.0123(8) -0.0032(7) -0.0043(7) N1 0.032(3) 0.044(3) 0.046(3) 0.000(2) 0.002(2) 0.005(2) N2 0.034(3) 0.030(2) 0.049(3) 0.000(2) -0.003(2) 0.003(2) O1 0.040(2) 0.042(2) 0.043(2) 0.0024(18) 0.0015(16) 0.0057(17) O2 0.040(2) 0.044(2) 0.039(2) -0.0017(18) -0.0047(16) 0.0058(18) S1 0.0460(9) 0.0607(10) 0.0485(9) 0.0012(8) -0.0075(7) 0.0004(8) S2 0.0497(9) 0.0457(9) 0.0519(9) -0.0020(7) -0.0042(7) 0.0133(7) C1 0.030(3) 0.035(3) 0.054(3) 0.005(3) 0.001(3) 0.010(2) C2 0.047(4) 0.039(4) 0.055(4) -0.002(3) -0.001(3) 0.006(3) C3 0.078(5) 0.043(4) 0.070(5) 0.009(3) 0.003(4) 0.023(3) C4 0.077(5) 0.054(4) 0.055(4) 0.011(3) -0.007(3) 0.021(4) C5 0.062(4) 0.053(4) 0.044(3) 0.005(3) -0.012(3) 0.013(3) C6 0.039(3) 0.037(3) 0.050(3) 0.006(3) -0.002(3) 0.006(3) C7 0.030(3) 0.048(4) 0.044(3) -0.002(3) 0.004(2) -0.001(3) C8 0.034(3) 0.041(4) 0.054(4) -0.008(3) -0.002(3) 0.000(3) C9 0.040(4) 0.057(4) 0.073(4) -0.004(4) 0.003(3) -0.003(3) C10 0.046(4) 0.043(4) 0.097(5) -0.018(4) -0.003(4) 0.004(3) C11 0.068(5) 0.069(5) 0.085(5) -0.029(4) 0.005(4) -0.012(4) C12 0.056(4) 0.064(5) 0.067(4) -0.009(4) -0.010(3) -0.008(4) C13 0.042(3) 0.046(4) 0.043(3) -0.010(3) 0.001(3) -0.005(3) C14 0.056(4) 0.044(4) 0.069(4) -0.007(3) -0.014(3) 0.019(3) C15 0.121(7) 0.070(5) 0.055(4) -0.011(4) -0.001(4) 0.019(5) C16 0.077(5) 0.072(5) 0.095(5) -0.021(4) -0.017(4) 0.001(4) C17 0.109(7) 0.064(5) 0.096(6) -0.027(4) -0.025(5) 0.016(4) C18 0.148(8) 0.093(6) 0.094(6) 0.013(5) -0.041(5) 0.045(6) C19 0.038(3) 0.038(3) 0.046(3) 0.008(3) -0.003(3) 0.001(3) C20 0.052(4) 0.054(4) 0.041(3) -0.004(3) -0.011(3) 0.015(3) C21 0.077(5) 0.054(4) 0.042(4) 0.004(3) -0.009(3) 0.013(3) C22 0.082(5) 0.051(4) 0.048(4) 0.007(3) -0.014(3) 0.016(4) C23 0.060(4) 0.047(4) 0.047(4) -0.006(3) -0.005(3) 0.007(3) C24 0.045(3) 0.032(3) 0.043(3) 0.001(3) -0.005(3) -0.003(3) C25 0.046(4) 0.024(3) 0.055(4) -0.001(3) -0.007(3) -0.001(2) C26 0.043(3) 0.040(3) 0.038(3) -0.002(3) -0.007(2) -0.001(3) C27 0.041(3) 0.050(4) 0.052(4) 0.005(3) 0.002(3) 0.010(3) C28 0.063(4) 0.057(4) 0.038(4) 0.000(3) -0.002(3) 0.010(3) C29 0.060(4) 0.058(4) 0.041(3) -0.013(3) 0.006(3) -0.001(3) C30 0.044(4) 0.055(4) 0.057(4) -0.010(3) 0.002(3) 0.002(3) C31 0.037(3) 0.042(3) 0.042(3) 0.000(3) 0.001(2) 0.002(3) C32 0.085(5) 0.064(5) 0.045(4) -0.010(3) -0.009(3) 0.023(4) C33 0.190(9) 0.109(7) 0.047(4) -0.023(4) -0.030(5) 0.065(6) C34 0.112(6) 0.060(5) 0.076(5) -0.021(4) -0.007(4) -0.004(4) C35 0.080(6) 0.109(6) 0.078(5) -0.018(5) 0.013(4) 0.028(5) C36 0.128(7) 0.063(5) 0.060(4) 0.006(4) -0.023(4) 0.023(5) _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 O1 1.829(3) . ? Ti1 O2 1.849(3) . ? Ti1 N2 2.219(4) . ? Ti1 N1 2.235(4) . ? Ti1 Cl1 2.3446(18) . ? Ti1 Cl2 2.3463(18) . ? N1 C7 1.343(6) . ? N1 C8 1.401(6) . ? N2 C25 1.325(6) . ? N2 C26 1.407(6) . ? O1 C1 1.352(5) . ? O2 C19 1.355(6) . ? S1 C13 1.726(6) . ? S1 C7 1.743(5) . ? S2 C31 1.730(5) . ? S2 C25 1.733(5) . ? C1 C2 1.393(7) . ? C1 C6 1.407(7) . ? C2 C3 1.390(7) . ? C2 C14 1.532(7) . ? C3 C4 1.399(8) . ? C4 C5 1.335(8) . ? C4 C18 1.541(8) . ? C5 C6 1.384(7) . ? C6 C7 1.438(7) . ? C8 C9 1.375(7) . ? C8 C13 1.380(7) . ? C9 C10 1.392(8) . ? C10 C11 1.354(8) . ? C11 C12 1.412(8) . ? C12 C13 1.387(7) . ? C14 C16 1.543(8) . ? C14 C15 1.557(9) . ? C14 C17 1.559(8) . ? C19 C24 1.382(7) . ? C19 C20 1.408(7) . ? C20 C21 1.385(7) . ? C20 C32 1.509(8) . ? C21 C22 1.368(7) . ? C22 C23 1.364(7) . ? C22 C36 1.533(8) . ? C23 C24 1.394(7) . ? C24 C25 1.459(7) . ? C26 C31 1.377(7) . ? C26 C27 1.391(7) . ? C27 C28 1.374(7) . ? C28 C29 1.355(7) . ? C29 C30 1.394(8) . ? C30 C31 1.390(7) . ? C32 C34 1.524(9) . ? C32 C33 1.548(8) . ? C32 C35 1.549(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 O1 Ti1 O2 104.50(15) . . ? O1 Ti1 N2 167.80(16) . . ? O2 Ti1 N2 83.78(15) . . ? O1 Ti1 N1 83.84(16) . . ? O2 Ti1 N1 167.03(17) . . ? N2 Ti1 N1 89.68(16) . . ? O1 Ti1 Cl1 87.02(12) . . ? O2 Ti1 Cl1 97.87(12) . . ? N2 Ti1 Cl1 82.93(12) . . ? N1 Ti1 Cl1 92.40(12) . . ? O1 Ti1 Cl2 97.97(12) . . ? O2 Ti1 Cl2 86.59(12) . . ? N2 Ti1 Cl2 91.38(12) . . ? N1 Ti1 Cl2 82.37(12) . . ? Cl1 Ti1 Cl2 172.31(7) . . ? C7 N1 C8 113.0(4) . . ? C7 N1 Ti1 116.8(3) . . ? C8 N1 Ti1 130.0(3) . . ? C25 N2 C26 111.1(4) . . ? C25 N2 Ti1 118.2(4) . . ? C26 N2 Ti1 130.4(3) . . ? C1 O1 Ti1 133.8(3) . . ? C19 O2 Ti1 131.7(3) . . ? C13 S1 C7 90.5(3) . . ? C31 S2 C25 89.6(3) . . ? O1 C1 C2 121.1(5) . . ? O1 C1 C6 117.8(5) . . ? C2 C1 C6 121.1(5) . . ? C3 C2 C1 117.0(5) . . ? C3 C2 C14 120.9(5) . . ? C1 C2 C14 122.1(5) . . ? C2 C3 C4 122.4(6) . . ? C5 C4 C3 118.5(5) . . ? C5 C4 C18 123.9(6) . . ? C3 C4 C18 117.7(6) . . ? C4 C5 C6 122.8(6) . . ? C5 C6 C1 118.1(5) . . ? C5 C6 C7 120.3(5) . . ? C1 C6 C7 121.5(5) . . ? N1 C7 C6 129.7(5) . . ? N1 C7 S1 112.2(4) . . ? C6 C7 S1 117.9(4) . . ? C9 C8 C13 119.9(5) . . ? C9 C8 N1 127.2(5) . . ? C13 C8 N1 112.9(5) . . ? C8 C9 C10 120.0(6) . . ? C11 C10 C9 119.7(6) . . ? C10 C11 C12 