# Supplementary Material (ESI) for Perkin Transactions # This journal is © The Royal Society of Chemistry 2001 data_cwdimr_s _database_code_CSD 165356 _audit_creation_method SHELXL-97 loop_ _publ_author_name 'Michael, Joseph P.' 'de Koning, C. B.' 'van der Westhuyzen, Christiaan W.' 'Fernandes, Manuel A.' _publ_contact_author_name 'Prof J P Michael' _publ_contact_author_email 'jmichael@aurum.chem.wits.ac.za' _publ_contact_author_address ;School of Chemistry, University of the Witwatersrand, Private Bag 3, Johannesburg, WITS 2050, South Africa ; _publ_requested_journal 'Journal of the Chemical Society, Perkin Transactions 1' _journal_coden_Cambridge 207 _publ_section_title ;Influence of ring size on the outcome of sulfide contractionreactions with thiolactams. Isolation of bicyclic ketene S,N-acetals andthioisom\"unchnones. ; _chemical_name_systematic ;meso-3,3'-dioxo-6,7,6',7'-tetrahydro- 5H,5H'-[2,2']bi([1,3]thiazolo[3,2-a]pyridinyl)-2,2',8,8'-tetracarboxylate ; _chemical_melting_point '252 deg C decomp.' _chemical_formula_moiety 'C26 H32 N2 O10 S2' _chemical_formula_sum 'C26 H32 N2 O10 S2' _chemical_formula_weight 596.66 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)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 9.1807(19) _cell_length_b 11.696(2) _cell_length_c 13.880(3) _cell_angle_alpha 90.00 _cell_angle_beta 105.103(4) _cell_angle_gamma 90.00 _cell_volume 1439.0(5) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_preparation 'Slow evaporation from acetone' _exptl_crystal_description Prismic _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.377 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 628 _exptl_absorpt_coefficient_mu 0.243 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.9373 _exptl_absorpt_correction_T_max 0.9761 _exptl_absorpt_process_details 'Sheldrick, G. M. (1996). SADABS. University of G\"ottingen, Germany.' _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_% ? _diffrn_reflns_number 7624 _diffrn_reflns_av_R_equivalents 0.0476 _diffrn_reflns_av_sigmaI/netI 0.0584 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.31 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2528 _reflns_number_gt 1405 _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, PLATON (Spek, 1990)' _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^)+(0.0838P)^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 2528 _refine_ls_number_parameters 203 _refine_ls_number_restraints 5 _refine_ls_R_factor_all 0.1044 _refine_ls_R_factor_gt 0.0516 _refine_ls_wR_factor_ref 0.1600 _refine_ls_wR_factor_gt 0.1381 _refine_ls_goodness_of_fit_ref 1.028 _refine_ls_restrained_S_all 1.027 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group S1 S 0.98854(10) 0.34335(8) 0.09047(6) 0.0585(3) Uani 1 1 d . . . N4 N 0.8930(3) 0.2795(2) -0.09548(18) 