# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2009 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Thomas Muller' _publ_contact_author_email THOMASJJ.MUELLER@UNI-DUESSELDORF.DE _publ_section_title ; Microwave assisted three-component coupling-addition-SNAr (CASNAR) sequences to annelated 4H thiopyran-4-ones ; loop_ _publ_author_name 'Thomas Muller' 'Walter Frank' 'Benjamin Willy' # Attachment 'cif_CCDC_745614_opus833.txt' data_opus833 _database_code_depnum_ccdc_archive 'CCDC 745614' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 2-(6-Methoxynaphthalen-2-yl)-4H-thiochromen-4-one _chemical_melting_point ? _chemical_formula_moiety 'C20 H14 O2 S' _chemical_formula_sum 'C20 H14 O2 S' _chemical_formula_weight 318.38 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/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 13.6458(10) _cell_length_b 5.7353(3) _cell_length_c 19.9386(14) _cell_angle_alpha 90.00 _cell_angle_beta 106.548(8) _cell_angle_gamma 90.00 _cell_volume 1495.82(18) _cell_formula_units_Z 4 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 2.15 _cell_measurement_theta_max 25.90 _exptl_crystal_description prismatic _exptl_crystal_colour yellow _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.414 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 664 _exptl_absorpt_coefficient_mu 0.223 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 291(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 'Stoe IPDS' _diffrn_measurement_method \f-scans _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 18476 _diffrn_reflns_av_R_equivalents 0.0826 _diffrn_reflns_av_sigmaI/netI 0.0491 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.12 _diffrn_reflns_theta_max 24.99 _reflns_number_total 2629 _reflns_number_gt 1854 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'EXPOSE (Stoe & Cie, 1996)' _computing_cell_refinement 'CELL (Stoe & Cie, 1996)' _computing_data_reduction 'INTEGRATE (Stoe & Cie, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1998)' _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 _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+0.9000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2629 _refine_ls_number_parameters 209 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0618 _refine_ls_R_factor_gt 0.0444 _refine_ls_wR_factor_ref 0.0930 _refine_ls_wR_factor_gt 0.0903 _refine_ls_goodness_of_fit_ref 0.994 _refine_ls_restrained_S_all 0.994 _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 0.27375(6) 0.68325(12) 0.47210(4) 0.0645(2) Uani 1 1 d . . . O1 O 0.43017(14) 0.0737(3) 0.58969(9) 0.0694(5) Uani 1 1 d . . . O2 O 0.46988(13) 0.5295(3) 0.08290(8) 0.0606(5) Uani 1 1 d . . . C1 C 0.35346(16) 0.4842(4) 0.44796(11) 0.0455(5) Uani 1 1 d . . . C2 C 0.39634(17) 0.3026(4) 0.48952(12) 0.0531(6) Uani 1 1 d . . . H2A