121.8(6) . . ? C13 C12 C11 117.2(6) . . ? C8 C13 C12 121.3(6) . . ? C8 C13 S1 111.2(4) . . ? C12 C13 S1 127.3(5) . . ? C2 C14 C16 109.4(5) . . ? C2 C14 C15 109.1(5) . . ? C16 C14 C15 110.9(5) . . ? C2 C14 C17 112.9(5) . . ? C16 C14 C17 107.7(5) . . ? C15 C14 C17 107.0(5) . . ? O2 C19 C24 118.3(5) . . ? O2 C19 C20 119.7(5) . . ? C24 C19 C20 121.9(5) . . ? C21 C20 C19 114.9(5) . . ? C21 C20 C32 122.3(5) . . ? C19 C20 C32 122.8(5) . . ? C22 C21 C20 125.3(5) . . ? C23 C22 C21 117.6(5) . . ? C23 C22 C36 119.6(6) . . ? C21 C22 C36 122.8(5) . . ? C22 C23 C24 121.3(5) . . ? C19 C24 C23 118.9(5) . . ? C19 C24 C25 122.0(5) . . ? C23 C24 C25 118.9(5) . . ? N2 C25 C24 127.6(5) . . ? N2 C25 S2 114.6(4) . . ? C24 C25 S2 117.7(4) . . ? C31 C26 C27 118.7(5) . . ? C31 C26 N2 113.8(4) . . ? C27 C26 N2 127.5(5) . . ? C28 C27 C26 119.1(5) . . ? C29 C28 C27 121.1(5) . . ? C28 C29 C30 122.2(5) . . ? C31 C30 C29 115.7(5) . . ? C26 C31 C30 123.3(5) . . ? C26 C31 S2 110.9(4) . . ? C30 C31 S2 125.8(4) . . ? C20 C32 C34 111.5(5) . . ? C20 C32 C33 112.7(5) . . ? C34 C32 C33 107.4(6) . . ? C20 C32 C35 110.2(5) . . ? C34 C32 C35 109.1(6) . . ? C33 C32 C35 105.8(6) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.499 _refine_diff_density_min -0.478 _refine_diff_density_rms 0.082 # Attachment '3b.cif' data_f80330a _database_code_depnum_ccdc_archive 'CCDC 727484' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H20 Cl2 N2 O2 S2 Zr' _chemical_formula_weight 642.70 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' S S 0.1246 0.1234 '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' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Fdd2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'x+1/4, -y+1/4, z+1/4' '-x+1/4, y+1/4, z+1/4' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' 'x+1/4, -y+3/4, z+3/4' '-x+1/4, y+3/4, z+3/4' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' 'x+3/4, -y+1/4, z+3/4' '-x+3/4, y+1/4, z+3/4' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' 'x+3/4, -y+3/4, z+1/4' '-x+3/4, y+3/4, z+1/4' _cell_length_a 28.606(8) _cell_length_b 30.227(9) _cell_length_c 13.172(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 11390(6) _cell_formula_units_Z 16 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 996 _cell_measurement_theta_min 2.643 _cell_measurement_theta_max 21.478 _exptl_crystal_description prism _exptl_crystal_colour white _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.499 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5184 _exptl_absorpt_coefficient_mu 0.749 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9289 _exptl_absorpt_correction_T_max 0.9425 _exptl_absorpt_process_details sadabs _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 4.01 _diffrn_reflns_number 13619 _diffrn_reflns_av_R_equivalents 0.0554 _diffrn_reflns_av_sigmaI/netI 0.0734 _diffrn_reflns_limit_h_min -36 _diffrn_reflns_limit_h_max 35 _diffrn_reflns_limit_k_min -38 _diffrn_reflns_limit_k_max 37 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 6 _diffrn_reflns_theta_min 1.83 _diffrn_reflns_theta_max 27.14 _reflns_number_total 4422 _reflns_number_gt 3167 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0347P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.00(14) _refine_ls_number_reflns 4422 _refine_ls_number_parameters 337 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0541 _refine_ls_R_factor_gt 0.0362 _refine_ls_wR_factor_ref 0.0802 _refine_ls_wR_factor_gt 0.0734 _refine_ls_goodness_of_fit_ref 0.868 _refine_ls_restrained_S_all 0.868 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.491147(17) 0.806339(13) 0.14889(6) 0.03785(12) Uani 1 1 d . . . N1 N 0.53342(14) 0.86868(13) 0.0858(4) 0.0405(10) Uani 1 1 d . . . N2 N 0.43986(13) 0.86233(13) 0.2063(3) 0.0382(10) Uani 1 1 d . . . O1 O 0.52842(12) 0.82563(10) 0.2676(3) 0.0412(9) Uani 1 1 d . . . O2 O 0.45139(12) 0.81853(11) 0.0304(3) 0.0465(9) Uani 1 1 d . . . S1 S 0.56711(7) 0.94718(5) 0.08180(12) 0.0658(5) Uani 1 1 d . . . S2 S 0.40248(5) 0.93978(4) 0.20646(12) 0.0517(4) Uani 1 1 d . . . Cl1 Cl 0.54722(5) 0.75679(4) 0.07173(12) 0.0574(4) Uani 1 1 d . . . Cl2 Cl 0.44263(5) 0.75113(4) 0.22786(13) 0.0659(5) Uani 1 1 d . . . C1 C 0.53894(17) 0.86464(18) 0.3129(4) 0.0437(14) Uani 1 1 d . . . C2 C 0.54622(19) 0.8650(2) 0.4175(4) 0.0532(15) Uani 1 1 d . . . C3 C 0.5530(2) 0.9050(2) 0.4657(5) 0.070(2) Uani 1 1 d . . . H3 H 0.5568 0.9058 0.5358 0.084 Uiso 1 1 calc R . . C4 C 0.5541(3) 0.9430(3) 0.4114(6) 0.093(2) Uani 1 1 d . . . H4 H 0.5585 0.9697 0.4450 0.112 Uiso 1 1 calc R . . C5 C 0.5487(2) 0.9429(2) 0.3060(5) 0.0696(19) Uani 1 1 d . . . H5 H 0.5493 0.9693 0.2700 0.084 Uiso 1 1 calc R . . C6 C 0.54242(19) 0.90324(17) 0.2555(4) 0.0443(13) Uani 1 1 d . . . C7 C 0.54430(15) 0.90160(15) 0.1457(5) 0.0428(12) Uani 1 1 d . . . C8 C 0.54408(19) 0.87765(16) -0.0163(4) 0.0391(13) Uani 1 1 d . . . C9 C 0.53967(17) 0.84896(18) -0.0981(5) 