0.0517(7) Uani 1 1 d . . . O3 O 0.9419(3) 0.4312(2) -0.18539(16) 0.0665(7) Uani 1 1 d . . . C2 C 1.0274(3) 0.4382(3) -0.0048(2) 0.0493(8) Uani 1 1 d . . . O2 O 1.2371(3) 0.3492(2) -0.0392(2) 0.0799(8) Uani 1 1 d . . . C3 C 0.9480(4) 0.3848(3) -0.1066(2) 0.0533(9) Uani 1 1 d . . . C8A C 0.9016(3) 0.2424(3) 0.0001(2) 0.0498(8) Uani 1 1 d . . . O1 O 1.2837(3) 0.5045(2) 0.0571(2) 0.0796(8) Uani 1 1 d . . . C8 C 0.8447(4) 0.1411(3) 0.0187(2) 0.0574(9) Uani 1 1 d . . . O4 O 0.9007(4) 0.1746(2) 0.19270(19) 0.0883(9) Uani 1 1 d . . . C9 C 1.1995(4) 0.4375(3) 0.0090(2) 0.0566(9) Uani 1 1 d . . . C5 C 0.8095(4) 0.2130(3) -0.1818(2) 0.0702(11) Uani 1 1 d . . . H5A H 0.8471 0.2302 -0.2393 0.084 Uiso 1 1 calc R . . H5B H 0.7033 0.2331 -0.1978 0.084 Uiso 1 1 calc R . . C6 C 0.8285(5) 0.0890(4) -0.1578(3) 0.0896(13) Uani 1 1 d . . . H6A H 0.9339 0.0684 -0.1473 0.108 Uiso 1 1 calc R . . H6B H 0.7703 0.0449 -0.2140 0.108 Uiso 1 1 calc R . . C7 C 0.7777(5) 0.0592(3) -0.0655(3) 0.0757(11) Uani 1 1 d . . . H7A H 0.6685 0.0624 -0.0809 0.091 Uiso 1 1 calc R . . H7B H 0.8089 -0.0182 -0.0448 0.091 Uiso 1 1 calc R . . C12 C 0.8434(5) 0.1155(4) 0.1213(3) 0.0717(11) Uani 1 1 d . A . C10 C 1.3995(4) 0.3302(4) -0.0295(4) 0.0985(15) Uani 1 1 d D . . H10A H 1.4185 0.3238 -0.0948 0.118 Uiso 1 1 calc R . . H10B H 1.4586 0.3932 0.0060 0.118 Uiso 1 1 calc R . . C11 C 1.4386(6) 0.2247(4) 0.0258(4) 0.142(2) Uani 1 1 d D . . H11A H 1.4194 0.2325 0.0903 0.214 Uiso 1 1 calc R . . H11B H 1.5435 0.2084 0.0339 0.214 Uiso 1 1 calc R . . H11C H 1.3787 0.1633 -0.0099 0.214 Uiso 1 1 calc R . . O5 O 0.7642(4) 0.0200(2) 0.1276(2) 0.0979(10) Uani 1 1 d D . . C13 C 0.7119(10) -0.0100(12) 0.2167(6) 0.088(4) Uani 0.63(2) 1 d PD A 1 H13A H 0.6955 0.0581 0.2524 0.105 Uiso 0.63(2) 1 calc PR A 1 H13B H 0.6192 -0.0539 0.1983 0.105 Uiso 0.63(2) 1 calc PR A 1 C14 C 0.8374(10) -0.0793(12) 0.2775(8) 0.091(4) Uani 0.63(2) 1 d PD A 1 H14A H 0.8499 -0.1469 0.2413 0.137 Uiso 0.63(2) 1 calc PR A 1 H14B H 0.8149 -0.1007 0.3389 0.137 Uiso 0.63(2) 1 calc PR A 1 H14C H 0.9288 -0.0353 0.2919 0.137 Uiso 0.63(2) 1 calc PR A 1 C13' C 0.793(4) -0.0045(14) 0.2356(3) 0.109(9) Uani 0.37(2) 1 d PD A 2 H13C H 0.8963 0.0147 0.2702 0.131 Uiso 0.37(2) 1 calc PR A 2 H13D H 0.7253 0.0391 0.2645 0.131 Uiso 0.37(2) 1 calc PR A 2 C14' C 0.766(4) -0.1286(12) 0.2428(18) 0.126(8) Uani 0.37(2) 1 d PD A 2 H14D H 0.6863 -0.1523 0.1868 0.188 Uiso 0.37(2) 1 calc PR A 2 H14E H 0.7384 -0.1442 0.3035 0.188 Uiso 0.37(2) 1 calc PR A 2 H14F H 0.8567 -0.1699 0.2427 0.188 Uiso 0.37(2) 1 calc PR A 2 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 S1 0.0565(6) 0.0735(7) 0.0402(5) 0.0028(4) 0.0033(4) -0.0010(5) N4 0.0443(15) 0.0648(19) 0.0415(16) -0.0004(14) 0.0031(12) -0.0020(14) O3 0.0781(17) 0.0768(16) 0.0423(14) 0.0061(13) 0.0117(12) 0.0010(13) C2 0.0383(18) 0.0637(19) 