# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name 'Asokan, V.' 'Chandran, R. Prakash' 'Deepa, S.' 'Joseph, Bubbly K.' 'Kumar, A.' 'Verghese, Babu' 'Viswam, Dhanya' _publ_contact_author_name 'Dr V Asokan' _publ_contact_author_address ; Dr V Asokan School of Chemical Sciences Mahatma Gandhi University Sr. Lecturer, School of Chemical ci Kottayam Kerala 686 560 INDIA ; _publ_contact_author_email 'ASOKANCV@YAHOO.COM' _publ_section_title ; Highly facile and stereospecific intramolecular [2+2]photocycloadditions of bis(alkenoylketenedithioacetals ; data_compound_2a _database_code_CSD 169427 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H18 O2 S2' _chemical_formula_weight 378.48 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 'S' 'S' 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21/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 8.998(4) _cell_length_b 16.579(6) _cell_length_c 13.372(6) _cell_angle_alpha 90.00 _cell_angle_beta 106.50 _cell_angle_gamma 90.00 _cell_volume 1912.7(14) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 25 _cell_measurement_theta_max 35 _exptl_crystal_description Prismatic _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.314 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 792 _exptl_absorpt_coefficient_mu 2.622 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54180 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CAD4-Diffractometer' _diffrn_measurement_method 'Omega-TwoTheta Scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '1 Hour' _diffrn_standards_decay_% ? _diffrn_reflns_number 3608 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0227 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 4.36 _diffrn_reflns_theta_max 69.88 _reflns_number_total 3608 _reflns_number_gt 3267 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4-Programs' _computing_cell_refinement 'CAD4-Programs' _computing_data_reduction Molen _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP _computing_publication_material '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^)+(0.0755P)^2^+1.0429P] 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 SHELXL _refine_ls_extinction_coef 0.0010(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 3608 _refine_ls_number_parameters 236 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0562 _refine_ls_R_factor_gt 0.0507 _refine_ls_wR_factor_ref 0.1455 _refine_ls_wR_factor_gt 0.1391 _refine_ls_goodness_of_fit_ref 1.050 _refine_ls_restrained_S_all 1.050 _refine_ls_shift/su_max 0.003 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group S1 S 0.53956(8) 0.19602(4) 0.78424(5) 0.0635(2) Uani 1 d . . . S2 S 0.74459(8) 0.10362(4) 0.69303(5) 0.0636(2) Uani 1 d . . . O1 O 0.8850(2) -0.00838(11) 0.82355(14) 0.0630(5) Uani 1 d . . . O2 O 0.5404(2) 0.13515(12) 0.96100(14) 0.0644(5) Uani 1 d . . . C1 C 0.9024(2) -0.13299(14) 0.96753(18) 0.0472(5) Uani 1 d . . . H1 