0.0505(14) Uani 1 1 d . . . H9 H 0.5288 0.8203 -0.0886 0.061 Uiso 1 1 calc R . . C10 C 0.5517(2) 0.8636(2) -0.1931(5) 0.0555(16) Uani 1 1 d . . . H10 H 0.5479 0.8451 -0.2489 0.067 Uiso 1 1 calc R . . C11 C 0.5692(2) 0.9053(2) -0.2063(5) 0.0618(18) Uani 1 1 d . . . H11 H 0.5771 0.9146 -0.2713 0.074 Uiso 1 1 calc R . . C12 C 0.5753(2) 0.9331(2) -0.1276(5) 0.0647(19) Uani 1 1 d . . . H12 H 0.5880 0.9611 -0.1375 0.078 Uiso 1 1 calc R . . C13 C 0.5623(2) 0.91942(18) -0.0331(5) 0.0497(15) Uani 1 1 d . . . C14 C 0.5478(3) 0.8203(2) 0.4768(5) 0.0712(19) Uani 1 1 d . . . H14A H 0.5193 0.8042 0.4654 0.107 Uiso 1 1 calc R . . H14B H 0.5513 0.8261 0.5481 0.107 Uiso 1 1 calc R . . H14C H 0.5739 0.8030 0.4535 0.107 Uiso 1 1 calc R . . C15 C 0.43486(18) 0.85389(17) -0.0186(4) 0.0443(14) Uani 1 1 d . . . C16 C 0.42544(19) 0.8519(2) -0.1234(4) 0.0527(16) Uani 1 1 d . . . C17 C 0.4124(2) 0.8900(2) -0.1728(5) 0.0616(17) Uani 1 1 d . . . H17 H 0.4075 0.8892 -0.2426 0.074 Uiso 1 1 calc R . . C18 C 0.4064(2) 0.9291(2) -0.1221(5) 0.0677(19) Uani 1 1 d . . . H18 H 0.3978 0.9543 -0.1581 0.081 Uiso 1 1 calc R . . C19 C 0.4127(2) 0.93172(18) -0.0205(5) 0.0555(16) Uani 1 1 d . . . H19 H 0.4076 0.9584 0.0130 0.067 Uiso 1 1 calc R . . C20 C 0.42705(18) 0.89399(16) 0.0348(4) 0.0399(12) Uani 1 1 d . . . C21 C 0.42648(15) 0.89522(15) 0.1454(5) 0.0379(11) Uani 1 1 d . . . C22 C 0.42853(19) 0.87199(18) 0.3067(4) 0.0438(14) Uani 1 1 d . . . C23 C 0.43446(18) 0.84447(18) 0.3919(5) 0.0524(14) Uani 1 1 d . . . H23 H 0.4476 0.8165 0.3837 0.063 Uiso 1 1 calc R . . C24 C 0.4213(2) 0.8581(2) 0.4857(5) 0.0611(18) Uani 1 1 d . . . H24 H 0.4248 0.8394 0.5412 0.073 Uiso 1 1 calc R . . C25 C 0.4023(2) 0.9009(2) 0.4984(5) 0.0647(18) Uani 1 1 d . . . H25 H 0.3939 0.9104 0.5630 0.078 Uiso 1 1 calc R . . C26 C 0.3962(2) 0.9284(2) 0.4182(5) 0.0572(17) Uani 1 1 d . . . H26 H 0.3839 0.9566 0.4277 0.069 Uiso 1 1 calc R . . C27 C 0.40854(18) 0.91390(18) 0.3213(4) 0.0441(14) Uani 1 1 d . . . C28 C 0.4326(2) 0.8072(2) -0.1787(6) 0.077(2) Uani 1 1 d . . . H28A H 0.4206 0.8093 -0.2465 0.115 Uiso 1 1 calc R . . H28B H 0.4164 0.7843 -0.1426 0.115 Uiso 1 1 calc R . . H28C H 0.4654 0.8004 -0.1811 0.115 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 Zr1 0.0473(2) 0.0297(2) 0.0366(2) 0.0019(3) -0.0052(3) -0.0029(2) N1 0.051(3) 0.028(2) 0.043(3) -0.003(2) 0.000(2) 0.0000(19) N2 0.041(2) 0.045(2) 0.029(3) 0.004(2) -0.002(2) -0.0012(19) O1 0.052(2) 0.0335(19) 0.038(2) 0.0069(17) -0.0088(18) -0.0059(16) O2 0.058(2) 0.044(2) 0.038(2) -0.0025(18) -0.0077(19) 0.0037(17) S1 0.1056(13) 0.0466(8) 0.0453(10) 0.0015(8) 0.0052(9) -0.0270(8) S2 0.0634(9) 0.0466(8) 0.0451(10) -0.0026(7) -0.0006(8) 0.0093(7) Cl1 0.0688(9) 0.0415(8) 0.0617(11) -0.0073(7) 0.0006(8) 0.0062(6) Cl2 0.0786(11) 0.0473(9) 0.0719(13) 0.0110(8) 0.0015(9) -0.0186(7) C1 0.040(3) 0.057(4) 0.034(4) 0.001(3) -0.003(3) -0.002(2) C2 0.057(3) 0.073(4) 0.030(4) -0.001(3) -0.002(3) -0.014(3) C3 0.104(5) 0.072(4) 0.035(4) 0.004(3) -0.002(4) -0.033(4) C4 0.137(6) 0.085(5) 0.058(5) -0.041(4) 0.011(5) -0.045(5) C5 0.111(6) 0.053(4) 0.045(4) -0.001(3) -0.002(4) -0.030(4) C6 0.058(4) 0.037(3) 0.039(4) -0.007(3) -0.003(3) -0.012(2) C7 0.040(3) 0.039(3) 0.049(4) 0.004(3) -0.002(3) -0.001(2) C8 0.044(3) 0.039(3) 0.034(3) 0.005(3) 0.005(2) 0.000(2) C9 0.047(3) 0.051(3) 0.054(4) 0.010(4) -0.001(4) 0.003(2) C10 0.056(4) 0.069(4) 0.041(4) 0.006(3) 0.003(3) 0.014(3) C11 0.071(4) 0.073(4) 0.041(4) 0.019(4) 0.006(3) 0.009(3) C12 0.091(5) 0.054(4) 0.048(5) 0.006(3) 0.007(4) -0.009(3) C13 0.066(4) 0.046(3) 0.037(4) -0.003(3) 0.003(3) -0.006(3) C14 0.093(5) 0.077(4) 0.043(4) 0.008(4) -0.010(4) -0.020(4) C15 0.040(3) 0.046(3) 0.047(4) -0.004(3) 0.002(3) 0.000(2) C16 0.052(3) 0.065(4) 0.041(4) -0.013(3) -0.008(3) 0.003(3) C17 0.074(4) 0.079(5) 0.032(4) 0.005(3) -0.012(3) 0.013(4) C18 0.086(5) 0.065(4) 0.052(5) 0.029(4) -0.007(4) 0.008(3) C19 0.072(4) 0.045(3) 0.050(4) -0.004(3) -0.004(3) 0.007(3) C20 0.042(3) 0.043(3) 0.034(3) 0.002(3) -0.004(3) -0.001(2) C21 0.036(3) 0.037(2) 0.040(3) 0.001(3) -0.008(3) -0.0034(19) C22 0.040(3) 0.052(3) 0.039(4) -0.005(3) 0.003(3) -0.004(3) C23 0.065(4) 0.053(3) 0.039(4) 0.008(3) -0.003(4) 0.002(3) C24 0.059(4) 0.085(5) 0.039(4) 0.002(4) 0.004(3) -0.001(3) C25 0.058(4) 0.094(5) 0.042(4) 0.000(4) 0.002(3) 0.000(4) C26 0.063(4) 0.061(4) 0.048(5) -0.011(3) 0.001(3) 0.006(3) C27 0.040(3) 0.053(3) 0.040(4) 0.000(3) -0.003(3) -0.005(3) C28 0.082(5) 0.086(5) 0.062(5) -0.024(4) -0.026(4) 0.011(4) _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 Zr1 O2 1.966(4) . ? Zr1 O1 1.980(4) . ? Zr1 N2 2.364(4) . ? Zr1 N1 2.388(4) . ? Zr1 Cl2 2.4069(15) . ? Zr1 Cl1 2.4186(16) . ? N1 C7 1.307(6) . ? N1 C8 1.406(7) . ? N2 C21 1.334(6) . ? N2 C22 1.393(7) . ? O1 C1 1.355(6) . ? O2 C15 1.335(6) . ? S1 C13 1.737(6) . ? S1 C7 1.741(5) . ? S2 C27 1.712(6) . ? S2 C21 1.713(5) . ? C1 C6 1.394(7) . ? C1 C2 1.394(8) . ? C2 C3 1.380(8) . ? C2 C14 1.561(8) . ? C3 C4 1.353(10) . ? C4 C5 1.398(10) . ? C5 C6 1.382(7) . ? C6 C7 1.449(8) . ? C8 C13 1.384(7) . ? C8 C9 1.389(8) . ? C9 C10 1.371(8) . ? C10 C11 1.366(8) . ? C11 C12 1.347(8) . ? C12 C13 1.363(8) . ? C15 C16 1.408(8) . ? C15 C20 1.419(7) . ? C16 C17 1.374(8) . ? C16 C28 1.548(7) . ? C17 C18 1.369(8) . ? C18 C19 1.353(9) . ? C19 C20 1.414(7) . ? C20 C21 1.457(8) . ? C22 C27 1.403(7) . ? C22 C23 1.407(8) . ? C23 C24 1.355(8) . ? C24 C25 1.415(9) . ? C25 C26 1.356(8) . ? C26 C27 1.396(8) . ? 