# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global #------------------ AUDIT DETAILS-------------------------------------------# _audit_creation_date 2002-11-05 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.2 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic _audit_update_record ? #------------------ SUBMISSION DETAILS --------------------------------------# _journal_coden_Cambridge 177 _publ_contact_letter # Include date of submission ; Date of submission 06.27.2003 Please consider this CIF submission for supplement to our publication in O.B.C.. ; _publ_section_title ; C-Glycosylmethylene Carbenes: Synthesis of Anhydro-aldose Tosylhydrazones as Precursors, Generation, and a New Route to exo-Glycals ; _publ_section_title_footnote ; ? ; loop_ _publ_author_name _publ_author_address 'Toth, Marietta' ; Department of Organic Chemistry University of Debrecen Debrecen, H-4010 Hungary ; 'Kover,E. Katalin' ; Department of Inorganic and Analytical Chemistry University of Debrecen Debrecen, H-4010 Hungary ; 'Benyei, Attila C.' ; Department of Physical Chemistry University of Debrecen Debrecen, H-4010 Hungary ; 'Somsak, Laszlo' ; Department of Organic Chemistry University of Debrecen Debrecen, H-4010 Hungary ; _publ_contact_author_name 'Prof Laszlo Somsak' _publ_contact_author_address ; Department of Organic Chemistry University of Debrecen Egyetem ter 1. POB 20 Debrecen H-4010 HUNGARY ; _publ_contact_author_email SOMSAK@TIGRIS.KLTE.HU _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993) J. Appl. Cryst. 26, 343-350. Altomare, A. Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999) J. Appl. Cryst. 32, 115-119. Enraf-Nonius (1996). MACH3/PC Software. Enraf-Nonius, Delft, The Netherlands. Farrugia, L. J. (1997) ORTEP-3 for Windows, J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999) WinGX, J. Appl. Cryst. 32, 837-838. Flack, H.D. (1983). Acta Cryst. A39, 876-881. Johnson, C.K. (1965). ORTEP. Report ORNL-3794. Oak Ridge National Laboratory, Tennessee, USA. Orpen, A. G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G., & Taylor, R. (1992). International Tables for Crystallography, Volume C. Sheldrick, G.M. (1997) SHELXL97. Program for crystal structure refinement. University of Gottingen, Germany. Spek, A.L. (1990). Acta Cryst. A46, C34 Streltsov, V. A. & Zavodnik, V. E. (1989) Sov. Phys. Crystallogr. 34, 824-828 Streltsov, V. A. & Zavodnik, V. E. (1990) Sov. Phys. Crystallogr. 35, 281. Wilson, A.J.C. (1992) Ed. International Tables for Crystallography, Volume C, Kluwer Academic Publishers, Dordrecht, The Netherlands. ; _publ_section_figure_captions ; Figure 1. View of (I) (50% probability displacement ellipsoids) ; _publ_section_acknowledgements ; A.C.B. is indebted for the Hungarian Academy of Sciences for a Bolyai Postdoctoral Fellowship. ; _publ_section_table_legends ; Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (\%A^2^) Table 2. Selected geometric parameters (\%A ,\% ) ; #------------------ SECTION 2. COMPOUND(S) DETAILS -------------------------# data_0044b _database_code_CSD 213880 _audit_creation_date 2002-11-05T10:01:47-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' #------------------ CHEMICAL INFORMATION ------------------------------------# _chemical_formula_moiety 'C19 H24 N2 O9 S1' _chemical_formula_sum 'C19 H24 N2 O9 S' _chemical_formula_weight 456.46 _chemical_melting_point 83 #------------------ UNIT CELL INFORMATION -----------------------------------# _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 9.939(7) _cell_length_b 12.907(5) _cell_length_c 20.160(3) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 2586(2) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 9.75 _cell_measurement_theta_max 13.89 #------------------ CRYSTAL INFORMATION -------------------------------------# _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.66 _exptl_crystal_size_mid 0.55 _exptl_crystal_size_min 0.4 _exptl_crystal_density_diffrn 1.172 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 960 _exptl_absorpt_coefficient_mu 0.17 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details ; North A.C.T., Phillips D.C. & Mathews F.S. (1968) Acta. Cryst. A24, 351 Number of psi-scan sets used was 3 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied. ; _exptl_absorpt_correction_T_min 0.8686 _exptl_absorpt_correction_T_max 0.9295 #------------------ DATA COLLECTION INFORMATION -----------------------------# _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_probe x-ray _diffrn_measurement_device_type 'Enraf Nonius MACH3' _diffrn_measurement_method 'non-profiled omega/2theta scans' _diffrn_refln_scan_mode ot _diffrn_refln_scan_width 2.64 _diffrn_refln_scan_mode_backgd mo _diffrn_standards_number 4 _diffrn_standards_interval_count 39 _diffrn_standards_interval_time 30 _diffrn_standards_decay_% 38 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 0 -7 4 -3 -2 7 3 -1 8 -4 0 9 _diffrn_reflns_number 5867 _diffrn_reflns_av_R_equivalents 0 _diffrn_reflns_limit_h_min -4 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.56 _diffrn_reflns_theta_max 25.33 _diffrn_reflns_theta_full 25.33 _diffrn_measured_fraction_theta_max 0.999 _diffrn_measured_fraction_theta_full 0.999 _reflns_number_total 5867 _reflns_number_gt 2786 _reflns_threshold_expression >2sigma(I) #------------------ COMPUTER PROGRAMS USED ----------------------------------# _computing_data_collection 'MACH3/PC (Enraf Nonius, 1996)' _computing_cell_refinement 'MACH3/PC (Enraf Nonius, 1996)' _computing_data_reduction 'PROFIT (Streltsov & Zavodnik, 1989)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #------------------ REFINEMENT INFORMATION ----------------------------------# _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^)+(0.0991P)^2^+0.0233P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_number_reflns 5867 _refine_ls_number_parameters 288 _refine_ls_number_restraints 0 _refine_ls_R_factor_gt 0.0533 _refine_ls_wR_factor_ref 0.1828 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _refine_ls_shift/su_max 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.1(2) _refine_diff_density_max 0.269 _refine_diff_density_min -0.196 #------------------ ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS --------# 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 0 '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 0.006 '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' 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_calc_flag _atom_site_refinement_flags _atom_site_disorder_group _atom_site_disorder_assembly C1 C 0.2367(7) 0.1079(6) 0.7504(4) 0.0753(18) Uani 1 d . . . C2 C 0.3229(5) 0.1897(5) 0.7787(3) 0.0728(18) Uani 1 d . . . H2 H 0.3012 0.2567 0.7584 0.087 Uiso 1 calc R . . C3 C 0.4762(5) 0.1643(5) 0.7686(3) 0.0656(15) Uani 