0.0431(18) 0.0030(17) 0.0054(14) 0.0042(15) O2 0.0427(15) 0.0825(18) 0.114(2) -0.0206(17) 0.0202(14) 0.0073(13) C3 0.0388(18) 0.073(2) 0.045(2) 0.0020(19) 0.0055(15) 0.0088(18) C8A 0.0403(18) 0.066(2) 0.0408(18) 0.0032(17) 0.0070(14) 0.0062(17) O1 0.0419(14) 0.0936(19) 0.094(2) -0.0262(16) 0.0016(13) -0.0016(13) C8 0.051(2) 0.067(2) 0.053(2) 0.0009(19) 0.0110(16) 0.0048(18) O4 0.118(2) 0.089(2) 0.0581(16) 0.0036(15) 0.0238(16) -0.0040(17) C9 0.041(2) 0.072(2) 0.054(2) 0.001(2) 0.0084(16) 0.0074(19) C5 0.069(2) 0.085(3) 0.048(2) -0.009(2) 0.0024(18) -0.009(2) C6 0.107(3) 0.094(3) 0.066(3) -0.020(2) 0.018(2) -0.017(3) C7 0.076(3) 0.071(2) 0.078(3) -0.005(2) 0.018(2) -0.012(2) C12 0.081(3) 0.067(3) 0.070(3) 0.004(2) 0.025(2) 0.008(2) C10 0.055(3) 0.094(3) 0.146(4) 0.005(3) 0.025(3) 0.015(2) C11 0.080(4) 0.121(4) 0.213(6) 0.003(5) 0.013(4) 0.014(3) O5 0.148(3) 0.078(2) 0.081(2) 0.0079(16) 0.054(2) -0.010(2) C13 0.067(6) 0.114(9) 0.091(6) 0.003(6) 0.036(4) -0.008(5) C14 0.086(6) 0.115(11) 0.074(6) 0.019(6) 0.023(4) -0.004(6) C13' 0.18(3) 0.072(11) 0.085(12) 0.027(9) 0.058(12) -0.019(16) C14' 0.18(2) 0.109(14) 0.092(14) 0.007(11) 0.048(14) -0.033(14) _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 S1 C8A 1.756(3) . ? S1 C2 1.831(3) . ? N4 C3 1.354(4) . ? N4 C8A 1.378(4) . ? N4 C5 1.466(4) . ? O3 C3 1.209(4) . ? C2 C9 1.542(4) . ? C2 C3 1.543(4) . ? C2 C2 1.548(6) 3_765 ? O2 C9 1.323(4) . ? O2 C10 1.478(4) . ? C8A C8 1.346(4) . ? O1 C9 1.179(4) . ? C8 C12 1.460(5) . ? C8 C7 1.513(4) . ? O4 C12 1.210(4) . ? C5 C6 1.489(5) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 C7 1.514(5) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C12 O5 1.348(5) . ? C10 C11 1.4486(11) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? O5 C13 1.4803(11) . ? O5 C13' 1.4804(11) . ? C13 C14 1.4798(11) . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C13' C14' 1.4799(11) . ? C13' H13C 0.9700 . ? C13' H13D 0.9700 . ? C14' H14D 0.9600 . ? C14' H14E 0.9600 . ? C14' H14F 0.9600 . ? 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 C8A S1 C2 91.66(15) . . ? C3 N4 C8A 117.8(3) . . ? C3 N4 C5 121.4(3) . . ? C8A N4 C5 120.4(3) . . ? C9 C2 C3 109.6(3) . . ? C9 C2 C2 109.9(3) . 3_765 ? C3 C2 C2 111.8(3) . 3_765 ? C9 C2 S1 107.0(2) . . ? C3 C2 S1 106.4(2) . . ? C2 C2 S1 112.0(3) 3_765 . ? C9 O2 C10 117.5(3) . . ? O3 C3 N4 125.5(3) . . ? O3 C3 C2 123.1(3) . . ? N4 C3 C2 111.4(3) . . ? C8 C8A N4 122.3(3) . . ? C8 C8A S1 125.6(2) . . ? N4 C8A S1 112.1(3) . . ? C8A C8 C12 118.0(3) . . ? C8A C8 C7 120.6(3) . . ? C12 C8 C7 121.3(3) . . ? O1 C9 O2 125.9(3) . . ? O1 C9 C2 124.5(3) . . ? O2 C9 C2 109.6(3) . . ? N4 C5 C6 109.2(3) . . ? N4 C5 H5A 109.8 . . ? C6 C5 H5A 109.8 . . ? N4 C5 H5B 109.8 . . ? C6 C5 H5B 109.8 . . ? H5A C5 H5B 108.3 . . ? C5 C6 C7 111.7(4) . . ? C5 C6 H6A 109.3 . . ? C7 C6 H6A 