H 0.9752 -0.1296 0.9303 0.057 Uiso 1 calc R . . C2 C 0.7960(2) -0.07493(13) 0.95015(17) 0.0430(5) Uani 1 d . . . H2 H 0.7158 -0.0783 0.9810 0.052 Uiso 1 calc R . . C3 C 0.8027(2) -0.00535(13) 0.88304(16) 0.0429(5) Uani 1 d . . . C4 C 0.7068(2) 0.06636(12) 0.88361(16) 0.0404(4) Uani 1 d . . . C5 C 0.6470(2) 0.08659(13) 0.97185(17) 0.0439(5) Uani 1 d . . . C6 C 0.7184(2) 0.05177(13) 1.07626(16) 0.0435(5) Uani 1 d . . . H6 H 0.8178 0.0302 1.0925 0.052 Uiso 1 calc R . . C7 C 0.6402(2) 0.05145(13) 1.14680(17) 0.0453(5) Uani 1 d . . . H7 H 0.5422 0.0748 1.1263 0.054 Uiso 1 calc R . . C8 C 0.6888(3) 0.01908(15) 1.25195(17) 0.0495(5) Uani 1 d . . . C9 C 0.6026(3) 0.03793(19) 1.3197(2) 0.0677(8) Uani 1 d . . . H9 H 0.5132 0.0688 1.2964 0.081 Uiso 1 calc R . . C10 C 0.6490(5) 0.0111(3) 1.4217(3) 0.0934(13) Uani 1 d . . . H10 H 0.5920 0.0252 1.4672 0.112 Uiso 1 calc R . . C11 C 0.7768(5) -0.0357(3) 1.4557(3) 0.1041(14) Uani 1 d . . . H11 H 0.8070 -0.0539 1.5243 0.125 Uiso 1 calc R . . C12 C 0.8608(4) -0.0561(3) 1.3896(3) 0.0912(11) Uani 1 d . . . H12 H 0.9479 -0.0886 1.4134 0.109 Uiso 1 calc R . . C13 C 0.8191(3) -0.02924(18) 1.2880(2) 0.0635(7) Uani 1 d . . . H13 H 0.8779 -0.0434 1.2437 0.076 Uiso 1 calc R . . C14 C 0.9177(2) -0.20120(13) 1.03807(18) 0.0477(5) Uani 1 d . . . C15 C 1.0432(3) -0.25292(16) 1.0502(2) 0.0601(6) Uani 1 d . . . H15 H 1.1123 -0.2442 1.0111 0.072 Uiso 1 calc R . . C16 C 1.0670(3) -0.31662(18) 1.1186(3) 0.0724(8) Uani 1 d . . . H16 H 1.1509 -0.3509 1.1247 0.087 Uiso 1 calc R . . C17 C 0.9679(4) -0.32975(19) 1.1777(3) 0.0775(8) Uani 1 d . . . H17 H 0.9845 -0.3725 1.2245 0.093 Uiso 1 calc R . . C18 C 0.8436(4) -0.2792(2) 1.1673(3) 0.0845(10) Uani 1 d . . . H18 H 0.7761 -0.2879 1.2075 0.101 Uiso 1 calc R . . C19 C 0.8176(3) -0.21575(18) 1.0980(2) 0.0688(8) Uani 1 d . . . H19 H 0.7323 -0.1824 1.0914 0.083 Uiso 1 calc R . . C20 C 0.6689(2) 0.11649(13) 0.79698(17) 0.0443(5) Uani 1 d . . . C21 C 0.5737(6) 0.2374(2) 0.6684(3) 0.1035(13) Uani 1 d . . . H21A H 0.4810 0.2646 0.6271 0.124 Uiso 1 calc R . . H21B H 0.6569 0.2767 0.6874 0.124 Uiso 1 calc R . . C22 C 0.6146(5) 0.1741(3) 0.6084(3) 0.1000(12) Uani 1 d . . . H22A H 0.6643 0.1969 0.5593 0.120 Uiso 1 calc R . . H22B H 0.5217 0.1461 0.5691 0.120 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 0.0640(4) 0.0526(4) 0.0700(4) 0.0155(3) 0.0127(3) 0.0157(3) S2 0.0683(4) 0.0722(4) 0.0544(4) 0.0132(3) 0.0241(3) 0.0029(3) O1 0.0637(11) 0.0682(11) 0.0678(11) 0.0108(9) 0.0358(9) 0.0187(9) O2 0.0596(10) 0.0721(11) 0.0631(11) 0.0060(9) 0.0199(8) 0.0309(9) C1 0.0382(11) 0.0485(12) 0.0554(13) 0.0001(10) 0.0141(9) 0.0069(9) C2 0.0346(10) 0.0452(11) 0.0485(11) -0.0004(9) 0.0108(8) 0.0050(8) C3 0.0329(10) 0.0498(12) 0.0454(11) 0.0003(9) 0.0102(8) 0.0055(8) C4 0.0339(10) 0.0416(10) 0.0439(11) 0.0025(8) 0.0084(8) 0.0013(8) C5 0.0354(10) 0.0444(11) 0.0506(12) -0.0009(9) 0.0100(9) 0.0051(8) C6 0.0364(10) 0.0476(11) 