1 d . . . H3 H 0.4946 0.0945 0.7855 0.079 Uiso 1 calc R . . C4 C 0.5593(5) 0.2398(5) 0.8054(3) 0.0650(16) Uani 1 d . . . H4 H 0.5518 0.3081 0.7845 0.078 Uiso 1 calc R . . C5 C 0.5207(6) 0.2476(5) 0.8761(3) 0.0772(17) Uani 1 d . . . H5 H 0.5719 0.3028 0.8978 0.093 Uiso 1 calc R . . C6 C 0.3701(7) 0.2679(5) 0.8828(3) 0.093(2) Uani 1 d . . . H6A H 0.3452 0.266 0.9293 0.111 Uiso 1 calc R . . H6B H 0.3494 0.3363 0.8658 0.111 Uiso 1 calc R . . C7 C 0.5304(7) 0.0789(8) 0.6670(4) 0.094(2) Uani 1 d . . . C8 C 0.5628(8) 0.0980(7) 0.5983(3) 0.123(3) Uani 1 d . . . H8A H 0.5621 0.1712 0.59 0.184 Uiso 1 calc R . . H8B H 0.4975 0.0647 0.5705 0.184 Uiso 1 calc R . . H8C H 0.6506 0.0707 0.5888 0.184 Uiso 1 calc R . . C9 C 0.7925(7) 0.2723(8) 0.7992(3) 0.090(2) Uani 1 d . . . C10 C 0.9317(7) 0.2267(6) 0.7993(4) 0.121(3) Uani 1 d . . . H10A H 0.9257 0.1524 0.7992 0.182 Uiso 1 calc R . . H10B H 0.9789 0.249 0.8383 0.182 Uiso 1 calc R . . H10C H 0.9794 0.2494 0.7606 0.182 Uiso 1 calc R . . C11 C 0.6630(11) 0.1418(9) 0.9378(4) 0.113(3) Uani 1 d . . . C12 C 0.6900(9) 0.0305(9) 0.9542(4) 0.160(4) Uani 1 d . . . H12A H 0.6132 -0.0107 0.9424 0.24 Uiso 1 calc R . . H12B H 0.7069 0.0238 1.0009 0.24 Uiso 1 calc R . . H12C H 0.7671 0.0069 0.9298 0.24 Uiso 1 calc R . . C13 C 0.1224(7) 0.0603(8) 0.5527(3) 0.095(2) Uani 1 d . . . C14 C 0.1645(9) 0.1529(8) 0.5280(5) 0.123(3) Uani 1 d . . . H14 H 0.1265 0.214 0.5438 0.148 Uiso 1 calc . . . C15 C 0.2608(11) 0.1573(7) 0.4808(5) 0.130(3) Uani 1 d . . . H15 H 0.2916 0.2218 0.467 0.156 Uiso 1 calc . . . C16 C 0.3156(9) 0.0688(10) 0.4521(4) 0.115(2) Uani 1 d . . . C17 C 0.2760(11) -0.0275(7) 0.4801(5) 0.122(3) Uani 1 d . . . H17 H 0.3158 -0.0888 0.4659 0.147 Uiso 1 calc . . . C18 C 0.1781(10) -0.0296(7) 0.5286(5) 0.114(3) Uani 1 d . . . H18 H 0.1492 -0.0929 0.5453 0.136 Uiso 1 calc . . . C19 C 0.4202(10) 0.0749(8) 0.3984(5) 0.154(3) Uani 1 d . . . H19A H 0.4364 0.1462 0.3873 0.231 Uiso 1 calc R . . H19B H 0.3888 0.0387 0.3598 0.231 Uiso 1 calc R . . H19C H 0.5022 0.0438 0.4137 0.231 Uiso 1 calc R . . N1 N 0.1597(6) 0.1264(4) 0.7033(3) 0.0848(16) Uani 1 d . . . N2 N 0.0760(6) 0.0458(6) 0.6838(3) 0.093(2) Uani 1 d . . . O1 O 0.2937(4) 0.1921(3) 0.8472(2) 0.0809(12) Uani 1 d . . . O2 O 0.5056(4) 0.1675(3) 0.7005(2) 0.0736(10) Uani 1 d . . . O3 O 0.5274(7) -0.0028(5) 0.6940(3) 0.133(2) Uani 1 d . . . O4 O 0.6963(4) 0.2032(3) 0.8002(2) 0.0788(12) Uani 1 d . . . O5 O 0.7720(5) 0.3641(4) 0.7983(3) 0.1196(19) Uani 1 d . . . O6 O 0.5462(5) 0.1508(4) 0.9075(2) 0.0886(14) Uani 1 d . . . O7 O 0.7377(7) 0.2111(6) 0.9505(3) 0.148(3) Uani 1 d . . . O8 O -0.0715(5) 0.1525(5) 0.6140(3) 0.139(2) Uani 1 d . . . O9 O -0.0722(5) -0.0426(4) 0.6068(3) 0.137(2) Uani 1 d . . . S1 S -0.0015(2) 0.05454(18) 0.61358(10) 0.1065(7) Uani 1 d . . . H1 H 0.248(5) 0.032(4) 0.777(2) 0.068(16) Uiso 1 d . . . H2N H 0.095(4) -0.003(3) 0.698(2) 0.012(13) Uiso 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 C1 0.050(4) 0.087(5) 0.089(5) 0.003(4) -0.003(4) 0.000(4) C2 0.057(4) 0.076(5) 0.085(4) 0.009(4) 0.008(3) 0.000(4) C3 0.056(4) 0.065(4) 0.076(4) -0.001(3) 0.004(3) 0.002(3) C4 0.045(3) 0.075(4) 0.074(4) -0.006(4) 0.000(3) 0.002(3) C5 0.058(4) 0.081(4) 0.092(5) -0.004(4) 0.002(4) 0.004(4) C6 0.093(5) 0.083(5) 0.102(5) -0.021(4) 0.014(4) 0.007(4) C7 0.066(5) 0.124(7) 0.091(6) -0.019(6) 0.018(4) -0.015(5) C8 0.110(6) 0.177(8) 0.080(5) -0.039(5) 0.018(5) -0.016(6) C9 