Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Kentaro Okuma' _publ_contact_author_address ; Department of Chemistry Fukuoka University Faculty of Science Jonan-ku Fukuoka 814-0180 JAPAN ; _publ_contact_author_email KOKUMA@FUKUOKA-U.AC.JP _publ_section_title ; Reaction of Thioketones with Propiolic Acids ; _publ_section_references ; Mackay, S., Gilmore, C. J.,Edwards, C., Stewart, N. & Shankland, K. (1999). maXus Computer Program for the Solution and Refinement of Crystal Structures. Bruker Nonius, The Netherlands, MacScience, Japan & The University of Glasgow. Johnson, C. K. (1976). ORTEP-II. A Fortran Thermal-Ellipsoid Plot Program. Report ORNL-5138. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Enraf-Nonius (1989). CAD-4 Software. Version 5.0. Enraf-Nonius, Delft, The Netherlands. Enraf-Nonius (1993). CAD-4/PC Software. Version 1.2. Enraf-Nonius, Delft, The Netherlands. Harms, K. & Wocadlo, S. (1996) XCAD-4. Program for Processing CAD-4 Diffractometer Data. University of Marburg, Germany. Altomare, A., Burla, M.C., Camalli, M., Cascarano, G.L., Giacovazzo, C., Guagliardi, A., Moliterni, A.G.G & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119. Sheldrick, G. M. (1997). SHELXL97. Program for the Refinement of Crystal Structures. University of Gottingen, Germany. ; loop_ _publ_author_name 'Kentaro Okuma' 'Tohru Inoue' 'Masahiro Koda' 'Tsutomu Kurisaki' 'Shinobu Maekawa' 'Kosei Shioji' 'Hisanobu Wakita' ; Y.Yokomori ; data_compound_1 _database_code_depnum_ccdc_archive 'CCDC 604020' _audit_creation_method maXus _publ_section_abstract ; We present the crystal and molecular structure of exo-Spiro[camphane-2,2'- [1,3]-oxathiin]-6'-one 3i ; _publ_section_comment ; The study of the titled structure was undertaken to establish its three dimensional structure. Geometries are tabulated below. All diagrams and calculations were performed using maXus (Bruker Nonius, Delft & MacScience, Japan). ; _chemical_compound_source 'K. Okuma' _exptl_crystal_description Plate _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.05 _cell_measurement_temperature 298 _refine_ls_hydrogen_treatment refxyz _diffrn_measurement_device 'Enraf Nonius CAD4, 1989' _computing_cell_refinement 'Enraf Nonius CAD4, 1989' _computing_data_collection 'Enraf Nonius CAD4, 1989' _computing_data_reduction 'maXus (Mackay et al., 1999)' _diffrn_radiation_source 'fine-focus sealed tube' loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 1 -4 5 5 -2 -3 4 -1 -1 _diffrn_standards_decay_% 4.091 _diffrn_standards_interval_time 5035 _diffrn_standards_number 3 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 24 loop_ _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_wavelength_id all _diffrn_orient_matrix_type X=UH _diffrn_orient_matrix_UB_11 0.04499 _diffrn_orient_matrix_UB_12 0.09637 _diffrn_orient_matrix_UB_13 0.01684 _diffrn_orient_matrix_UB_21 0.11956 _diffrn_orient_matrix_UB_22 -0.04148 _diffrn_orient_matrix_UB_23 0.00504 _diffrn_orient_matrix_UB_31 0.02450 _diffrn_orient_matrix_UB_32 0.02544 _diffrn_orient_matrix_UB_33 -0.05557 _cell_formula_units_Z 4 _exptl_crystal_density_diffrn 1.296 _exptl_crystal_density_method 'not measured' _exptl_special_details ; ? ; _chemical_formula_weight 238.349 _diffrn_radiation_type ' MoK\a' 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' _symmetry_space_group_name_H-M 'P 21 21 21 ' _symmetry_cell_setting Orthorhombic _chemical_formula_moiety 'C13 H18 O2 S ' _chemical_formula_sum 'C13 H18 O2 S ' _chemical_name_systematic ; ? ; _cell_length_a 7.69(5) _cell_length_b 9.26(5) _cell_length_c 17.15(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1221.(11) _diffrn_reflns_number 4013 _diffrn_reflns_theta_max 29.91 _diffrn_reflns_av_R_equivalents 0.033 _diffrn_measurement_method '\w-2\q scan' # Nonius CAD4 data collection loop_ _diffrn_attenuator_code _diffrn_attenuator_scale 1 19.200 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 11.5800 _cell_measurement_theta_max 15.0000 loop_ _diffrn_orient_refln_index_h _diffrn_orient_refln_index_k _diffrn_orient_refln_index_l _diffrn_orient_refln_angle_theta _diffrn_orient_refln_angle_kappa _diffrn_orient_refln_angle_omega _diffrn_orient_refln_angle_phi 1 5 4 12.3300 -93.5900 15.1900 -8.9200 -1 5 4 12.3400 -116.3900 17.2000 -15.1900 1 -5 4 12.3300 61.1600 26.4800 -43.1400 1 5 -4 12.3300 -120.0300 -4.6300 50.5600 1 -5 -4 12.3300 54.3300 7.1500 14.7900 -1 5 -4 12.3300 -147.2600 -1.9200 42.8500 -1 -5 4 12.3200 93.9400 29.2800 -51.0900 -1 -5 -4 12.3200 80.7800 9.5000 8.5600 4 2 1 11.5900 -48.1200 7.6300 12.2300 -4 2 1 11.5900 -172.3700 16.0400 -14.0700 4 -2 1 11.5800 0.0500 11.9300 -1.2300 4 2 -1 11.5800 -51.3000 2.6400 27.5600 4 -2 -1 11.5800 -1.2700 7.2200 13.5100 -4 2 -1 11.5900 179.3900 11.2500 0.8100 -4 -2 1 11.5800 146.8200 20.6500 -28.1600 -4 -2 -1 11.5900 139.9400 15.6100 -12.7900 5 3 1 14.9800 -52.7000 10.2400 14.7500 -5 3 1 14.9800 -170.0400 18.3600 -10.7700 5 -3 1 14.9800 4.1000 15.2400 -0.9900 5 3 -1 14.9800 -55.3400 6.3400 26.6300 5 -3 -1 14.9700 3.1400 11.6200 10.4000 -5 3 -1 15.0000 -176.4400 14.7000 0.7000 -5 -3 1 14.9800 142.1400 23.7000 -27.1600 -5 -3 -1 14.9800 136.9300 19.7600 -15.1300 1 5 6 13.4600 -88.3800 20.3000 -21.1200 _exptl_crystal_F_000 512.0 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_correction_T_min 0.904 _exptl_absorpt_correction_T_max 0.988 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _exptl_absorpt_coefficient_mu 0.248 _reflns_number_total 2044 _reflns_number_gt 1458 _reflns_threshold_expression >2sigma(I) _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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 w=1/[\s^2^(Fo^2^)+ (0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _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 -0.10(18) _refine_ls_number_reflns 2044 _refine_ls_number_parameters 145 