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 O2 Zr1 O1 152.01(12) . . ? O2 Zr1 N2 76.13(14) . . ? O1 Zr1 N2 82.59(14) . . ? O2 Zr1 N1 82.48(15) . . ? O1 Zr1 N1 76.68(15) . . ? N2 Zr1 N1 81.98(13) . . ? O2 Zr1 Cl2 98.01(11) . . ? O1 Zr1 Cl2 99.98(11) . . ? N2 Zr1 Cl2 90.02(10) . . ? N1 Zr1 Cl2 171.64(11) . . ? O2 Zr1 Cl1 99.58(11) . . ? O1 Zr1 Cl1 99.03(11) . . ? N2 Zr1 Cl1 171.64(11) . . ? N1 Zr1 Cl1 90.39(11) . . ? Cl2 Zr1 Cl1 97.74(5) . . ? C7 N1 C8 112.2(5) . . ? C7 N1 Zr1 120.8(4) . . ? C8 N1 Zr1 126.5(3) . . ? C21 N2 C22 110.4(4) . . ? C21 N2 Zr1 121.3(3) . . ? C22 N2 Zr1 126.7(3) . . ? C1 O1 Zr1 136.3(3) . . ? C15 O2 Zr1 137.6(3) . . ? C13 S1 C7 90.5(3) . . ? C27 S2 C21 90.9(3) . . ? O1 C1 C6 120.4(5) . . ? O1 C1 C2 118.3(5) . . ? C6 C1 C2 121.3(5) . . ? C3 C2 C1 118.8(6) . . ? C3 C2 C14 121.6(5) . . ? C1 C2 C14 119.5(5) . . ? C4 C3 C2 120.3(6) . . ? C3 C4 C5 121.4(6) . . ? C6 C5 C4 119.6(6) . . ? C5 C6 C1 118.3(5) . . ? C5 C6 C7 120.3(5) . . ? C1 C6 C7 121.0(5) . . ? N1 C7 C6 128.3(5) . . ? N1 C7 S1 113.6(5) . . ? C6 C7 S1 118.0(4) . . ? C13 C8 C9 118.6(5) . . ? C13 C8 N1 114.3(5) . . ? C9 C8 N1 127.0(5) . . ? C10 C9 C8 118.9(5) . . ? C11 C10 C9 120.4(6) . . ? C12 C11 C10 121.7(6) . . ? C11 C12 C13 118.5(6) . . ? C12 C13 C8 121.7(6) . . ? C12 C13 S1 128.9(5) . . ? C8 C13 S1 109.3(4) . . ? O2 C15 C16 120.5(5) . . ? O2 C15 C20 120.0(5) . . ? C16 C15 C20 119.5(5) . . ? C17 C16 C15 118.7(5) . . ? C17 C16 C28 123.0(6) . . ? C15 C16 C28 118.2(5) . . ? C18 C17 C16 121.9(6) . . ? C19 C18 C17 121.0(6) . . ? C18 C19 C20 120.1(6) . . ? C19 C20 C15 118.6(5) . . ? C19 C20 C21 119.4(5) . . ? C15 C20 C21 121.3(5) . . ? N2 C21 C20 125.4(5) . . ? N2 C21 S2 114.7(4) . . ? C20 C21 S2 119.6(4) . . ? N2 C22 C27 114.5(5) . . ? N2 C22 C23 127.3(5) . . ? C27 C22 C23 118.3(5) . . ? C24 C23 C22 121.0(5) . . ? C23 C24 C25 119.5(6) . . ? C26 C25 C24 121.3(6) . . ? C25 C26 C27 119.1(6) . . ? C26 C27 C22 120.8(6) . . ? C26 C27 S2 129.7(5) . . ? C22 C27 S2 109.4(4) . . ? _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 27.14 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.342 _refine_diff_density_min -0.278 _refine_diff_density_rms 0.053 # Attachment '3c.cif' data_f90324a _database_code_depnum_ccdc_archive 'CCDC 727485' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C36 H36 Cl2 N2 O2 S2 Zr' _chemical_formula_weight 754.91 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' S S 0.1246 0.1234 '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' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, -y, z+1/2' 'x+1/2, y+1/2, z' 'x+1/2, -y+1/2, z+1/2' '-x, -y, -z' '-x, y, -z-1/2' '-x+1/2, -y+1/2, -z' '-x+1/2, y+1/2, -z-1/2' _cell_length_a 20.663(10) _cell_length_b 9.303(4) _cell_length_c 17.749(8) _cell_angle_alpha 90.00 _cell_angle_beta 92.766(7) _cell_angle_gamma 90.00 _cell_volume 3408(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 788 _cell_measurement_theta_min 2.683 _cell_measurement_theta_max 22.910 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.471 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1552 _exptl_absorpt_coefficient_mu 0.637 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9274 _exptl_absorpt_correction_T_max 0.9390 _exptl_absorpt_process_details sadabs _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 4.56 _diffrn_reflns_number 7950 _diffrn_reflns_av_R_equivalents 0.0568 _diffrn_reflns_av_sigmaI/netI 0.1081 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.97 _diffrn_reflns_theta_max 27.01 _reflns_number_total 3654 _reflns_number_gt 2159 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0266P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3654 _refine_ls_number_parameters 208 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0865 _refine_ls_R_factor_gt 0.0435 _refine_ls_wR_factor_ref 0.0780 _refine_ls_wR_factor_gt 0.0712 _refine_ls_goodness_of_fit_ref 0.806 _refine_ls_restrained_S_all 0.806 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.0000 0.72115(5) 0.2500 0.03321(15) Uani 1 2 d S . . S1 S -0.04004(4) 1.19379(9) 0.34398(5) 0.0416(2) Uani 1 1 d . . . Cl1 Cl -0.07812(5) 0.56103(10) 0.30255(5) 0.0596(3) Uani 1 1 d . . . N1 N -0.04805(12) 0.9256(3) 0.30701(14) 0.0348(7) Uani 1 1 d . . . C1 C 0.07000(15) 0.8428(3) 0.39946(17) 0.0314(8) Uani 1 1 d . . . C2 C 0.11639(14) 0.7997(3) 0.45639(16) 0.0318(8) Uani 1 1 d . . . C3 C 0.14027(15) 0.9077(4) 