0.0448(11) -0.0020(9) 0.0091(8) 0.0033(8) C7 0.0359(10) 0.0496(12) 0.0501(12) -0.0082(9) 0.0116(9) -0.0041(9) C8 0.0448(12) 0.0578(13) 0.0475(12) -0.0096(10) 0.0156(10) -0.0190(10) C9 0.0599(15) 0.0871(19) 0.0650(16) -0.0174(14) 0.0319(13) -0.0286(14) C10 0.099(3) 0.134(3) 0.0595(18) -0.0191(19) 0.0427(18) -0.058(2) C11 0.104(3) 0.148(4) 0.0548(18) 0.020(2) 0.0136(18) -0.045(3) C12 0.083(2) 0.118(3) 0.0639(18) 0.0281(19) 0.0063(16) -0.014(2) C13 0.0563(15) 0.0787(18) 0.0532(14) 0.0070(12) 0.0118(11) -0.0067(13) C14 0.0393(11) 0.0459(12) 0.0546(12) 0.0011(9) 0.0082(9) 0.0095(9) C15 0.0482(13) 0.0578(14) 0.0741(16) 0.0048(12) 0.0167(12) 0.0170(11) C16 0.0631(16) 0.0603(16) 0.088(2) 0.0138(14) 0.0125(15) 0.0263(13) C17 0.086(2) 0.0650(17) 0.0773(19) 0.0218(15) 0.0156(16) 0.0204(15) C18 0.088(2) 0.081(2) 0.096(2) 0.0336(18) 0.0454(19) 0.0234(17) C19 0.0590(15) 0.0688(17) 0.0870(19) 0.0230(15) 0.0342(14) 0.0236(13) C20 0.0376(10) 0.0424(11) 0.0496(12) 0.0032(9) 0.0070(9) -0.0029(8) C21 0.136(3) 0.081(2) 0.091(2) 0.041(2) 0.028(2) 0.022(2) C22 0.132(3) 0.098(3) 0.070(2) 0.0355(19) 0.029(2) 0.019(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 S1 C20 1.735(2) . ? S1 C21 1.799(4) . ? S2 C20 1.726(2) . ? S2 C22 1.806(4) . ? O1 C3 1.232(3) . ? O2 C5 1.229(3) . ? C1 C2 1.330(3) . ? C1 C14 1.454(3) . ? C1 H1 0.9300 . ? C2 C3 1.473(3) . ? C2 H2 0.9300 . ? C3 C4 1.471(3) . ? C4 C20 1.387(3) . ? C4 C5 1.468(3) . ? C5 C6 1.479(3) . ? C6 C7 1.328(3) . ? C6 H6 0.9300 . ? C7 C8 1.451(3) . ? C7 H7 0.9300 . ? C8 C9 1.384(3) . ? C8 C13 1.389(4) . ? C9 C10 1.382(5) . ? C9 H9 0.9300 . ? C10 C11 1.354(6) . ? C10 H10 0.9300 . ? C11 C12 1.359(6) . ? C11 H11 0.9300 . ? C12 C13 1.377(4) . ? C12 H12 0.9300 . ? C13 H13 0.9300 . ? C14 C19 1.386(3) . ? C14 C15 1.390(3) . ? C15 C16 1.374(4) . ? C15 H15 0.9300 . ? C16 C17 1.367(5) . ? C16 H16 0.9300 . ? C17 C18 1.373(4) . ? C17 H17 0.9300 . ? C18 C19 1.377(4) . ? C18 H18 0.9300 . ? C19 H19 0.9300 . ? C21 C22 1.431(6) . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C22 H22A 0.9700 . ? C22 H22B 0.9700 . ? 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 C20 S1 C21 95.78(16) . . ? C20 S2 C22 95.24(15) . . ? C2 C1 C14 127.4(2) . . ? C2 C1 H1 116.3 . . ? C14 C1 H1 116.3 . . ? C1 C2 C3 121.4(2) . . ? C1 C2 H2 119.3 . . ? C3 C2 H2 119.3 . . ? O1 C3 C4 119.8(2) . . ? O1 C3 C2 119.83(19) . . ? C4 C3 C2 120.28(18) . . ? C20 C4 C5 118.38(19) . . ? C20 C4 C3 119.02(19) . . ? C5 C4 C3 122.59(18) . . ? O2 C5 C4 120.4(2) . . ? O2 C5 C6 118.9(2) . . ? C4 C5 C6 120.62(18) . . ? C7 C6 C5 119.7(2) . . ? C7 C6 H6 120.1 . . ? C5 C6 H6 120.1 . . ? C6 C7 C8 128.0(2) . . ? C6 C7 H7 116.0 . . ? C8 C7 H7 116.0 . . ? C9 C8 C13 118.5(2) . . ? C9 C8 C7 118.7(2) . . ? C13 C8 C7 122.8(2) . . ? C10 C9 C8 120.3(3) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C11 C10 C9 120.4(3) . . ? C11 C10 H10 119.8 . . ? C9 C10 H10 119.8 . . ? C10 C11 C12 120.0(3) . . ? C10 C11 H11 