H 0.4375 0.2041 0.4721 0.064 Uiso 1 1 calc R . . C3 C 0.38583(17) 0.2438(4) 0.55752(12) 0.0518(6) Uani 1 1 d . . . C4 C 0.31975(17) 0.3899(4) 0.58775(11) 0.0487(6) Uani 1 1 d . . . C5 C 0.26823(18) 0.5858(4) 0.55376(12) 0.0519(6) Uani 1 1 d . . . C6 C 0.2047(2) 0.7133(5) 0.58394(13) 0.0639(7) Uani 1 1 d . . . H61 H 0.1706 0.8438 0.5610 0.077 Uiso 1 1 calc R . . C7 C 0.1922(2) 0.6484(5) 0.64654(13) 0.0672(8) Uani 1 1 d . . . H71 H 0.1493 0.7338 0.6661 0.081 Uiso 1 1 calc R . . C8 C 0.2433(2) 0.4554(5) 0.68125(13) 0.0679(8) Uani 1 1 d . . . H81 H 0.2352 0.4117 0.7243 0.081 Uiso 1 1 calc R . . C9 C 0.30574(19) 0.3293(5) 0.65223(13) 0.0631(7) Uani 1 1 d . . . H91 H 0.3397 0.1999 0.6760 0.076 Uiso 1 1 calc R . . C10 C 0.36806(16) 0.5329(4) 0.37828(11) 0.0437(5) Uani 1 1 d . . . C11 C 0.42118(17) 0.3811(4) 0.34806(12) 0.0472(6) Uani 1 1 d . . . H111 H 0.4489 0.2468 0.3722 0.057 Uiso 1 1 calc R . . C12 C 0.43468(16) 0.4231(4) 0.28187(12) 0.0443(5) Uani 1 1 d . . . C13 C 0.39229(16) 0.6275(4) 0.24418(11) 0.0425(5) Uani 1 1 d . . . C14 C 0.33950(16) 0.7824(4) 0.27617(12) 0.0469(5) Uani 1 1 d . . . H141 H 0.3120 0.9183 0.2529 0.056 Uiso 1 1 calc R . . C15 C 0.32770(16) 0.7381(4) 0.34032(12) 0.0471(6) Uani 1 1 d . . . H151 H 0.2924 0.8445 0.3599 0.056 Uiso 1 1 calc R . . C16 C 0.48829(17) 0.2673(4) 0.24979(13) 0.0547(6) Uani 1 1 d . . . H161 H 0.5177 0.1340 0.2738 0.066 Uiso 1 1 calc R . . C17 C 0.49755(18) 0.3077(4) 0.18542(13) 0.0571(6) Uani 1 1 d . . . H171 H 0.5326 0.2016 0.1655 0.068 Uiso 1 1 calc R . . C18 C 0.45454(17) 0.5106(4) 0.14748(12) 0.0486(6) Uani 1 1 d . . . C19 C 0.40325(16) 0.6672(4) 0.17649(11) 0.0473(5) Uani 1 1 d . . . H191 H 0.3754 0.8005 0.1518 0.057 Uiso 1 1 calc R . . C20 C 0.4249(2) 0.7252(5) 0.04140(13) 0.0677(7) Uani 1 1 d . . . H201 H 0.4402 0.7191 -0.0027 0.102 Uiso 1 1 calc R . . H202 H 0.4521 0.8664 0.0654 0.102 Uiso 1 1 calc R . . H203 H 0.3522 0.7218 0.0335 0.102 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 S1 0.0913(5) 0.0500(4) 0.0594(4) 0.0124(3) 0.0330(3) 0.0194(4) O1 0.0712(12) 0.0663(12) 0.0661(11) 0.0224(10) 0.0120(9) 0.0172(10) O2 0.0677(11) 0.0614(11) 0.0580(10) -0.0005(9) 0.0263(9) 0.0088(9) C1 0.0418(12) 0.0413(13) 0.0496(13) 0.0001(10) 0.0067(10) -0.0050(10) C2 0.0510(13) 0.0502(14) 0.0568(14) 0.0044(12) 0.0133(11) 0.0072(12) C3 0.0445(13) 0.0529(16) 0.0505(13) 0.0084(11) 0.0017(11) -0.0026(11) C4 0.0434(12) 0.0514(14) 0.0450(13) 0.0028(11) 0.0024(10) -0.0073(11) C5 0.0561(14) 0.0495(14) 0.0489(13) -0.0016(11) 0.0129(11) -0.0059(12) C6 0.0755(18) 0.0607(17) 0.0568(16) 0.0047(13) 0.0208(13) 0.0123(14) C7 0.0669(17) 0.082(2) 0.0536(16) -0.0021(14) 0.0184(13) 0.0044(15) C8 0.0620(16) 0.095(2) 0.0470(14) 0.0097(15) 0.0155(13) -0.0006(16) C9 0.0563(15) 0.0745(19) 0.0531(15) 0.0135(14) 0.0068(12) 0.0012(14) C10 0.0405(12) 0.0379(13) 0.0504(13) 