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0781 _refine_ls_R_factor_gt 0.0485 _refine_ls_wR_factor_ref 0.1502 _refine_ls_wR_factor_gt 0.1291 _refine_ls_goodness_of_fit_ref 0.991 _refine_ls_restrained_S_all 0.991 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group S1 S 0.29459(12) 0.00257(10) -0.00847(4) 0.0542(3) Uani 1 d . . . O1 O 0.1971(3) -0.1293(2) 0.12183(12) 0.0414(5) Uani 1 d . . . O2 O 0.2403(5) -0.3581(3) 0.14968(18) 0.0782(9) Uani 1 d . . . C1 C 0.2830(3) 0.0015(3) 0.09834(13) 0.0361(5) Uani 1 d . . . C2 C 0.1775(4) 0.1313(3) 0.12973(15) 0.0343(6) Uani 1 d . . . C3 C 0.2475(5) 0.2670(3) 0.0892(2) 0.0489(8) Uani 1 d . . . C4 C 0.4334(5) 0.2845(4) 0.1235(2) 0.0586(9) Uani 1 d . . . C5 C 0.4443(4) 0.1615(4) 0.18250(19) 0.0479(7) Uani 1 d . . . C6 C 0.4642(4) 0.0197(4) 0.13740(18) 0.0487(7) Uani 1 d . . . C7 C 0.2561(4) 0.1511(3) 0.21316(15) 0.0372(6) Uani 1 d . . . C8 C 0.2756(5) -0.2591(4) 0.1069(2) 0.0545(9) Uani 1 d . . . C9 C 0.3767(6) -0.2696(5) 0.0362(2) 0.0717(12) Uani 1 d . . . C10 C 0.3786(5) -0.1680(5) -0.0185(2) 0.0713(12) Uani 1 d . . . C11 C -0.0192(4) 0.1144(3) 0.1231(2) 0.0451(7) Uani 1 d . . . C12 C 0.2260(5) 0.0273(3) 0.27082(17) 0.0494(8) Uani 1 d . . . C13 C 0.1926(6) 0.2888(4) 0.2541(2) 0.0559(8) Uani 1 d . . . H3A H 0.1760 0.3504 0.1011 0.059 Uiso 1 calc R . . H3B H 0.2515 0.2540 0.0331 0.059 Uiso 1 calc R . . H4A H 0.5213 0.2743 0.0832 0.070 Uiso 1 calc R . . H4B H 0.4472 0.3775 0.1487 0.070 Uiso 1 calc R . . H5 H 0.5318 0.1760 0.2233 0.057 Uiso 1 calc R . . H6A H 0.4893 -0.0601 0.1723 0.058 Uiso 1 calc R . . H6B H 0.5557 0.0266 0.0986 0.058 Uiso 1 calc R . . H9 H 0.4440 -0.3518 0.0286 0.086 Uiso 1 calc R . . H10 H 0.4296 -0.1913 -0.0660 0.086 Uiso 1 calc R . . H11A H -0.0509 0.1043 0.0693 0.054 Uiso 1 calc R . . H11B H -0.0752 0.1981 0.1446 0.054 Uiso 1 calc R . . H11C H -0.0554 0.0301 0.1514 0.054 Uiso 1 calc R . . H12A H 0.2358 -0.0633 0.2440 0.059 Uiso 1 calc R . . H12B H 0.1119 0.0357 0.2931 0.059 Uiso 1 calc R . . H12C H 0.3115 0.0318 0.3115 0.059 Uiso 1 calc R . . H13A H 0.2573 0.3028 0.3014 0.067 Uiso 1 calc R . . H13B H 0.0712 0.2795 0.2662 0.067 Uiso 1 calc R . . H13C H 0.2097 0.3702 0.2204 0.067 Uiso 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 S1 0.0585(5) 0.0702(5) 0.0338(3) -0.0008(4) 0.0030(3) 0.0018(5) O1 0.0467(11) 0.0324(10) 0.0452(10) -0.0011(8) 0.0005(11) 0.0043(10) O2 0.105(2) 0.0370(11) 0.0921(19) 0.0039(14) -0.0118(19) 0.0123(16) C1 0.0373(12) 0.0404(13) 0.0307(10) 0.0016(11) 0.0002(10) 0.0022(15) C2 0.0343(13) 0.0333(12) 0.0352(12) 0.0046(10) -0.0022(12) -0.0008(12) C3 0.056(2) 0.0387(15) 0.0514(17) 0.0113(13) -0.0037(15) -0.0103(15) C4 0.0541(19) 0.0562(19) 0.065(2) 0.0036(17) 0.0023(18) -0.0230(17) C5 0.0385(15) 0.0580(18) 0.0472(15) -0.0052(15) -0.0104(13) -0.0074(16) C6 0.0330(13) 0.065(2) 0.0482(14) -0.0043(15) -0.0061(12) 0.0045(15) C7 0.0394(14) 0.0373(13) 0.0348(12) -0.0018(11) -0.0038(10) -0.0016(12) C8 