0.50375(17) 0.0370(8) Uani 1 1 d . . . H3 H 0.1715 0.8831 0.5410 0.044 Uiso 1 1 calc R . . C4 C 0.12059(16) 1.0511(4) 0.49921(17) 0.0383(9) Uani 1 1 d . . . C5 C 0.07084(15) 1.0852(4) 0.44834(17) 0.0376(8) Uani 1 1 d . . . H5 H 0.0545 1.1784 0.4471 0.045 Uiso 1 1 calc R . . C6 C 0.04417(15) 0.9822(3) 0.39831(16) 0.0318(8) Uani 1 1 d . . . C7 C -0.01276(15) 1.0164(3) 0.34861(16) 0.0331(8) Uani 1 1 d . . . C8 C -0.10326(15) 0.9927(3) 0.27509(17) 0.0338(8) Uani 1 1 d . . . C9 C -0.15454(16) 0.9250(4) 0.23520(18) 0.0426(9) Uani 1 1 d . . . H9 H -0.1547 0.8258 0.2286 0.051 Uiso 1 1 calc R . . C10 C -0.20488(17) 1.0074(4) 0.20578(19) 0.0498(10) Uani 1 1 d . . . H10 H -0.2392 0.9631 0.1791 0.060 Uiso 1 1 calc R . . C11 C -0.20544(17) 1.1545(4) 0.2151(2) 0.0576(11) Uani 1 1 d . . . H11 H -0.2394 1.2081 0.1933 0.069 Uiso 1 1 calc R . . C12 C -0.15673(17) 1.2228(4) 0.25591(19) 0.0544(10) Uani 1 1 d . . . H12 H -0.1577 1.3219 0.2628 0.065 Uiso 1 1 calc R . . C13 C -0.10594(15) 1.1412(4) 0.28669(17) 0.0377(8) Uani 1 1 d . . . C14 C 0.13703(16) 0.6411(4) 0.46390(18) 0.0381(9) Uani 1 1 d . . . C15 C 0.17447(16) 0.5935(4) 0.39620(18) 0.0517(10) Uani 1 1 d . . . H15A H 0.2101 0.6578 0.3898 0.078 Uiso 1 1 calc R . . H15B H 0.1462 0.5949 0.3516 0.078 Uiso 1 1 calc R . . H15C H 0.1906 0.4978 0.4046 0.078 Uiso 1 1 calc R . . C16 C 0.18040(16) 0.6161(4) 0.53560(18) 0.0488(10) Uani 1 1 d . . . H16A H 0.2197 0.6702 0.5324 0.073 Uiso 1 1 calc R . . H16B H 0.1905 0.5157 0.5402 0.073 Uiso 1 1 calc R . . H16C H 0.1580 0.6469 0.5789 0.073 Uiso 1 1 calc R . . C17 C 0.07649(17) 0.5477(4) 0.4718(2) 0.0549(11) Uani 1 1 d . . . H17A H 0.0892 0.4492 0.4790 0.082 Uiso 1 1 calc R . . H17B H 0.0489 0.5559 0.4270 0.082 Uiso 1 1 calc R . . H17C H 0.0535 0.5796 0.5145 0.082 Uiso 1 1 calc R . . C18 C 0.15304(18) 1.1634(4) 0.54930(19) 0.0561(11) Uani 1 1 d . . . H18A H 0.1842 1.2151 0.5214 0.084 Uiso 1 1 calc R . . H18B H 0.1745 1.1175 0.5920 0.084 Uiso 1 1 calc R . . H18C H 0.1210 1.2291 0.5663 0.084 Uiso 1 1 calc R . . O1 O 0.05158(10) 0.7512(2) 0.34466(11) 0.0354(5) Uani 1 1 d . . . 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 Zr1 0.0390(3) 0.0222(2) 0.0375(3) 0.000 -0.0086(2) 0.000 S1 0.0423(6) 0.0294(5) 0.0521(6) -0.0057(4) -0.0081(5) 0.0042(4) Cl1 0.0684(7) 0.0485(6) 0.0607(6) 0.0124(5) -0.0083(5) -0.0223(5) N1 0.0351(17) 0.0276(15) 0.0411(16) -0.0008(13) -0.0041(13) 0.0010(13) C1 0.0301(19) 0.0309(19) 0.0331(18) -0.0003(15) 0.0007(15) -0.0065(15) C2 0.0320(19) 0.032(2) 0.0316(17) 0.0033(15) 0.0015(15) -0.0034(16) C3 0.032(2) 0.045(2) 0.0335(19) 0.0044(16) -0.0066(16) -0.0050(16) C4 0.041(2) 0.036(2) 0.038(2) -0.0039(16) -0.0007(17) -0.0039(16) C5 0.043(2) 0.0282(19) 0.042(2) -0.0037(15) -0.0011(17) 0.0007(16) C6 0.034(2) 0.0294(19) 0.0319(18) -0.0014(15) 0.0000(15) -0.0008(15) C7 0.039(2) 0.0265(19) 0.0338(19) -0.0011(15) 0.0019(16) 0.0017(15) C8 0.0301(19) 0.035(2) 0.0360(18) 0.0010(16) 0.0012(16) 0.0030(15) C9 0.039(2) 0.038(2) 0.051(2) -0.0042(17) -0.0035(18) -0.0009(17) C10 0.035(2) 0.056(3) 0.058(2) -0.007(2) -0.0084(19) -0.0007(19) C11 0.043(2) 0.052(3) 0.076(3) -0.003(2) -0.017(2) 0.017(2) C12 0.052(2) 0.040(2) 0.070(2) -0.005(2) -0.016(2) 0.010(2) C13 0.035(2) 0.036(2) 0.042(2) -0.0032(16) -0.0026(16) 0.0046(16) C14 0.039(2) 0.034(2) 0.040(2) 0.0047(16) -0.0092(17) -0.0021(16) C15 0.054(3) 0.045(2) 0.055(2) -0.0033(19) -0.014(2) 0.0110(19) C16 0.046(2) 0.044(2) 0.055(2) 0.0111(18) -0.0108(19) -0.0009(18) C17 0.056(3) 0.038(2) 0.068(3) 0.0159(19) -0.017(2) -0.0111(19) C18 0.067(3) 0.046(2) 0.054(2) -0.0083(19) -0.019(2) -0.005(2) O1 0.0433(14) 0.0245(14) 0.0374(12) -0.0016(9) -0.0086(10) 0.0021(10) _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 Zr1 O1 1.966(2) . ? Zr1 O1 1.966(2) 6_556 ? Zr1 N1 2.392(3) . ? Zr1 N1 2.392(3) 6_556 ? Zr1 Cl1 2.4166(12) . ? Zr1 Cl1 2.4166(12) 6_556 ? S1 C13 1.730(3) . ? S1 C7 1.744(3) . ? N1 C7 1.319(4) . ? N1 C8 1.396(4) . ? C1 O1 1.335(3) . ? C1 C6 1.402(4) . ? C1 C2 1.417(4) . ? C2 C3 1.386(4) . ? C2 C14 1.539(4) . ? C3 C4 1.395(4) . ? C4 C5 1.372(4) . ? C4 C18 1.508(4) . ? C5 C6 1.401(4) . ? C6 C7 1.471(4) . ? C8 C9 1.396(4) . ? C8 C13 1.398(4) . ? C9 C10 1.375(4) . ? C10 C11 1.378(5) . ? C11 C12 1.368(4) . ? C12 C13 1.386(4) . ? C14 C15 1.526(4) . ? C14 C17 1.535(4) . ? C14 C16 1.538(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 O1 Zr1 O1 163.67(11) . 6_556 ? O1 Zr1 N1 75.20(8) . . ? O1 Zr1 N1 91.70(9) 6_556 . ? O1 Zr1 N1 91.70(9) . 6_556 ? O1 Zr1 N1 75.20(8) 6_556 6_556 ? N1 Zr1 N1 74.70(13) . 6_556 ? O1 Zr1 Cl1 95.88(7) . . ? O1 Zr1 Cl1 94.17(7) 6_556 . ? N1 Zr1 Cl1 91.61(7) . . ? N1 Zr1 Cl1 162.14(7) 6_556 . ? O1 Zr1 Cl1 94.17(7) . 6_556 ? O1 Zr1 Cl1 95.88(7) 6_556 6_556 ? N1 Zr1 Cl1 162.14(7) . 6_556 ? N1 Zr1 Cl1 91.61(7) 6_556 6_556 ? Cl1 Zr1 Cl1 103.90(6) . 