0.0000(10) 0.0088(10) -0.0028(10) C11 0.0482(13) 0.0364(13) 0.0534(14) 0.0065(10) 0.0084(11) 0.0031(10) C12 0.0403(12) 0.0371(13) 0.0536(13) -0.0013(10) 0.0104(10) -0.0015(10) C13 0.0398(11) 0.0369(13) 0.0495(13) -0.0010(10) 0.0107(10) -0.0033(9) C14 0.0484(13) 0.0368(12) 0.0543(14) 0.0058(11) 0.0125(10) 0.0053(10) C15 0.0484(13) 0.0410(14) 0.0535(14) 0.0000(11) 0.0173(11) 0.0059(10) C16 0.0562(14) 0.0433(14) 0.0638(15) 0.0048(12) 0.0157(12) 0.0112(11) C17 0.0588(15) 0.0479(15) 0.0686(16) -0.0053(13) 0.0245(12) 0.0095(12) C18 0.0461(13) 0.0487(14) 0.0514(13) -0.0043(11) 0.0145(11) -0.0038(11) C19 0.0476(13) 0.0399(13) 0.0537(14) 0.0032(11) 0.0135(11) 0.0020(11) C20 0.0810(18) 0.0701(19) 0.0538(15) 0.0037(14) 0.0222(13) 0.0100(15) _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 C5 1.743(2) . ? S1 C1 1.737(2) . ? O1 C3 1.228(3) . ? O2 C18 1.366(3) . ? O2 C20 1.425(3) . ? C1 C2 1.356(3) . ? C1 C10 1.485(3) . ? C2 C3 1.443(3) . ? C2 H2A 0.9300 . ? C3 C4 1.479(3) . ? C4 C5 1.394(3) . ? C4 C9 1.397(3) . ? C5 C6 1.395(3) . ? C6 C7 1.359(3) . ? C6 H61 0.9300 . ? C7 C8 1.384(4) . ? C7 H71 0.9300 . ? C8 C9 1.365(4) . ? C8 H81 0.9300 . ? C9 H91 0.9300 . ? C10 C15 1.422(3) . ? C10 C11 1.377(3) . ? C11 C12 1.404(3) . ? C11 H111 0.9300 . ? C12 C16 1.418(3) . ? C12 C13 1.423(3) . ? C13 C14 1.406(3) . ? C13 C19 1.418(3) . ? C14 C15 1.358(3) . ? C14 H141 0.9300 . ? C15 H151 0.9300 . ? C16 C17 1.345(3) . ? C16 H161 0.9300 . ? C17 C18 1.420(3) . ? C17 H171 0.9300 . ? C18 C19 1.365(3) . ? C19 H191 0.9300 . ? C20 H201 0.9600 . ? C20 H202 0.9600 . ? C20 H203 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 C5 S1 C1 104.19(11) . . ? C18 O2 C20 116.97(19) . . ? C2 C1 C10 124.5(2) . . ? C2 C1 S1 122.07(19) . . ? C10 C1 S1 113.39(16) . . ? C1 C2 C3 127.8(2) . . ? C1 C2 H2A 116.1 . . ? C3 C2 H2A 116.1 . . ? O1 C3 C2 120.7(2) . . ? O1 C3 C4 120.3(2) . . ? C2 C3 C4 119.0(2) . . ? C5 C4 C9 117.8(2) . . ? C5 C4 C3 122.7(2) . . ? C9 C4 C3 119.6(2) . . ? C4 C5 C6 120.1(2) . . ? C4 C5 S1 124.22(19) . . ? C6 C5 S1 115.61(19) . . ? C7 C6 C5 120.6(3) . . ? C7 C6 H61 119.7 . . ? C5 C6 H61 119.7 . . ? C6 C7 C8 120.1(3) . . ? C6 C7 H71 120.0 . . ? C8 C7 H71 120.0 . . ? C9 C8 C7 119.9(2) . . ? C9 C8 H81 120.1 . . ? C7 C8 H81 120.1 . . ? C8 C9 C4 121.6(3) . . ? C8 C9 H91 119.2 . . ? C4 C9 H91 119.2 . . ? C15 C10 C11 117.5(2) . . ? C15 C10 C1 121.3(2) . . ? C11 C10 C1 121.2(2) . . ? C12 C11 C10 122.0(2) . . ? C12 C11 H111 119.0 . . ? C10 C11 H111 119.0 . . ? C16 C12 C11 122.6(2) . . ? C16 C12 C13 117.7(2) . . ? C11 C12 C13 119.7(2) . . ? C12 C13 C14 117.7(2) . . ? C12 C13 C19 119.9(2) . . ? C14 C13 C19 122.5(2) . . ? C15 C14 C13 121.5(2) . . ? C15 C14 H141 119.2 . . ? C13 C14 H141 119.2 . . ? C10 C15 C14 121.6(2) . . ? C10 C15 H151 119.2 . . ? C14 C15 H151 119.2 . . ? C12 C16 C17 121.5(2) . . ? C12 C16 H161 