120.0 . . ? C12 C11 H11 120.0 . . ? C11 C12 C13 121.0(4) . . ? C11 C12 H12 119.5 . . ? C13 C12 H12 119.5 . . ? C12 C13 C8 119.7(3) . . ? C12 C13 H13 120.1 . . ? C8 C13 H13 120.1 . . ? C19 C14 C15 117.7(2) . . ? C19 C14 C1 123.6(2) . . ? C15 C14 C1 118.7(2) . . ? C16 C15 C14 121.3(3) . . ? C16 C15 H15 119.3 . . ? C14 C15 H15 119.3 . . ? C17 C16 C15 120.2(2) . . ? C17 C16 H16 119.9 . . ? C15 C16 H16 119.9 . . ? C16 C17 C18 119.4(3) . . ? C16 C17 H17 120.3 . . ? C18 C17 H17 120.3 . . ? C17 C18 C19 120.8(3) . . ? C17 C18 H18 119.6 . . ? C19 C18 H18 119.6 . . ? C18 C19 C14 120.5(2) . . ? C18 C19 H19 119.7 . . ? C14 C19 H19 119.7 . . ? C4 C20 S2 122.63(17) . . ? C4 C20 S1 122.41(18) . . ? S2 C20 S1 114.96(13) . . ? C22 C21 S1 109.7(3) . . ? C22 C21 H21A 109.7 . . ? S1 C21 H21A 109.7 . . ? C22 C21 H21B 109.7 . . ? S1 C21 H21B 109.7 . . ? H21A C21 H21B 108.2 . . ? C21 C22 S2 110.3(3) . . ? C21 C22 H22A 109.6 . . ? S2 C22 H22A 109.6 . . ? C21 C22 H22B 109.6 . . ? S2 C22 H22B 109.6 . . ? H22A C22 H22B 108.1 . . ? 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 C14 C1 C2 C3 174.6(2) . . . . ? C1 C2 C3 O1 16.4(3) . . . . ? C1 C2 C3 C4 -166.1(2) . . . . ? O1 C3 C4 C20 21.4(3) . . . . ? C2 C3 C4 C20 -156.1(2) . . . . ? O1 C3 C4 C5 -159.6(2) . . . . ? C2 C3 C4 C5 22.9(3) . . . . ? C20 C4 C5 O2 15.7(3) . . . . ? C3 C4 C5 O2 -163.3(2) . . . . ? C20 C4 C5 C6 -161.5(2) . . . . ? C3 C4 C5 C6 19.5(3) . . . . ? O2 C5 C6 C7 21.7(3) . . . . ? C4 C5 C6 C7 -161.1(2) . . . . ? C5 C6 C7 C8 178.8(2) . . . . ? C6 C7 C8 C9 168.1(2) . . . . ? C6 C7 C8 C13 -11.1(4) . . . . ? C13 C8 C9 C10 2.0(4) . . . . ? C7 C8 C9 C10 -177.3(3) . . . . ? C8 C9 C10 C11 -1.7(5) . . . . ? C9 C10 C11 C12 0.4(6) . . . . ? C10 C11 C12 C13 0.6(6) . . . . ? C11 C12 C13 C8 -0.3(5) . . . . ? C9 C8 C13 C12 -1.0(4) . . . . ? C7 C8 C13 C12 178.2(3) . . . . ? C2 C1 C14 C19 0.9(4) . . . . ? C2 C1 C14 C15 -176.0(2) . . . . ? C19 C14 C15 C16 0.4(4) . . . . ? C1 C14 C15 C16 177.5(3) . . . . ? C14 C15 C16 C17 -0.9(5) . . . . ? C15 C16 C17 C18 0.6(5) . . . . ? C16 C17 C18 C19 0.1(6) . . . . ? C17 C18 C19 C14 -0.6(6) . . . . ? C15 C14 C19 C18 0.4(4) . . . . ? C1 C14 C19 C18 -176.6(3) . . . . ? C5 C4 C20 S2 174.71(15) . . . . ? C3 C4 C20 S2 -6.2(3) . . . . ? C5 C4 C20 S1 -6.3(3) . . . . ? C3 C4 C20 S1 172.79(15) . . . . ? C22 S2 C20 C4 169.0(2) . . . . ? C22 S2 C20 S1 -10.1(2) . . . . ? C21 S1 C20 C4 172.3(2) . . . . ? C21 S1 C20 S2 -8.6(2) . . . . ? C20 S1 C21 C22 30.3(4) . . . . ? S1 C21 C22 S2 -41.2(4) . . . . ? C20 S2 C22 C21 31.4(3) . . . . ? _diffrn_measured_fraction_theta_max 0.964 _diffrn_reflns_theta_full 69.88 _diffrn_measured_fraction_theta_full 0.964 _refine_diff_density_max 0.430 _refine_diff_density_min -0.278 _refine_diff_density_rms 0.047 data_compound_3a _database_code_CSD 169428 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H18 O2 S2' _chemical_formula_weight 378.48 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 