6_556 ? C13 S1 C7 90.20(15) . . ? C7 N1 C8 111.1(3) . . ? C7 N1 Zr1 121.1(2) . . ? C8 N1 Zr1 122.11(19) . . ? O1 C1 C6 119.0(3) . . ? O1 C1 C2 119.9(3) . . ? C6 C1 C2 121.1(3) . . ? C3 C2 C1 115.8(3) . . ? C3 C2 C14 123.6(3) . . ? C1 C2 C14 120.6(3) . . ? C2 C3 C4 124.3(3) . . ? C5 C4 C3 117.8(3) . . ? C5 C4 C18 121.7(3) . . ? C3 C4 C18 120.5(3) . . ? C4 C5 C6 121.2(3) . . ? C5 C6 C1 119.0(3) . . ? C5 C6 C7 120.7(3) . . ? C1 C6 C7 120.1(3) . . ? N1 C7 C6 127.0(3) . . ? N1 C7 S1 114.3(2) . . ? C6 C7 S1 118.7(2) . . ? C9 C8 N1 126.1(3) . . ? C9 C8 C13 119.1(3) . . ? N1 C8 C13 114.8(3) . . ? C10 C9 C8 118.9(3) . . ? C9 C10 C11 121.3(3) . . ? C12 C11 C10 121.0(3) . . ? C11 C12 C13 118.6(4) . . ? C12 C13 C8 121.2(3) . . ? C12 C13 S1 129.5(3) . . ? C8 C13 S1 109.3(2) . . ? C15 C14 C17 110.7(3) . . ? C15 C14 C16 108.1(3) . . ? C17 C14 C16 106.5(3) . . ? C15 C14 C2 111.0(3) . . ? C17 C14 C2 109.1(3) . . ? C16 C14 C2 111.4(3) . . ? C1 O1 Zr1 146.84(19) . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 27.01 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.669 _refine_diff_density_min -0.404 _refine_diff_density_rms 0.070 # Attachment '4b-Revised.cif' data_f80423d _database_code_depnum_ccdc_archive 'CCDC 727486' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H19 Cl4 N O2 S Zr' _chemical_formula_weight 546.42 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' S S 0.1246 0.1234 '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' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.223(4) _cell_length_b 12.381(7) _cell_length_c 12.661(7) _cell_angle_alpha 90.178(7) _cell_angle_beta 90.091(7) _cell_angle_gamma 106.687(7) _cell_volume 1084.5(11) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 997 _cell_measurement_theta_min 2.348 _cell_measurement_theta_max 26.870 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.673 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 548 _exptl_absorpt_coefficient_mu 1.110 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8783 _exptl_absorpt_correction_T_max 0.8971 _exptl_absorpt_process_details sadabs _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 8.00 _diffrn_reflns_number 4434 _diffrn_reflns_av_R_equivalents 0.0558 _diffrn_reflns_av_sigmaI/netI 0.0481 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.61 _diffrn_reflns_theta_max 25.01 _reflns_number_total 3696 _reflns_number_gt 3275 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1537P)^2^+34.6658P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.048(8) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3696 _refine_ls_number_parameters 246 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1469 _refine_ls_R_factor_gt 0.1399 _refine_ls_wR_factor_ref 0.3891 _refine_ls_wR_factor_gt 0.3855 _refine_ls_goodness_of_fit_ref 1.137 _refine_ls_restrained_S_all 1.137 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.6218(2) 0.76048(12) 0.78535(12) 0.0402(7) Uani 1 1 d . . . Cl1 Cl 0.8530(9) 0.9420(5) 0.7401(4) 0.0747(16) Uani 1 1 d . . . Cl2 Cl 0.4783(9) 0.8721(4) 0.9086(4) 0.0674(15) Uani 1 1 d . . . Cl3 Cl 0.4211(10) 0.5893(4) 0.8688(5) 0.0746(16) Uani 1 1 d . . . Cl4 Cl 0.7971(10) 0.6660(6) 0.6733(6) 0.091(2) Uani 1 1 d . . . N1 N 0.373(2) 0.9828(12) 0.6901(12) 0.052(4) Uani 1 1 d . . . H1 H 0.4052 0.9366 0.7321 0.062 Uiso 1 1 calc R . . O1 O 0.427(2) 0.7692(10) 0.6773(10) 0.056(3) Uani 1 1 d . . . O2 O 0.827(2) 0.7518(12) 0.9128(12) 0.068(4) Uani 1 1 d . . . S1 S 0.2622(7) 1.0675(4) 0.5305(3) 0.0488(11) Uani 1 1 d . . . C1 C 0.321(3) 0.7533(15) 0.5897(14) 0.049(4) Uani 1 1 d . . . C2 C 0.270(3) 0.6500(14) 0.5376(16) 0.052(4) Uani 1 1 d . . . C3 C 0.169(3) 0.6378(18) 0.4425(18) 0.067(6) Uani 1 1 d . . . H3 H 0.1272 0.5671 0.4107 0.081 Uiso 1 1 calc R . . C4 C 0.128(3) 0.7289(17) 0.3943(14) 0.056(5) Uani 1 1 d . . . H4 H 0.0753 0.7216 0.3267 0.067 Uiso 1 1 calc R . . C5 C 0.166(3) 0.8288(15) 0.4466(13) 0.049(4) Uani 1 1 d . . . H5 H 0.1251 0.8870 0.4174 0.059 Uiso 1 1 calc R . . C6 C 0.267(3) 0.8473(14) 0.5463(14) 0.048(4) Uani 1 1 d . . . C7 C 0.299(2) 0.9500(15) 0.5926(13) 0.047(4) Uani 1 1 d . . . C8 C 0.339(2) 1.1522(13) 0.6387(14) 0.043(4) Uani 1 1 d . . . C9 C 0.363(3) 1.2692(14) 0.6498(16) 0.055(5) Uani 1 1 d . . . H9 H 0.3375 1.3114 0.5938 0.066 Uiso 1 1 calc R . . C10 C 0.424(3) 1.3178(16) 0.7451(17) 0.066(6) Uani 1 1 d . . . H10 H 0.4279 1.3927 0.7565 0.079 Uiso 1 1 calc R . . C11 C 0.481(3) 1.2572(17) 0.8266(17) 0.064(5) Uani 1 1 d . . . H11 H 0.5296 1.2940 0.8892 0.076 Uiso 1 1 calc R . . C12 C 0.465(3) 1.1452(18) 0.8153(15) 0.058(5) Uani 1 1 d . . . H12 H 0.4999 1.1047 0.8699 0.070 Uiso 1 1 calc R . . C13 C 0.395(3) 1.0929(14) 0.7189(13) 0.047(4) Uani 1 1 d . . . C14 C 0.312(4) 0.543(2) 0.592(2) 0.084(7) Uani 1 1 d . . . H14A H 0.4486 0.5572 0.6015 0.126 Uiso 1 1 calc R . . H14B H 0.2629 0.4781 0.5480 0.126 Uiso 1 1 calc R . . H14C H 0.2491 0.5303 0.6596 0.126 Uiso 1 1 calc R . . C15 C 0.951(4) 0.841(3) 0.975(2) 0.097(9) Uani 1 1 d . . . H15A H 0.8802 0.8933 0.9960 0.116 Uiso 1 1 calc R . . H15B H 