119.2 . . ? C17 C16 H161 119.2 . . ? C16 C17 C18 120.8(2) . . ? C16 C17 H171 119.6 . . ? C18 C17 H171 119.6 . . ? O2 C18 C19 125.6(2) . . ? O2 C18 C17 114.6(2) . . ? C19 C18 C17 119.8(2) . . ? C18 C19 C13 120.2(2) . . ? C18 C19 H191 119.9 . . ? C13 C19 H191 119.9 . . ? O2 C20 H201 109.5 . . ? O2 C20 H202 109.5 . . ? H201 C20 H202 109.5 . . ? O2 C20 H203 109.5 . . ? H201 C20 H203 109.5 . . ? H202 C20 H203 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 C5 S1 C1 C2 -0.2(2) . . . . ? C5 S1 C1 C10 179.24(16) . . . . ? C10 C1 C2 C3 -180.0(2) . . . . ? S1 C1 C2 C3 -0.6(3) . . . . ? C1 C2 C3 O1 -179.4(2) . . . . ? C1 C2 C3 C4 1.3(4) . . . . ? O1 C3 C4 C5 179.5(2) . . . . ? C2 C3 C4 C5 -1.2(3) . . . . ? O1 C3 C4 C9 -1.9(3) . . . . ? C2 C3 C4 C9 177.5(2) . . . . ? C9 C4 C5 C6 -0.4(3) . . . . ? C3 C4 C5 C6 178.2(2) . . . . ? C9 C4 C5 S1 -178.25(18) . . . . ? C3 C4 C5 S1 0.4(3) . . . . ? C1 S1 C5 C4 0.3(2) . . . . ? C1 S1 C5 C6 -177.63(19) . . . . ? C4 C5 C6 C7 0.0(4) . . . . ? S1 C5 C6 C7 178.0(2) . . . . ? C5 C6 C7 C8 0.5(4) . . . . ? C6 C7 C8 C9 -0.5(4) . . . . ? C7 C8 C9 C4 0.0(4) . . . . ? C5 C4 C9 C8 0.5(4) . . . . ? C3 C4 C9 C8 -178.2(2) . . . . ? C2 C1 C10 C15 -174.5(2) . . . . ? S1 C1 C10 C15 6.0(3) . . . . ? C2 C1 C10 C11 5.5(3) . . . . ? S1 C1 C10 C11 -173.97(17) . . . . ? C15 C10 C11 C12 -0.8(3) . . . . ? C1 C10 C11 C12 179.2(2) . . . . ? C10 C11 C12 C16 -179.4(2) . . . . ? C10 C11 C12 C13 -0.3(3) . . . . ? C16 C12 C13 C14 -179.7(2) . . . . ? C11 C12 C13 C14 1.1(3) . . . . ? C16 C12 C13 C19 0.9(3) . . . . ? C11 C12 C13 C19 -178.2(2) . . . . ? C12 C13 C14 C15 -1.0(3) . . . . ? C19 C13 C14 C15 178.3(2) . . . . ? C11 C10 C15 C14 0.9(3) . . . . ? C1 C10 C15 C14 -179.1(2) . . . . ? C13 C14 C15 C10 0.0(3) . . . . ? C11 C12 C16 C17 177.9(2) . . . . ? C13 C12 C16 C17 -1.2(3) . . . . ? C12 C16 C17 C18 0.7(4) . . . . ? C20 O2 C18 C19 -2.6(3) . . . . ? C20 O2 C18 C17 177.6(2) . . . . ? C16 C17 C18 O2 179.9(2) . . . . ? C16 C17 C18 C19 0.1(4) . . . . ? O2 C18 C19 C13 179.9(2) . . . . ? C17 C18 C19 C13 -0.3(3) . . . . ? C12 C13 C19 C18 -0.2(3) . . . . ? C14 C13 C19 C18 -179.5(2) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.337 _refine_diff_density_min -0.317 _refine_diff_density_rms 0.041 # Attachment 'cif_CCDC_745615_opus819.txt' data_opus819 _database_code_depnum_ccdc_archive 'CCDC 745615' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2-Cyclopropyl-4H-thiopyrano[2,3-b]pyridin-4-one ; _chemical_name_common 2-Cyclopropyl-4H-thiopyrano(2,3-b)pyridin-4-one _chemical_melting_point 364 _chemical_formula_moiety 'C11 H9 N O S' _chemical_formula_sum 'C11 H9 N O S' _chemical_formula_weight 203.25 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 8.2503(9) _cell_length_b 22.330(3) _cell_length_c 10.694(2) _cell_angle_alpha 90.00 _cell_angle_beta 103.40(3) _cell_angle_gamma 90.00 _cell_volume 1916.5(5) _cell_formula_units_Z 8 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 2823 _cell_measurement_theta_min 2.15 _cell_measurement_theta_max 22.10 _exptl_crystal_description isometric _exptl_crystal_colour yellow _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.409 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 848 _exptl_absorpt_coefficient_mu 0.299 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 291(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 'Stoe IPDS' _diffrn_measurement_method \f-scans _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 11642 _diffrn_reflns_av_R_equivalents 0.0983 _diffrn_reflns_av_sigmaI/netI 0.1675 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.16 _diffrn_reflns_theta_max 24.99 _reflns_number_total 3360 _reflns_number_gt 1076 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'EXPOSE (Stoe & Cie, 1996)' _computing_cell_refinement 'CELL (Stoe & Cie, 1996)' _computing_data_reduction 'INTEGRATE (Stoe & Cie, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1998)' _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 _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3360 _refine_ls_number_parameters 253 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.1429 _refine_ls_R_factor_gt 0.0423 _refine_ls_wR_factor_ref 0.0532 _refine_ls_wR_factor_gt 0.0469 _refine_ls_goodness_of_fit_ref 0.848 _refine_ls_restrained_S_all 0.856 _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 S1 S 0.79839(14) 0.32794(4) 0.35833(9) 0.0790(3) Uani 1 1 d . . . S2 S 0.33011(15) 0.39358(4) 0.36607(9) 0.0872(4) Uani 1 1 d . . . O1 O 0.4957(3) 0.38123(10) -0.0207(2) 0.1135(10) Uani 1 1 d . . . O2 O -0.0044(3) 0.39893(10) -0.0185(2) 0.1000(9) Uani 1 1 d . . . N1 N 0.8646(4) 0.43989(16) 0.3719(3) 0.0796(10) Uani 1 1 d . . . N2 N 0.2625(4) 0.28269(14) 0.3425(3) 0.0761(10) Uani 1 1 d . . . C1 C 0.6851(5) 0.28381(14) 0.2372(3) 0.0675(11) Uani 1 1 d . . . C2 C 0.6008(5) 0.30483(15) 0.1250(3) 0.0753(13) Uani 1 1 d . . . H21 H 0.5441 0.2767 0.0669 0.090 Uiso 1 1 calc R . . C3 C 0.5869(5) 0.36619(15) 0.0830(3) 0.0733(12) Uani 1 1 d . . . C4 C 0.6871(5) 0.41118(14) 0.1675(3) 0.0623(11) Uani 1 1 d . . . C5 C 0.7797(5) 0.39919(15) 0.2905(3) 0.0617(10) Uani 1 1 d . . . C6 C 0.6928(5) 0.46964(17) 0.1253(4) 0.0807(12) Uani 1 1 d . . . H61 H 0.6365 0.4801 0.0424 0.097 Uiso 1 1 calc R . . C7 C 0.7797(5) 0.51150(17) 0.2043(5) 0.0886(13) Uani 1 1 d . . . H71 H 0.7844 0.5508 0.1763 0.106 Uiso 1 1 calc R . . C8 C 0.8612(5) 0.4952(2) 0.3266(4) 0.0892(12) Uani 1 1 d . . . H81 H 0.9173 0.5249 0.3809 0.107 Uiso 1 1 calc R . . C9 C 0.6967(6) 0.21974(16) 0.2738(4) 0.0897(13) Uani 1 1 d . . . H91 H 0.7596 0.2112 0.3616 0.108 Uiso 1 1 calc R . . C10 C 0.7100(6) 0.17383(18) 0.1767(4) 0.1044(14) Uani 1 1 d . . . H101 H 0.7069 0.1874 0.0900 0.125 