'S' 'S' 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pna21 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z' _cell_length_a 31.600(7) _cell_length_b 5.6302(12) _cell_length_c 10.199(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1814.5(11) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 25 _cell_measurement_theta_max 35 _exptl_crystal_description 'Needle shaped' _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.385 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 792 _exptl_absorpt_coefficient_mu 2.764 _exptl_absorpt_correction_type 'Psi scan' _exptl_absorpt_correction_T_min 0.751 _exptl_absorpt_correction_T_max 0.995 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54180 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CAD4-Diffractometer' _diffrn_measurement_method 'Omega TwoTheta Scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '1 Hour' ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1687 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0252 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 37 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.80 _diffrn_reflns_theta_max 67.90 _reflns_number_total 1687 _reflns_number_gt 1501 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4-Programs' _computing_cell_refinement 'CAD4-Programs' _computing_data_reduction Molen _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP _computing_publication_material '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^)+(0.0754P)^2^+0.7952P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.18(4) _refine_ls_number_reflns 1687 _refine_ls_number_parameters 235 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0561 _refine_ls_R_factor_gt 0.0479 _refine_ls_wR_factor_ref 0.1375 _refine_ls_wR_factor_gt 0.1263 _refine_ls_goodness_of_fit_ref 1.143 _refine_ls_restrained_S_all 1.143 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group S1 S -0.01599(4) -0.2534(3) 0.13747(19) 0.0551(4) Uani 1 d . . . S2 S 0.04370(4) 0.0249(2) 0.29376(17) 0.0551(4) Uani 1 d . . . O1 O 0.02969(12) -0.6212(8) 0.0102(5) 0.0609(11) Uani 1 d . . . O2 O 0.12761(13) -0.1649(10) 0.2486(5) 0.0741(14) Uani 1 d . . . C1 C 0.10643(17) -0.6514(10) 0.0331(6) 0.0486(13) Uani 1 d . . . H1 H 0.1080 -0.8251 0.0312 0.058 Uiso 1 calc R . . C2 C 0.06277(16) -0.5522(9) 0.0607(6) 0.0483(13) Uani 1 d . . . C3 C 0.06778(15) -0.3544(9) 0.1503(6) 0.0452(12) Uani 1 d . . . C4 C 0.11257(17) -0.3269(11) 0.1856(6) 0.0516(14) Uani 1 d . . . C5 C 0.13688(16) -0.5328(10) 0.1277(6) 0.0500(13) Uani 1 d . . . H5 H 0.1494 -0.6401 0.1926 0.060 Uiso 1 calc R . . C6 C 0.16655(16) -0.4663(9) 0.0131(6) 0.0479(13) Uani 1 d . . . H6 H 0.1728 -0.2958 0.0134 0.057 Uiso 1 calc R . . C7 C 0.12884(18) -0.5249(10) -0.0836(6) 0.0451(13) Uani 1 d . . . H7 H 0.1136 -0.3764 -0.1006 0.054 Uiso 1 calc R . . C8 C 0.13436(15) -0.6512(9) -0.2140(6) 0.0453(12) Uani 1 d . . . C9 C 