0.055(4) 0.117(6) 0.097(5) -0.017(5) -0.004(4) 0.002(5) C10 0.062(4) 0.122(6) 0.179(8) -0.010(6) 0.012(5) 0.016(4) C11 0.113(8) 0.140(9) 0.087(6) -0.001(6) 0.011(6) 0.015(7) C12 0.112(7) 0.215(11) 0.153(8) 0.071(8) 0.024(6) 0.042(7) C13 0.084(5) 0.089(5) 0.111(5) 0.013(6) -0.018(4) -0.003(5) C14 0.097(6) 0.113(8) 0.160(8) 0.000(6) 0.017(6) 0.008(6) C15 0.136(8) 0.090(6) 0.165(8) 0.011(6) 0.001(7) -0.002(6) C16 0.093(6) 0.149(8) 0.104(6) -0.001(7) -0.007(5) -0.022(7) C17 0.127(8) 0.095(7) 0.145(8) -0.021(6) -0.020(7) -0.004(6) C18 0.106(6) 0.109(7) 0.127(7) -0.018(5) 0.002(6) -0.019(6) C19 0.129(7) 0.191(9) 0.142(8) -0.008(7) 0.021(7) -0.013(7) N1 0.057(3) 0.082(4) 0.115(5) -0.004(4) -0.003(4) -0.004(3) N2 0.078(4) 0.081(4) 0.120(5) 0.013(5) -0.022(3) 0.013(4) O1 0.065(2) 0.082(3) 0.096(3) -0.007(3) 0.014(2) 0.002(2) O2 0.064(2) 0.079(3) 0.077(3) -0.005(3) 0.005(2) -0.002(3) O3 0.156(6) 0.091(3) 0.151(5) -0.023(4) 0.050(5) -0.009(4) O4 0.043(2) 0.084(3) 0.109(3) -0.010(3) 0.004(2) -0.001(2) O5 0.058(3) 0.079(3) 0.222(6) -0.005(4) -0.008(3) -0.007(3) O6 0.068(3) 0.110(4) 0.088(3) 0.000(3) -0.003(2) 0.001(3) O7 0.116(5) 0.196(7) 0.133(5) -0.003(4) -0.034(4) -0.010(5) O8 0.081(3) 0.146(5) 0.188(5) 0.039(4) -0.023(4) 0.039(3) O9 0.087(3) 0.146(5) 0.179(5) 0.004(4) -0.036(4) -0.046(4) S1 0.0655(10) 0.1268(16) 0.1273(16) 0.0099(15) -0.0257(12) 0.0007(15) #------------------ MOLECULAR GEOMETRY --------------------------------------# _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 C1 N1 1.243(7) . ? C1 C2 1.474(8) . ? C2 O1 1.412(6) . ? C2 C3 1.572(8) . ? C3 O2 1.404(6) . ? C3 C4 1.478(7) . ? C4 O4 1.446(6) . ? C4 C5 1.478(7) . ? C5 O6 1.424(7) . ? C5 C6 1.525(9) . ? C6 O1 1.431(7) . ? C7 O3 1.188(8) . ? C7 O2 1.351(8) . ? C7 C8 1.442(9) . ? C9 O5 1.202(8) . ? C9 O4 1.308(8) . ? C9 C10 1.504(9) . ? C11 O7 1.189(10) . ? C11 O6 1.317(10) . ? C11 C12 1.499(12) . ? C13 C14 1.361(10) . ? C13 C18 1.374(10) . ? C13 S1 1.741(8) . ? C14 C15 1.350(12) . ? C15 C16 1.392(12) . ? C16 C17 1.421(11) . ? C16 C19 1.503(11) . ? C17 C18 1.379(12) . ? N1 N2 1.390(7) . ? N2 S1 1.615(6) . ? O8 S1 1.443(5) . ? O9 S1 1.444(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 C2 120.9(7) . . ? O1 C2 C1 105.9(5) . . ? O1 C2 C3 109.2(5) . . ? C1 C2 C3 111.3(5) . . ? O2 C3 C4 110.8(5) . . ? O2 C3 C2 108.7(5) . . ? C4 C3 C2 109.8(5) . . ? O4 C4 C5 109.7(5) . . ? O4 C4 C3 105.9(4) . . ? C5 C4 C3 112.6(5) . . ? O6 C5 C4 108.9(5) . . ? O6 C5 C6 106.6(5) . . ? C4 C5 C6 110.6(5) . . ? O1 C6 C5 111.0(5) . . ? O3 C7 O2 121.2(7) . . ? O3 C7 C8 126.6(9) . . ? O2 C7 C8 112.2(8) . . ? O5 C9 O4 123.3(6) . . ? O5 C9 C10 122.8(7) . . ? O4 C9 C10 113.9(7) . . ? O7 C11 O6 125.7(10) . . ? O7 C11 C12 124.1(10) . . ? O6 C11 C12 110.1(10) . . ? C14 C13 C18 119.2(8) . . ? C14 C13 S1 120.9(8) . . ? C18 C13 S1 119.9(8) . . ? C15 C14 C13 120.8(9) . . ? C14 C15 C16 122.4(9) . . ? C15 C16 C17 116.3(8) . . ? C15 C16 C19 121.8(10) . . ? C17 C16 C19 121.6(11) . . ? C18 C17 C16 119.6(9) . . ? C13 C18 C17 121.2(8) . . ? C1 N1 N2 116.2(6) . . ? N1 N2 S1 118.8(6) . . ? C2 O1 C6 113.4(5) . . ? C7 O2 C3 120.2(5) . . ? C9 O4 C4 117.8(5) . . ? C11 O6 C5 116.2(7) . . ? O8 S1 O9 121.8(3) . . ? O8 S1 N2 106.6(4) . . ? O9 S1 N2 104.8(4) . . ? O8 S1 C13 107.9(4) . . ? O9 S1 C13 108.4(4) . . ? N2 S1 C13 106.5(3) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N2 H2N O5 0.72(4) 2.17(4) 2.813(9) 150(4) 4_646