Uiso 1 1 calc R . . H102 H 0.7821 0.1397 0.2049 0.125 Uiso 1 1 calc R . . C11 C 0.5563(5) 0.17818(17) 0.2223(4) 0.0927(12) Uani 1 1 d . . . H111 H 0.5337 0.1468 0.2787 0.111 Uiso 1 1 calc R . . H112 H 0.4585 0.1944 0.1638 0.111 Uiso 1 1 calc R . . C12 C 0.2685(5) 0.45380(16) 0.2681(4) 0.0789(12) Uani 1 1 d . . . C13 C 0.1682(5) 0.45050(14) 0.1529(4) 0.0712(11) Uani 1 1 d . . . H131 H 0.1444 0.4864 0.1081 0.085 Uiso 1 1 calc R . . C14 C 0.0911(5) 0.39753(17) 0.0885(3) 0.0677(11) Uani 1 1 d . . . C15 C 0.1298(4) 0.33963(13) 0.1560(3) 0.0567(10) Uani 1 1 d . . . C16 C 0.2286(4) 0.33401(15) 0.2760(3) 0.0588(9) Uani 1 1 d . . . C17 C 0.0612(5) 0.28715(16) 0.0959(3) 0.0743(11) Uani 1 1 d . . . H171 H -0.0061 0.2883 0.0131 0.089 Uiso 1 1 calc R . . C18 C 0.0941(5) 0.23358(17) 0.1604(4) 0.0833(13) Uani 1 1 d . . . H181 H 0.0497 0.1979 0.1223 0.100 Uiso 1 1 calc R . . C19 C 0.1927(5) 0.23400(16) 0.2806(4) 0.0828(12) Uani 1 1 d . . . H191 H 0.2133 0.1975 0.3233 0.099 Uiso 1 1 calc R . . C20 C 0.3457(8) 0.51035(18) 0.3355(5) 0.149(3) Uani 1 1 d D . . H201 H 0.4188 0.5022 0.4200 0.179 Uiso 1 1 calc R . . C21 C 0.2679(7) 0.5640(2) 0.3309(6) 0.1290(19) Uani 1 1 d D . . H211 H 0.1577 0.5677 0.2748 0.155 Uiso 1 1 calc R . . H212 H 0.2847 0.5870 0.4099 0.155 Uiso 1 1 calc R . . C22 C 0.3980(8) 0.5583(2) 0.2757(6) 0.153(2) Uani 1 1 d D . . H221 H 0.5022 0.5772 0.3178 0.184 Uiso 1 1 calc R . . H222 H 0.3751 0.5579 0.1826 0.184 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 S1 0.0911(9) 0.0844(6) 0.0547(5) 0.0078(5) 0.0035(5) 0.0061(7) S2 0.1012(9) 0.0710(7) 0.0732(6) -0.0026(6) -0.0131(6) -0.0032(6) O1 0.141(3) 0.0898(17) 0.0816(17) 0.0148(15) -0.0326(17) 0.0028(18) O2 0.126(2) 0.0978(18) 0.0626(15) 0.0042(14) -0.0059(15) 0.0211(17) N1 0.088(3) 0.083(2) 0.068(2) 0.0004(19) 0.0181(19) -0.0083(19) N2 0.084(3) 0.068(2) 0.0688(19) 0.0088(18) 0.0028(17) 0.0066(19) C1 0.080(3) 0.065(2) 0.054(2) 0.0034(19) 0.009(2) 0.004(2) C2 0.089(3) 0.060(2) 0.069(2) -0.0037(19) 0.002(2) 0.002(2) C3 0.082(3) 0.071(3) 0.055(2) 0.0027(19) -0.007(2) 0.006(2) C4 0.075(3) 0.057(2) 0.056(2) 0.0093(18) 0.018(2) 0.015(2) C5 0.067(3) 0.065(2) 0.056(2) 0.0005(19) 0.0194(19) 0.005(2) C6 0.086(3) 0.074(3) 0.084(3) 0.015(2) 0.022(2) 0.020(2) C7 0.103(4) 0.067(3) 0.104(4) -0.004(3) 0.041(3) 0.005(2) C8 0.092(4) 0.092(3) 0.088(3) -0.015(3) 0.032(3) -0.006(3) C9 0.112(4) 0.070(3) 0.079(3) 0.011(2) 0.006(2) -0.001(3) C10 0.135(5) 0.071(2) 0.126(4) 0.019(3) 0.068(3) 0.023(3) C11 0.091(4) 0.084(3) 0.107(3) 0.017(2) 0.033(3) 0.001(3) C12 0.085(3) 0.067(2) 0.079(3) -0.012(2) 0.007(2) -0.004(2) C13 0.090(3) 0.051(2) 0.074(3) 0.013(2) 0.023(2) 0.006(2) C14 0.063(3) 0.091(3) 0.047(2) 0.011(2) 0.0100(18) 0.015(2) C15 0.060(3) 0.060(2) 0.048(2) -0.0071(18) 0.0093(18) 0.0041(19) C16 0.052(3) 0.062(2) 0.060(2) -0.0009(19) 0.0096(18) 