0.059(2) 0.0399(15) 0.0644(19) -0.0098(15) -0.0165(19) 0.0101(16) C9 0.074(3) 0.072(3) 0.069(2) -0.024(2) -0.003(2) 0.030(2) C10 0.067(2) 0.095(3) 0.0520(19) -0.026(2) 0.0072(19) 0.016(2) C11 0.0353(13) 0.0451(16) 0.0549(17) 0.0014(14) -0.0056(13) 0.0023(13) C12 0.0597(18) 0.0546(19) 0.0340(12) 0.0004(12) -0.0027(13) 0.0021(16) C13 0.063(2) 0.0484(17) 0.0561(18) -0.0144(14) 0.0026(17) -0.0002(18) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag S1 C10 1.716(9) . ? S1 C1 1.834(6) . ? O1 C8 1.370(7) . ? O1 C1 1.438(7) . ? O2 C8 1.205(7) . ? C1 C2 1.546(8) . ? C1 C6 1.555(9) . ? C2 C11 1.525(11) . ? C2 C3 1.534(7) . ? C2 C7 1.564(6) . ? C3 C4 1.554(10) . ? C4 C5 1.526(7) . ? C5 C6 1.533(8) . ? C5 C7 1.542(10) . ? C7 C12 1.532(7) . ? C7 C13 1.536(8) . ? C8 C9 1.443(7) . ? C9 C10 1.329(8) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 H5 0.9800 . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C9 H9 0.9300 . ? C10 H10 0.9300 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C12 H12C 0.9600 . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 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 C10 S1 C1 96.5(3) . . ? C8 O1 C1 119.0(5) . . ? O1 C1 C2 108.5(4) . . ? O1 C1 C6 112.5(3) . . ? C2 C1 C6 103.6(4) . . ? O1 C1 S1 107.9(3) . . ? C2 C1 S1 111.7(3) . . ? C6 C1 S1 112.7(3) . . ? C11 C2 C3 113.5(3) . . ? C11 C2 C1 114.5(4) . . ? C3 C2 C1 107.2(4) . . ? C11 C2 C7 117.6(3) . . ? C3 C2 C7 100.5(3) . . ? C1 C2 C7 101.9(3) . . ? C2 C3 C4 103.7(4) . . ? C5 C4 C3 102.9(3) . . ? C4 C5 C6 108.1(4) . . ? C4 C5 C7 102.8(3) . . ? C6 C5 C7 102.2(3) . . ? C5 C6 C1 102.8(3) . . ? C12 C7 C13 106.2(4) . . ? C12 C7 C5 114.1(3) . . ? C13 C7 C5 113.7(4) . . ? C12 C7 C2 116.4(3) . . ? C13 C7 C2 113.1(3) . . ? C5 C7 C2 93.3(4) . . ? O2 C8 O1 117.1(5) . . ? O2 C8 C9 125.5(4) . . ? O1 C8 C9 117.0(4) . . ? C10 C9 C8 123.5(4) . . ? C9 C10 S1 125.3(4) . . ? C2 C3 H3A 111.0 . . ? C4 C3 H3A 111.0 . . ? C2 C3 H3B 111.0 . . ? C4 C3 H3B 111.0 . . ? H3A C3 H3B 109.0 . . ? C5 C4 H4A 111.2 . . ? C3 C4 H4A 111.2 . . ? C5 C4 H4B 111.2 . . ? C3 C4 H4B 111.2 . . ? H4A C4 H4B 109.1 . . ? C4 C5 H5 114.2 . . ? C6 C5 H5 114.2 . . ? C7 C5 H5 114.2 . . ? C5 C6 H6A 111.2 . . ? C1 C6 H6A 111.2 . . ? C5 C6 H6B 111.2 . . ? C1 C6 H6B 111.2 . . ? H6A C6 H6B 109.1 . . ? C10 C9 H9 118.3 . . ? C8 C9 H9 118.3 . . ? C9 C10 H10 117.4 . . ? S1 C10 H10 117.4 . . ? C2 C11 H11A 109.5 . . ? C2 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C2 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C7 C12 H12A 109.5 . . ? C7 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C7 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C7 C13 H13A 109.5 . . ? C7 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C7 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 29.92 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.275 _refine_diff_density_min -0.235 _refine_diff_density_rms 0.051