109.3 . . ? C5 C6 H6B 109.3 . . ? C7 C6 H6B 109.3 . . ? H6A C6 H6B 107.9 . . ? C8 C7 C6 110.8(3) . . ? C8 C7 H7A 109.5 . . ? C6 C7 H7A 109.5 . . ? C8 C7 H7B 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 108.1 . . ? O4 C12 O5 123.2(4) . . ? O4 C12 C8 124.7(4) . . ? O5 C12 C8 112.0(4) . . ? C11 C10 O2 106.3(4) . . ? C11 C10 H10A 110.5 . . ? O2 C10 H10A 110.5 . . ? C11 C10 H10B 110.5 . . ? O2 C10 H10B 110.5 . . ? H10A C10 H10B 108.7 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C12 O5 C13 123.2(7) . . ? C12 O5 C13' 105.5(7) . . ? C13 O5 C13' 28.4(12) . . ? C14 C13 O5 103.5(6) . . ? C14 C13 H13A 111.1 . . ? O5 C13 H13A 111.1 . . ? C14 C13 H13B 111.1 . . ? O5 C13 H13B 111.1 . . ? H13A C13 H13B 109.0 . . ? C14' C13' O5 105.6(11) . . ? C14' C13' H13C 110.6 . . ? O5 C13' H13C 110.6 . . ? C14' C13' H13D 110.6 . . ? O5 C13' H13D 110.6 . . ? H13C C13' H13D 108.7 . . ? C13' C14' H14D 109.5 . . ? C13' C14' H14E 109.5 . . ? H14D C14' H14E 109.5 . . ? C13' C14' H14F 109.5 . . ? H14D C14' H14F 109.5 . . ? H14E C14' H14F 109.5 . . ? 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 C8A S1 C2 C9 -110.6(2) . . . . ? C8A S1 C2 C3 6.5(2) . . . . ? C8A S1 C2 C2 128.9(3) . . . 3_765 ? C8A N4 C3 O3 -176.2(3) . . . . ? C5 N4 C3 O3 -4.0(5) . . . . ? C8A N4 C3 C2 6.2(4) . . . . ? C5 N4 C3 C2 178.4(3) . . . . ? C9 C2 C3 O3 -70.5(4) . . . . ? C2 C2 C3 O3 51.6(5) 3_765 . . . ? S1 C2 C3 O3 174.1(3) . . . . ? C9 C2 C3 N4 107.2(3) . . . . ? C2 C2 C3 N4 -130.7(3) 3_765 . . . ? S1 C2 C3 N4 -8.2(3) . . . . ? C3 N4 C8A C8 177.3(3) . . . . ? C5 N4 C8A C8 5.1(5) . . . . ? C3 N4 C8A S1 -1.0(3) . . . . ? C5 N4 C8A S1 -173.2(2) . . . . ? C2 S1 C8A C8 178.1(3) . . . . ? C2 S1 C8A N4 -3.6(2) . . . . ? N4 C8A C8 C12 -172.8(3) . . . . ? S1 C8A C8 C12 5.2(5) . . . . ? N4 C8A C8 C7 4.3(5) . . . . ? S1 C8A C8 C7 -177.6(3) . . . . ? C10 O2 C9 O1 2.1(5) . . . . ? C10 O2 C9 C2 -176.4(3) . . . . ? C3 C2 C9 O1 151.4(3) . . . . ? C2 C2 C9 O1 28.2(5) 3_765 . . . ? S1 C2 C9 O1 -93.6(4) . . . . ? C3 C2 C9 O2 -30.1(4) . . . . ? C2 C2 C9 O2 -153.3(3) 3_765 . . . ? S1 C2 C9 O2 84.9(3) . . . . ? C3 N4 C5 C6 152.4(3) . . . . ? C8A N4 C5 C6 -35.6(4) . . . . ? N4 C5 C6 C7 56.9(4) . . . . ? C8A C8 C7 C6 17.8(5) . . . . ? C12 C8 C7 C6 -165.1(4) . . . . ? C5 C6 C7 C8 -48.5(5) . . . . ? C8A C8 C12 O4 -6.3(6) . . . . ? C7 C8 C12 O4 176.6(4) . . . . ? C8A C8 C12 O5 170.9(3) . . . . ? C7 C8 C12 O5 -6.3(5) . . . . ? C9 O2 C10 C11 112.7(4) . . . . ? O4 C12 O5 C13 13.1(7) . . . . ? C8 C12 O5 C13 -164.1(4) . . . . ? O4 C12 O5 C13' -11.5(16) . . . . ? C8 C12 O5 C13' 171.3(15) . . . . ? C12 O5 C13 C14 -90.7(13) . . . . ? C13' O5 C13 C14 -33.2(16) . . . . ? C12 O5 C13' C14' -156(3) . . . . ? C13 O5 C13' C14' 71(2) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.354 _refine_diff_density_min -0.213 _refine_diff_density_rms 0.045