0.0005(18) C17 0.077(3) 0.084(3) 0.058(2) -0.008(2) 0.008(2) 0.004(2) C18 0.083(3) 0.070(3) 0.091(3) -0.014(2) 0.010(3) -0.010(2) C19 0.091(3) 0.064(3) 0.092(3) 0.014(2) 0.018(3) 0.011(2) C20 0.186(6) 0.066(3) 0.140(4) 0.022(3) -0.074(4) 0.000(4) C21 0.131(5) 0.093(4) 0.174(5) -0.050(4) 0.059(4) -0.024(3) C22 0.176(6) 0.124(5) 0.201(6) -0.074(4) 0.128(5) -0.056(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 C1 1.721(3) . ? S1 C5 1.740(3) . ? S2 C12 1.708(4) . ? S2 C16 1.739(3) . ? O1 C3 1.234(3) . ? O2 C14 1.230(3) . ? N1 C8 1.325(4) . ? N1 C5 1.339(4) . ? N2 C19 1.332(4) . ? N2 C16 1.343(3) . ? C1 C2 1.325(4) . ? C1 C9 1.481(4) . ? C2 C3 1.438(4) . ? C2 H21 0.9300 . ? C3 C4 1.471(4) . ? C4 C5 1.386(4) . ? C4 C6 1.386(4) . ? C6 C7 1.349(4) . ? C6 H61 0.9300 . ? C7 C8 1.374(5) . ? C7 H71 0.9300 . ? C8 H81 0.9300 . ? C9 C10 1.481(5) . ? C9 C11 1.487(5) . ? C9 H91 0.9800 . ? C10 C11 1.463(5) . ? C10 H101 0.9700 . ? C10 H102 0.9700 . ? C11 H111 0.9700 . ? C11 H112 0.9700 . ? C12 C13 1.317(4) . ? C12 C20 1.519(5) . ? C13 C14 1.440(5) . ? C13 H131 0.9300 . ? C14 C15 1.479(4) . ? C15 C16 1.358(4) . ? C15 C17 1.392(4) . ? C17 C18 1.376(4) . ? C17 H171 0.9300 . ? C18 C19 1.353(4) . ? C18 H181 0.9300 . ? C19 H191 0.9300 . ? C20 C21 1.355(5) . ? C20 C22 1.367(6) . ? C20 H201 0.9800 . ? C21 C22 1.346(6) . ? C21 H211 0.9700 . ? C21 H212 0.9700 . ? C22 H221 0.9700 . ? C22 H222 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 C1 S1 C5 103.27(17) . . ? C12 S2 C16 103.05(17) . . ? C8 N1 C5 115.6(3) . . ? C19 N2 C16 114.8(3) . . ? C2 C1 C9 124.8(3) . . ? C2 C1 S1 123.9(3) . . ? C9 C1 S1 111.3(2) . . ? C1 C2 C3 127.4(3) . . ? C1 C2 H21 116.3 . . ? C3 C2 H21 116.3 . . ? O1 C3 C2 121.9(3) . . ? O1 C3 C4 120.4(3) . . ? C2 C3 C4 117.8(3) . . ? C5 C4 C6 116.0(3) . . ? C5 C4 C3 124.0(3) . . ? C6 C4 C3 120.0(3) . . ? N1 C5 C4 125.2(3) . . ? N1 C5 S1 111.5(3) . . ? C4 C5 S1 123.3(3) . . ? C7 C6 C4 120.2(4) . . ? C7 C6 H61 119.9 . . ? C4 C6 H61 119.9 . . ? C6 C7 C8 119.0(4) . . ? C6 C7 H71 120.5 . . ? C8 C7 H71 120.5 . . ? N1 C8 C7 124.0(4) . . ? N1 C8 H81 118.0 . . ? C7 C8 H81 118.0 . . ? C1 C9 C10 119.6(3) . . ? C1 C9 C11 120.5(3) . . ? C10 C9 C11 59.1(2) . . ? C1 C9 H91 115.4 . . ? C10 C9 H91 115.4 . . ? C11 C9 H91 115.4 . . ? C11 C10 C9 60.6(3) . . ? C11 C10 H101 117.7 . . ? C9 C10 H101 117.7 . . ? C11 C10 H102 117.7 . . ? C9 C10 H102 117.7 . . ? H101 C10 H102 114.8 . . ? C10 C11 C9 60.3(3) . . ? C10 C11 H111 117.7 . . ? C9 C11 H111 117.7 . . ? C10 C11 H112 117.7 . . ? C9 C11 H112 117.7 . . ? H111 C11 H112 114.9 . . ? C13 C12 C20 126.4(3) . . ? C13 C12 S2 124.3(3) . . ? C20 C12 S2 109.3(3) . . ? C12 C13 C14 127.2(3) . . ? C12 C13 H131 116.4 . . ? C14 C13 H131 116.4 . . ? O2 C14 C13 122.7(4) . . ? O2 C14 C15 119.7(3) . . ? C13 C14 C15 117.6(3) . . ? C16 C15 C17 116.7(3) . . ? C16 C15 C14 123.8(3) . . ? C17 