0.11799(18) -0.5513(12) -0.3250(7) 0.0550(15) Uani 1 d . . . H9 H 0.1043 -0.4055 -0.3194 0.066 Uiso 1 calc R . . C10 C 0.1214(2) -0.6637(15) -0.4467(7) 0.0693(18) Uani 1 d . . . H10 H 0.1096 -0.5951 -0.5211 0.083 Uiso 1 calc R . . C11 C 0.1421(2) -0.8739(16) -0.4549(8) 0.075(2) Uani 1 d . . . H11 H 0.1448 -0.9501 -0.5354 0.090 Uiso 1 calc R . . C12 C 0.1593(2) -0.9740(12) -0.3440(9) 0.073(2) Uani 1 d . . . H12 H 0.1741 -1.1161 -0.3503 0.087 Uiso 1 calc R . . C13 C 0.15471(18) -0.8671(11) -0.2247(7) 0.0566(15) Uani 1 d . . . H13 H 0.1654 -0.9403 -0.1500 0.068 Uiso 1 calc R . . C14 C 0.20645(16) -0.6108(10) -0.0037(6) 0.0489(13) Uani 1 d . . . C15 C 0.23503(19) -0.5459(12) -0.1006(7) 0.0630(18) Uani 1 d . . . H15 H 0.2305 -0.4074 -0.1482 0.076 Uiso 1 calc R . . C16 C 0.26998(19) -0.6833(14) -0.1272(8) 0.0703(19) Uani 1 d . . . H16 H 0.2885 -0.6382 -0.1936 0.084 Uiso 1 calc R . . C17 C 0.2778(2) -0.8867(14) -0.0565(8) 0.0712(19) Uani 1 d . . . H17 H 0.3015 -0.9787 -0.0750 0.085 Uiso 1 calc R . . C18 C 0.2505(2) -0.9535(12) 0.0417(7) 0.0683(19) Uani 1 d . . . H18 H 0.2558 -1.0895 0.0908 0.082 Uiso 1 calc R . . C19 C 0.21470(19) -0.8152(11) 0.0670(7) 0.0583(15) Uani 1 d . . . H19 H 0.1961 -0.8616 0.1327 0.070 Uiso 1 calc R . . C20 C 0.03558(17) -0.2090(9) 0.1910(6) 0.0461(13) Uani 1 d . . . C21 C -0.0360(2) 0.0240(12) 0.2017(10) 0.076(2) Uani 1 d . . . H21A H -0.0345 0.1449 0.1341 0.091 Uiso 1 calc R . . H21B H -0.0655 0.0047 0.2263 0.091 Uiso 1 calc R . . C22 C -0.0117(2) 0.1015(14) 0.3160(9) 0.078(2) Uani 1 d . . . H22A H -0.0225 0.0249 0.3943 0.094 Uiso 1 calc R . . H22B H -0.0145 0.2719 0.3270 0.094 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 0.0376(6) 0.0548(7) 0.0731(9) -0.0080(8) 0.0009(8) 0.0030(6) S2 0.0513(7) 0.0553(8) 0.0589(9) -0.0124(8) -0.0017(7) 0.0041(6) O1 0.050(2) 0.064(2) 0.069(3) -0.012(2) -0.002(2) -0.003(2) O2 0.048(2) 0.091(3) 0.083(3) -0.037(3) -0.012(2) 0.009(2) C1 0.047(3) 0.044(3) 0.055(4) 0.000(3) 0.005(3) 0.005(2) C2 0.039(3) 0.045(3) 0.060(4) 0.000(3) 0.003(3) -0.002(2) C3 0.040(2) 0.049(3) 0.047(3) -0.008(3) -0.002(2) 0.004(2) C4 0.041(3) 0.060(3) 0.054(4) -0.007(3) -0.006(3) 0.009(3) C5 0.042(3) 0.054(3) 0.054(3) 0.000(3) -0.006(3) 0.013(2) C6 0.045(3) 0.046(3) 0.053(3) 0.000(3) 0.001(3) 0.004(2) C7 0.043(3) 0.041(3) 0.051(3) 0.000(2) 0.000(2) 0.002(2) C8 0.036(2) 0.049(3) 0.050(3) -0.008(3) 0.001(2) 0.000(2) C9 0.046(3) 0.060(4) 0.059(4) 0.002(3) 0.001(3) 0.000(3) C10 0.065(4) 0.090(5) 0.053(4) 0.001(4) 0.002(3) -0.012(4) C11 0.067(4) 0.097(5) 0.060(4) -0.028(4) 0.004(4) -0.019(4) C12 0.058(3) 0.066(4) 0.094(6) -0.031(4) 0.008(4) -0.001(3) C13 0.054(3) 0.054(3) 0.062(4) -0.004(3) -0.002(3) 0.000(3) C14 0.040(3) 0.051(3) 0.056(3) -0.001(3) -0.002(3) 0.001(2) C15 0.046(3) 0.062(4) 0.081(5) 0.008(3) 0.004(3) -0.002(3) C16 0.045(3) 0.089(5) 0.076(5) 0.005(4) 0.011(3) 0.003(3) C17 0.044(3) 0.080(4) 0.090(5) -0.007(4) -0.002(4) 0.019(3) C18 