1.0602 0.8818 0.9324 0.116 Uiso 1 1 calc R . . C16 C 1.019(4) 0.794(3) 1.069(2) 0.092(8) Uani 1 1 d . . . H16A H 0.9380 0.7947 1.1299 0.110 Uiso 1 1 calc R . . H16B H 1.1521 0.8348 1.0863 0.110 Uiso 1 1 calc R . . C17 C 1.002(6) 0.677(3) 1.033(3) 0.132(14) Uani 1 1 d . . . H17A H 1.1302 0.6690 1.0213 0.158 Uiso 1 1 calc R . . H17B H 0.9404 0.6243 1.0879 0.158 Uiso 1 1 calc R . . C18 C 0.892(6) 0.652(3) 0.938(3) 0.119(13) Uani 1 1 d . . . H18A H 0.7809 0.5868 0.9479 0.143 Uiso 1 1 calc R . . H18B H 0.9699 0.6367 0.8813 0.143 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 Zr1 0.0534(11) 0.0323(9) 0.0335(9) 0.0001(6) 0.0015(6) 0.0103(7) Cl1 0.078(4) 0.070(3) 0.061(3) 0.014(2) -0.005(3) -0.002(3) Cl2 0.099(4) 0.057(3) 0.055(3) -0.002(2) 0.000(3) 0.036(3) Cl3 0.099(4) 0.047(3) 0.072(3) 0.008(2) 0.003(3) 0.013(3) Cl4 0.077(4) 0.099(5) 0.100(5) -0.039(4) 0.005(3) 0.032(3) N1 0.072(10) 0.041(8) 0.050(8) 0.003(6) -0.009(7) 0.026(7) O1 0.081(9) 0.038(6) 0.052(7) -0.001(5) 0.000(6) 0.021(6) O2 0.078(10) 0.056(8) 0.071(9) 0.003(7) -0.022(8) 0.019(7) S1 0.062(3) 0.040(2) 0.044(2) 0.0031(17) -0.0018(19) 0.0139(19) C1 0.055(10) 0.044(9) 0.048(10) -0.003(7) 0.006(8) 0.016(8) C2 0.050(10) 0.033(8) 0.070(12) 0.003(8) 0.002(9) 0.010(7) C3 0.056(12) 0.060(12) 0.081(15) -0.035(11) -0.014(10) 0.010(9) C4 0.058(11) 0.066(12) 0.039(9) -0.003(8) 0.001(8) 0.009(9) C5 0.065(11) 0.048(10) 0.032(8) 0.007(7) 0.010(7) 0.014(8) C6 0.051(10) 0.040(9) 0.054(10) 0.000(7) 0.007(8) 0.015(7) C7 0.046(9) 0.054(10) 0.036(9) 0.004(7) 0.005(7) 0.005(8) C8 0.047(9) 0.029(8) 0.052(10) -0.008(7) -0.006(7) 0.010(7) C9 0.072(12) 0.030(8) 0.063(11) 0.008(8) -0.002(9) 0.017(8) C10 0.092(15) 0.034(9) 0.072(13) -0.020(9) -0.011(11) 0.018(10) C11 0.075(13) 0.053(11) 0.064(12) -0.005(9) -0.004(10) 0.019(10) C12 0.060(11) 0.066(12) 0.046(10) -0.017(9) -0.003(8) 0.012(9) C13 0.049(10) 0.045(9) 0.042(9) -0.003(7) -0.001(7) 0.005(7) C14 0.096(18) 0.068(15) 0.079(16) -0.024(12) -0.002(13) 0.010(13) C15 0.071(16) 0.11(2) 0.10(2) 0.011(16) -0.017(14) 0.003(15) C16 0.083(17) 0.13(3) 0.070(16) 0.020(16) 0.004(13) 0.035(17) C17 0.14(3) 0.15(3) 0.11(2) 0.07(2) -0.04(2) 0.04(2) C18 0.19(4) 0.09(2) 0.11(2) -0.021(17) -0.04(2) 0.09(2) _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 Zr1 O1 1.986(14) . ? Zr1 O2 2.214(14) . ? Zr1 Cl4 2.414(6) . ? Zr1 Cl3 2.442(6) . ? Zr1 Cl1 2.455(6) . ? Zr1 Cl2 2.496(5) . ? N1 C7 1.36(2) . ? N1 C13 1.37(2) . ? O1 C1 1.33(2) . ? O2 C15 1.43(3) . ? O2 C18 1.47(3) . ? S1 C8 1.715(16) . ? S1 C7 1.741(19) . ? C1 C2 1.39(2) . ? C1 C6 1.44(2) . ? C2 C3 1.39(3) . ? C2 C14 1.60(3) . ? C3 C4 1.39(3) . ? C4 C5 1.36(3) . ? C5 C6 1.44(3) . ? C6 C7 1.36(2) . ? C8 C13 1.38(2) . ? C8 C9 1.41(2) . ? C9 C10 1.36(3) . ? C10 C11 1.41(3) . ? C11 C12 1.37(3) . ? C12 C13 1.40(2) . ? C15 C16 1.48(4) . ? C16 C17 1.49(5) . ? C17 C18 1.43(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 O1 Zr1 O2 176.7(6) . . ? O1 Zr1 Cl4 95.8(4) . . ? O2 Zr1 Cl4 87.2(5) . . ? O1 Zr1 Cl3 95.4(4) . . ? O2 Zr1 Cl3 83.1(4) . . ? Cl4 Zr1 Cl3 95.6(3) . . ? O1 Zr1 Cl1 95.4(4) . . ? O2 Zr1 Cl1 85.9(4) . . ? Cl4 Zr1 Cl1 89.5(3) . . ? Cl3 Zr1 Cl1 167.6(2) . . ? O1 Zr1 Cl2 89.2(4) . . ? O2 Zr1 Cl2 87.9(4) . . ? Cl4 Zr1 Cl2 173.3(2) . . ? Cl3 Zr1 Cl2 88.4(2) . . ? Cl1 Zr1 Cl2 85.6(2) . . ? C7 N1 C13 117.2(15) . . ? C1 O1 Zr1 162.2(12) . . ? C15 O2 C18 104(2) . . ? C15 O2 Zr1 129.4(15) . . ? C18 O2 Zr1 125.3(15) . . ? C8 S1 C7 92.8(8) . . ? O1 C1 C2 121.4(16) . . ? O1 C1 C6 118.6(15) . . ? C2 C1 C6 120.0(17) . . ? C1 C2 C3 120.0(17) . . ? C1 C2 C14 119.6(18) . . ? C3 C2 C14 120.2(17) . . ? C4 C3 C2 121.4(17) . . ? C5 C4 C3 119.5(17) . . ? C4 C5 C6 121.8(17) . . ? C7 C6 C1 125.5(17) . . ? C7 C6 C5 117.6(16) . . ? C1 C6 C5 116.8(16) . . ? C6 C7 N1 127.9(17) . . ? C6 C7 S1 124.3(14) . . ? N1 C7 S1 107.7(13) . . ? C13 C8 C9 120.4(16) . . ? C13 C8 S1 110.8(12) . . ? C9 C8 S1 128.7(14) . . ? C10 C9 C8 117.8(17) . . ? C9 C10 C11 121.4(17) . . ? C12 C11 C10 121.1(19) . . ? C11 C12 C13 118(2) . . ? N1 C13 C8 111.5(15) . . ? N1 C13 C12 127.4(17) . . ? C8 C13 C12 121.1(17) . . ? O2 C15 C16 110(2) . . ? C15 C16 C17 101(2) . . ? C18 C17 C16 110(2) . . ? C17 C18 O2 107(3) . . ? _diffrn_measured_fraction_theta_max 0.967 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.967 _refine_diff_density_max 2.152 _refine_diff_density_min -0.898 _refine_diff_density_rms 0.255 # Attachment 'La.cif' data_f80927b _database_code_depnum_ccdc_archive 'CCDC 727487' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H9 N O S' _chemical_formula_weight 227.27 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' S S 0.1246 0.1234 '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 12.432(5) _cell_length_b 5.863(3) _cell_length_c 15.623(7) _cell_angle_alpha 90.00 _cell_angle_beta 111.696(6) _cell_angle_gamma 90.00 _cell_volume 1058.2(8) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 701 _cell_measurement_theta_min 