C15 C14 119.5(3) . . ? N2 C16 C15 125.8(3) . . ? N2 C16 S2 110.2(2) . . ? C15 C16 S2 124.0(3) . . ? C18 C17 C15 119.2(3) . . ? C18 C17 H171 120.4 . . ? C15 C17 H171 120.4 . . ? C19 C18 C17 118.4(3) . . ? C19 C18 H181 120.8 . . ? C17 C18 H181 120.8 . . ? N2 C19 C18 125.0(3) . . ? N2 C19 H191 117.5 . . ? C18 C19 H191 117.5 . . ? C21 C20 C22 59.3(3) . . ? C21 C20 C12 125.1(5) . . ? C22 C20 C12 124.9(5) . . ? C21 C20 H201 112.5 . . ? C22 C20 H201 112.5 . . ? C12 C20 H201 112.5 . . ? C22 C21 C20 60.8(4) . . ? C22 C21 H211 117.7 . . ? C20 C21 H211 117.7 . . ? C22 C21 H212 117.7 . . ? C20 C21 H212 117.7 . . ? H211 C21 H212 114.8 . . ? C21 C22 C20 59.9(4) . . ? C21 C22 H221 117.8 . . ? C20 C22 H221 117.8 . . ? C21 C22 H222 117.8 . . ? C20 C22 H222 117.8 . . ? H221 C22 H222 114.9 . . ? 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 S1 C1 C2 -3.3(4) . . . . ? C5 S1 C1 C9 175.8(3) . . . . ? C9 C1 C2 C3 -178.9(4) . . . . ? S1 C1 C2 C3 0.0(7) . . . . ? C1 C2 C3 O1 -175.1(4) . . . . ? C1 C2 C3 C4 5.5(7) . . . . ? O1 C3 C4 C5 173.3(4) . . . . ? C2 C3 C4 C5 -7.3(6) . . . . ? O1 C3 C4 C6 -6.7(6) . . . . ? C2 C3 C4 C6 172.7(4) . . . . ? C8 N1 C5 C4 -2.1(6) . . . . ? C8 N1 C5 S1 178.1(3) . . . . ? C6 C4 C5 N1 3.8(6) . . . . ? C3 C4 C5 N1 -176.2(4) . . . . ? C6 C4 C5 S1 -176.4(3) . . . . ? C3 C4 C5 S1 3.6(6) . . . . ? C1 S1 C5 N1 -178.7(3) . . . . ? C1 S1 C5 C4 1.5(4) . . . . ? C5 C4 C6 C7 -2.4(6) . . . . ? C3 C4 C6 C7 177.6(4) . . . . ? C4 C6 C7 C8 -0.4(6) . . . . ? C5 N1 C8 C7 -1.0(6) . . . . ? C6 C7 C8 N1 2.2(7) . . . . ? C2 C1 C9 C10 38.1(7) . . . . ? S1 C1 C9 C10 -140.9(4) . . . . ? C2 C1 C9 C11 -31.3(7) . . . . ? S1 C1 C9 C11 149.6(3) . . . . ? C1 C9 C10 C11 -109.9(4) . . . . ? C1 C9 C11 C10 108.4(4) . . . . ? C16 S2 C12 C13 -0.4(5) . . . . ? C16 S2 C12 C20 179.0(4) . . . . ? C20 C12 C13 C14 -178.6(5) . . . . ? S2 C12 C13 C14 0.6(7) . . . . ? C12 C13 C14 O2 178.3(4) . . . . ? C12 C13 C14 C15 -1.4(6) . . . . ? O2 C14 C15 C16 -177.4(4) . . . . ? C13 C14 C15 C16 2.3(6) . . . . ? O2 C14 C15 C17 1.8(5) . . . . ? C13 C14 C15 C17 -178.4(3) . . . . ? C19 N2 C16 C15 1.3(6) . . . . ? C19 N2 C16 S2 -178.8(3) . . . . ? C17 C15 C16 N2 -1.7(6) . . . . ? C14 C15 C16 N2 177.6(4) . . . . ? C17 C15 C16 S2 178.4(3) . . . . ? C14 C15 C16 S2 -2.3(5) . . . . ? C12 S2 C16 N2 -178.7(3) . . . . ? C12 S2 C16 C15 1.2(4) . . . . ? C16 C15 C17 C18 1.0(6) . . . . ? C14 C15 C17 C18 -178.4(4) . . . . ? C15 C17 C18 C19 0.0(6) . . . . ? C16 N2 C19 C18 -0.2(6) . . . . ? C17 C18 C19 N2 -0.4(7) . . . . ? C13 C12 C20 C21 38.4(10) . . . . ? S2 C12 C20 C21 -140.9(7) . . . . ? C13 C12 C20 C22 -35.8(10) . . . . ? S2 C12 C20 C22 144.8(6) . . . . ? C12 C20 C21 C22 -113.3(7) . . . . ? C12 C20 C22 C21 113.7(6) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.252 _refine_diff_density_min -0.157 _refine_diff_density_rms 0.030