0.059(4) 0.070(4) 0.077(5) -0.001(4) -0.006(4) 0.016(3) C19 0.049(3) 0.058(3) 0.068(4) 0.001(3) 0.004(3) 0.003(3) C20 0.047(3) 0.040(3) 0.051(3) 0.000(2) 0.000(2) 0.004(2) C21 0.048(3) 0.065(4) 0.115(7) -0.009(4) 0.000(4) 0.012(3) C22 0.068(4) 0.076(4) 0.090(6) -0.022(4) 0.006(4) 0.016(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 S1 C20 1.737(6) . ? S1 C21 1.808(7) . ? S2 C20 1.703(6) . ? S2 C22 1.817(7) . ? O1 C2 1.228(7) . ? O2 C4 1.213(7) . ? C1 C2 1.514(7) . ? C1 C5 1.518(8) . ? C1 C7 1.557(8) . ? C1 H1 0.9800 . ? C2 C3 1.449(8) . ? C3 C20 1.370(7) . ? C3 C4 1.469(7) . ? C4 C5 1.511(8) . ? C5 C6 1.544(8) . ? C5 H5 0.9800 . ? C6 C14 1.510(7) . ? C6 C7 1.582(8) . ? C6 H6 0.9800 . ? C7 C8 1.518(8) . ? C7 H7 0.9800 . ? C8 C9 1.365(9) . ? C8 C13 1.379(8) . ? C9 C10 1.397(10) . ? C9 H9 0.9300 . ? C10 C11 1.355(12) . ? C10 H10 0.9300 . ? C11 C12 1.375(11) . ? C11 H11 0.9300 . ? C12 C13 1.365(10) . ? C12 H12 0.9300 . ? C13 H13 0.9300 . ? C14 C19 1.383(8) . ? C14 C15 1.388(9) . ? C15 C16 1.375(9) . ? C15 H15 0.9300 . ? C16 C17 1.376(10) . ? C16 H16 0.9300 . ? C17 C18 1.374(10) . ? C17 H17 0.9300 . ? C18 C19 1.397(9) . ? C18 H18 0.9300 . ? C19 H19 0.9300 . ? C21 C22 1.463(12) . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C22 H22A 0.9700 . ? C22 H22B 0.9700 . ? 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 C20 S1 C21 95.2(3) . . ? C20 S2 C22 96.6(3) . . ? C2 C1 C5 107.3(5) . . ? C2 C1 C7 112.8(5) . . ? C5 C1 C7 89.8(4) . . ? C2 C1 H1 114.7 . . ? C5 C1 H1 114.7 . . ? C7 C1 H1 114.7 . . ? O1 C2 C3 126.9(5) . . ? O1 C2 C1 125.5(5) . . ? C3 C2 C1 107.5(5) . . ? C20 C3 C2 124.7(5) . . ? C20 C3 C4 125.3(5) . . ? C2 C3 C4 109.9(5) . . ? O2 C4 C3 126.0(5) . . ? O2 C4 C5 125.8(5) . . ? C3 C4 C5 108.2(5) . . ? C4 C5 C1 105.3(4) . . ? C4 C5 C6 114.7(5) . . ? C1 C5 C6 90.6(5) . . ? C4 C5 H5 114.5 . . ? C1 C5 H5 114.5 . . ? C6 C5 H5 114.5 . . ? C14 C6 C5 117.5(5) . . ? C14 C6 C7 116.4(5) . . ? C5 C6 C7 87.9(4) . . ? C14 C6 H6 111.0 . . ? C5 C6 H6 111.0 . . ? C7 C6 H6 111.0 . . ? C8 C7 C1 120.5(5) . . ? C8 C7 C6 123.9(5) . . ? C1 C7 C6 87.8(4) . . ? C8 C7 H7 107.6 . . ? C1 C7 H7 107.6 . . ? C6 C7 H7 107.6 . . ? C9 C8 C13 118.3(6) . . ? C9 C8 C7 119.3(5) . . ? C13 C8 C7 122.4(5) . . ? C8 C9 C10 121.4(6) . . ? C8 C9 H9 119.3 . . ? C10 C9 H9 119.3 . . ? C11 C10 C9 119.2(7) . . ? C11 C10 H10 120.4 . . ? C9 C10 H10 120.4 . . ? C10 C11 C12 119.8(7) . . ? C10 C11 H11 120.1 . . ? C12 C11 H11 120.1 . . ? C13 C12 C11 120.7(6) . . ? C13 C12 H12 119.6 . . ? C11 C12 H12 119.6 . . ? C12 C13 C8 120.5(6) . . ? C12 C13 H13 119.7 . . ? C8 C13 H13 119.7 . . ? C19 C14 C15 117.9(5) . . ? C19 C14 C6 123.1(5) . . ? C15 C14 C6 118.8(5) . . ? C16 C15 C14 121.0(6) . . ? C16 C15 H15 119.5 . . ? C14 C15 H15 119.5 . . ? C15 C16 C17 120.6(7) . . ? C15 C16 H16 119.7 . . ? C17 C16 H16 119.7 . . ? C18 C17 C16 119.8(6) . . ? C18 C17 H17 120.1 . . ? C16 C17 H17 120.1 . . ? C17 C18 C19 