2.806 _cell_measurement_theta_max 19.104 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.427 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 472 _exptl_absorpt_coefficient_mu 0.279 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9462 _exptl_absorpt_correction_T_max 0.9780 _exptl_absorpt_process_details sadabs _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 5.31 _diffrn_reflns_number 4851 _diffrn_reflns_av_R_equivalents 0.0652 _diffrn_reflns_av_sigmaI/netI 0.1428 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 5 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.76 _diffrn_reflns_theta_max 27.08 _reflns_number_total 2262 _reflns_number_gt 889 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1011P)^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 2262 _refine_ls_number_parameters 149 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.1575 _refine_ls_R_factor_gt 0.0771 _refine_ls_wR_factor_ref 0.1996 _refine_ls_wR_factor_gt 0.1803 _refine_ls_goodness_of_fit_ref 0.830 _refine_ls_restrained_S_all 0.830 _refine_ls_shift/su_max 0.005 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.5678(3) 0.8303(6) 0.6282(2) 0.0471(10) Uani 1 1 d . . . O1 O 0.7691(4) 0.6324(6) 0.6861(3) 0.0763(12) Uani 1 1 d D . . S1 S 0.52287(11) 1.2214(2) 0.68458(9) 0.0566(5) Uani 1 1 d . . . C1 C 0.8062(4) 0.8025(9) 0.7452(3) 0.0548(13) Uani 1 1 d D . . C2 C 0.9220(4) 0.8013(10) 0.8052(4) 0.0664(16) Uani 1 1 d . . . H2 H 0.9710 0.6830 0.8035 0.080 Uiso 1 1 calc R . . C3 C 0.9622(5) 0.9774(11) 0.8666(4) 0.0738(17) Uani 1 1 d . . . H3 H 1.0390 0.9756 0.9070 0.089 Uiso 1 1 calc R . . C4 C 0.8928(5) 1.1559(11) 0.8706(4) 0.0719(16) Uani 1 1 d . . . H4 H 0.9223 1.2733 0.9128 0.086 Uiso 1 1 calc R . . C5 C 0.7825(5) 1.1587(8) 0.8128(4) 0.0596(14) Uani 1 1 d . . . H5 H 0.7360 1.2805 0.8155 0.071 Uiso 1 1 calc R . . C6 C 0.7343(4) 0.9876(8) 0.7488(3) 0.0454(12) Uani 1 1 d . . . C7 C 0.6125(4) 0.9921(7) 0.6850(3) 0.0472(12) Uani 1 1 d . . . C8 C 0.4478(4) 0.8762(8) 0.5760(3) 0.0474(12) Uani 1 1 d . . . C9 C 0.4098(4) 1.0825(8) 0.5975(3) 0.0472(12) Uani 1 1 d . . . C10 C 0.2957(5) 1.1548(8) 0.5529(4) 0.0579(14) Uani 1 1 d . . . H10 H 0.2697 1.2917 0.5684 0.069 Uiso 1 1 calc R . . C11 C 0.2226(4) 1.0148(8) 0.4847(3) 0.0561(14) Uani 1 1 d . . . H11 H 0.1460 1.0572 0.4529 0.067 Uiso 1 1 calc R . . C12 C 0.2637(4) 0.8140(9) 0.4642(3) 0.0551(13) Uani 1 1 d . . . H12 H 0.2136 0.7225 0.4180 0.066 Uiso 1 1 calc R . . C13 C 0.3762(4) 0.7411(9) 0.5090(3) 0.0535(13) Uani 1 1 d . . . H13 H 0.4018 0.6037 0.4936 0.064 Uiso 1 1 calc R . . H1 H 0.698(4) 0.637(17) 0.661(7) 0.32(7) Uiso 1 1 d D . . 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 N1 0.067(3) 0.037(2) 0.047(3) -0.0019(19) 0.032(2) -0.002(2) O1 0.090(3) 0.056(2) 0.076(3) -0.012(2) 0.023(2) 0.020(2) S1 0.0719(10) 0.0445(8) 0.0580(9) -0.0066(6) 0.0293(7) 0.0022(6) C1 0.071(4) 0.052(3) 0.043(3) -0.001(2) 0.023(3) -0.002(3) C2 0.058(3) 0.072(4) 0.061(4) -0.007(3) 0.012(3) 0.021(3) C3 0.051(3) 0.100(5) 0.064(4) -0.003(4) 0.013(3) 0.014(3) C4 0.059(4) 0.080(4) 0.071(4) -0.011(3) 0.018(3) -0.010(3) C5 0.069(4) 0.054(3) 0.058(3) 0.001(3) 0.027(3) 0.003(3) C6 0.038(3) 0.056(3) 0.042(3) 0.014(2) 0.014(2) 0.002(2) C7 0.068(3) 0.041(3) 0.044(3) 0.002(2) 0.034(3) 0.000(2) C8 0.055(3) 0.046(3) 0.049(3) 0.013(2) 0.027(3) 0.007(2) C9 0.051(3) 0.052(3) 0.037(3) 0.003(2) 0.016(2) -0.010(2) C10 0.081(4) 0.042(3) 0.062(4) 0.007(3) 0.040(3) 0.007(3) C11 0.050(3) 0.056(3) 0.061(4) 0.007(3) 0.020(3) 0.004(3) C12 0.056(3) 0.062(4) 0.046(3) -0.007(3) 0.018(3) -0.019(3) C13 0.053(3) 0.058(3) 0.050(3) -0.006(3) 0.021(3) -0.019(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag N1 C7 1.277(5) . ? N1 C8 1.437(6) . ? O1 C1 1.321(6) . ? S1 C7 1.744(5) . ? S1 C9 1.754(5) . ? C1 C2 1.398(7) . ? C1 C6 1.420(6) . ? C2 C3 1.372(7) . ? C3 C4 1.372(7) . ? C4 C5 1.335(6) . ? C5 C6 1.386(6) . ? C6 C7 1.473(6) . ? C8 C13 1.352(6) . ? C8 C9 1.384(7) . ? C9 C10 1.396(6) . ? C10 C11 1.385(6) . ? C11 C12 1.367(6) . ? C12 C13 1.380(6) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C7 N1 C8 110.4(4) . . ? C7 S1 C9 88.4(2) . . ? O1 C1 C2 118.1(5) . . ? O1 C1 C6 122.9(5) . . ? C2 C1 C6 119.0(5) . . ? C3 C2 C1 119.0(5) . . ? C4 C3 C2 122.2(5) . . ? C5 C4 C3 119.0(5) . . ? C4 C5 C6 122.8(5) . . ? C5 C6 C1 118.1(4) . . ? C5 C6 C7 122.5(4) . . ? C1 C6 C7 119.4(4) . . ? N1 C7 C6 122.0(4) . . ? N1 C7 S1 117.2(4) . . ? C6 C7 S1 120.8(3) . . ? C13 C8 C9 120.9(5) . . ? C13 C8 N1 125.3(4) . . ? C9 C8 N1 113.7(4) . . ? C8 C9 C10 121.3(4) . . ? C8 C9 S1 110.2(4) . . ? C10 C9 S1 128.4(4) . . ? C11 C10 C9 117.4(5) . . ? C12 C11 C10 119.6(5) . . ? C11 C12 C13 123.0(5) . . ? C8 C13 C12 117.7(5) . . ? _diffrn_measured_fraction_theta_max 0.971 _diffrn_reflns_theta_full 27.08 _diffrn_measured_fraction_theta_full 0.971 _refine_diff_density_max 1.334 _refine_diff_density_min -0.223 _refine_diff_density_rms 0.087