119.4(7) . . ? C17 C18 H18 120.3 . . ? C19 C18 H18 120.3 . . ? C14 C19 C18 121.3(6) . . ? C14 C19 H19 119.3 . . ? C18 C19 H19 119.3 . . ? C3 C20 S2 122.5(4) . . ? C3 C20 S1 121.0(4) . . ? S2 C20 S1 116.5(3) . . ? C22 C21 S1 111.3(5) . . ? C22 C21 H21A 109.4 . . ? S1 C21 H21A 109.4 . . ? C22 C21 H21B 109.4 . . ? S1 C21 H21B 109.4 . . ? H21A C21 H21B 108.0 . . ? C21 C22 S2 109.6(5) . . ? C21 C22 H22A 109.7 . . ? S2 C22 H22A 109.7 . . ? C21 C22 H22B 109.7 . . ? S2 C22 H22B 109.7 . . ? H22A C22 H22B 108.2 . . ? 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 C5 C1 C2 O1 -173.8(6) . . . . ? C7 C1 C2 O1 88.9(7) . . . . ? C5 C1 C2 C3 9.7(7) . . . . ? C7 C1 C2 C3 -87.6(6) . . . . ? O1 C2 C3 C20 -1.2(10) . . . . ? C1 C2 C3 C20 175.3(6) . . . . ? O1 C2 C3 C4 -178.6(6) . . . . ? C1 C2 C3 C4 -2.1(7) . . . . ? C20 C3 C4 O2 -4.8(11) . . . . ? C2 C3 C4 O2 172.6(6) . . . . ? C20 C3 C4 C5 176.3(6) . . . . ? C2 C3 C4 C5 -6.3(7) . . . . ? O2 C4 C5 C1 -166.9(6) . . . . ? C3 C4 C5 C1 12.0(6) . . . . ? O2 C4 C5 C6 -69.0(8) . . . . ? C3 C4 C5 C6 109.9(6) . . . . ? C2 C1 C5 C4 -13.1(6) . . . . ? C7 C1 C5 C4 100.8(5) . . . . ? C2 C1 C5 C6 -129.0(5) . . . . ? C7 C1 C5 C6 -15.1(4) . . . . ? C4 C5 C6 C14 148.8(5) . . . . ? C1 C5 C6 C14 -104.0(5) . . . . ? C4 C5 C6 C7 -92.3(5) . . . . ? C1 C5 C6 C7 14.9(4) . . . . ? C2 C1 C7 C8 -107.8(6) . . . . ? C5 C1 C7 C8 143.5(5) . . . . ? C2 C1 C7 C6 123.5(5) . . . . ? C5 C1 C7 C6 14.8(4) . . . . ? C14 C6 C7 C8 -20.5(8) . . . . ? C5 C6 C7 C8 -140.4(6) . . . . ? C14 C6 C7 C1 105.4(5) . . . . ? C5 C6 C7 C1 -14.5(4) . . . . ? C1 C7 C8 C9 122.2(6) . . . . ? C6 C7 C8 C9 -127.8(6) . . . . ? C1 C7 C8 C13 -56.4(7) . . . . ? C6 C7 C8 C13 53.5(7) . . . . ? C13 C8 C9 C10 0.3(9) . . . . ? C7 C8 C9 C10 -178.5(6) . . . . ? C8 C9 C10 C11 -1.3(10) . . . . ? C9 C10 C11 C12 0.4(11) . . . . ? C10 C11 C12 C13 1.7(11) . . . . ? C11 C12 C13 C8 -2.8(10) . . . . ? C9 C8 C13 C12 1.8(8) . . . . ? C7 C8 C13 C12 -179.6(5) . . . . ? C5 C6 C14 C19 8.5(8) . . . . ? C7 C6 C14 C19 -93.8(7) . . . . ? C5 C6 C14 C15 -176.0(5) . . . . ? C7 C6 C14 C15 81.7(7) . . . . ? C19 C14 C15 C16 1.4(10) . . . . ? C6 C14 C15 C16 -174.4(7) . . . . ? C14 C15 C16 C17 -1.2(11) . . . . ? C15 C16 C17 C18 0.0(12) . . . . ? C16 C17 C18 C19 0.9(11) . . . . ? C15 C14 C19 C18 -0.4(9) . . . . ? C6 C14 C19 C18 175.2(6) . . . . ? C17 C18 C19 C14 -0.8(10) . . . . ? C2 C3 C20 S2 -178.6(5) . . . . ? C4 C3 C20 S2 -1.6(9) . . . . ? C2 C3 C20 S1 0.6(8) . . . . ? C4 C3 C20 S1 177.6(5) . . . . ? C22 S2 C20 C3 -173.7(6) . . . . ? C22 S2 C20 S1 7.2(5) . . . . ? C21 S1 C20 C3 -169.5(5) . . . . ? C21 S1 C20 S2 9.6(5) . . . . ? C20 S1 C21 C22 -28.1(6) . . . . ? S1 C21 C22 S2 36.2(8) . . . . ? C20 S2 C22 C21 -26.3(6) . . . . ? _diffrn_measured_fraction_theta_max 0.966 _diffrn_reflns_theta_full 67.90 _diffrn_measured_fraction_theta_full 0.966 _refine_diff_density_max 0.417 _refine_diff_density_min -0.262 _refine_diff_density_rms 0.061