# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2010 data_global2 _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Maguire, Anita' _publ_contact_author_email a.maguire@ucc.ie _publ_section_title ; The Influence of Reaction Conditions on the Diels Alder Cycloadditions of 2-Thio-3-Chloroacrylamides; Investigation of Thermal, Catalytic and Microwave Conditions ; loop_ _publ_author_name A.Maguire M.Kissane S.Lawrence J.Chopra D.Lynch # Attachment '- Maguire_OBM.cif' data_endo-4b _database_code_depnum_ccdc_archive 'CCDC 784305' #TrackingRef '- Maguire_OBM.cif' #===================================================================== _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H18 Cl N O2 S' _chemical_formula_sum 'C16 H18 Cl N O2 S' _chemical_formula_weight 323.82 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.221(4) _cell_length_b 9.997(3) _cell_length_c 10.709(6) _cell_angle_alpha 114.90(4) _cell_angle_beta 92.12(5) _cell_angle_gamma 99.43(3) _cell_volume 782.0(6) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 22 _cell_measurement_theta_min 3.82 _cell_measurement_theta_max 11.59 _exptl_crystal_description blocks _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.48 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.35 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.375 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 340 _exptl_absorpt_coefficient_mu 0.381 _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 150(2) _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius MACH3' _diffrn_measurement_method '\w-2\q scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 0 _diffrn_reflns_number 2870 _diffrn_reflns_av_R_equivalents 0.0200 _diffrn_reflns_av_sigmaI/netI 0.0587 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.11 _diffrn_reflns_theta_max 25.33 _reflns_number_total 2668 _reflns_number_gt 1828 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CAD4 data collection software, Nonius BV, Delft, The Netherlands, 1988. ; _computing_cell_refinement ; CAD4 data collection software, Nonius BV, Delft, The Netherlands, 1988. ; _computing_data_reduction ; S.Mackay, S; Gilmore, C.J.; Edwards, C.; Tremayne, M.; Stuart, N.; Shankland, K; maXus, : a computer program for the solution and refinement of crystal structures from diffraction data University of Glasgow, Scotland, UK, Nonius BV, Delft, The Netherlands & MacScience Co. Ltd., Yokohama, Japan, 1998. ; _computing_structure_solution ; SHELXS-86, Sheldrick, G.M. Acta Cryst. A, 2008, 64, 112-122. ; _computing_structure_refinement ; SHELXL-97, Sheldrick, G.M. Acta Cryst. A, 2008, 64, 112-122. ; _computing_molecular_graphics ; PLATON, Spek, A.L., Acta Cryst., 2009, D65, 148-155. ; _computing_publication_material 'SHELXL-97; PLATON' _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^)+(0.0954P)^2^+1.5269P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2668 _refine_ls_number_parameters 190 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.1162 _refine_ls_R_factor_gt 0.0669 _refine_ls_wR_factor_ref 0.2003 _refine_ls_wR_factor_gt 0.1553 _refine_ls_goodness_of_fit_ref 1.112 _refine_ls_restrained_S_all 1.112 _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 C1 C 0.0848(7) 0.3582(5) 0.6591(6) 0.0331(12) Uani 1 1 d . . . H1 H 0.0222 0.3478 0.5726 0.040 Uiso 1 1 calc R . . C2 C 0.2238(6) 0.5036(5) 0.7357(5) 0.0239(11) Uani 1 1 d . . . C3 C 0.3302(7) 0.4602(6) 0.8304(5) 0.0325(12) Uani 1 1 d . . . H3 H 0.3266 0.5294 0.9297 0.039 Uiso 1 1 calc R . . C4 C 0.2385(8) 0.2984(6) 0.7998(6) 0.0423(14) Uani 1 1 d . . . H4 H 0.3019 0.2379 0.8302 0.051 Uiso 1 1 calc R . . C5 C 0.0731(8) 0.3186(6) 0.8533(7) 0.0479(16) Uani 1 1 d . . . H5 H 0.0395 0.3081 0.9332 0.058 Uiso 1 1 calc R . . C6 C -0.0173(7) 0.3530(5) 0.7713(6) 0.0397(14) Uani 1 1 d . . . H6 H -0.1270 0.3713 0.7811 0.048 Uiso 1 1 calc R . . C7 C 0.1850(7) 0.2355(5) 0.6426(6) 0.0389(14) Uani 1 1 d . . . H7A H 0.2800 0.2381 0.5889 0.047 Uiso 1 1 calc R . . H7B H 0.1152 0.1332 0.6030 0.047 Uiso 1 1 calc R . . C8 C 0.1556(6) 0.6445(5) 0.8173(5) 0.0225(10) Uani 1 1 d U . . O9 O 0.2113(4) 0.7276(3) 0.9403(3) 0.0318(8) Uani 1 1 d . . . N10 N 0.0354(5) 0.6684(4) 0.7484(4) 0.0283(10) Uani 1 1 d . . . H10 H 0.0024 0.6037 0.6615 0.034 Uiso 1 1 calc R . . C11 C -0.0444(7) 0.7966(6) 0.8098(6) 0.0372(13) Uani 1 1 d . . . H11A H -0.0337 0.8313 0.9115 0.045 Uiso 1 1 calc R . . H11B H -0.1642 0.7641 0.7752 0.045 Uiso 1 1 calc R . . C12 C 0.0252(10) 0.9244(7) 0.7795(7) 0.061(2) Uani 1 1 d . . . H12A H -0.0341 1.0068 0.8242 0.091 Uiso 1 1 calc R . . H12B H 0.0123 0.8921 0.6791 0.091 Uiso 1 1 calc R . . H12C H 0.1433 0.9591 0.8153 0.091 Uiso 1 1 calc R . . S13 S 0.33858(15) 0.52749(13) 0.59456(12) 0.0253(4) Uani 1 1 d . . . O14 O 0.2070(5) 0.5013(4) 0.4831(4) 0.0384(9) Uani 1 1 d . . . C15 C 0.4160(6) 0.7268(5) 0.6711(5) 0.0262(11) Uani 1 1 d . . . C16 C 0.3818(7) 0.8023(6) 0.5941(6) 0.0372(13) Uani 1 1 d . . . H16 H 0.3142 0.7506 0.5073 0.045 Uiso 1 1 calc R . . C17 C 0.4484(9) 0.9563(7) 0.6461(7) 0.0498(16) Uani 1 1 d . . . H17 H 0.4225 1.0104 0.5958 0.060 Uiso 1 1 calc R . . C18 C 0.5510(8) 1.0301(6) 0.7694(7) 0.0481(16) Uani 1 1 d . . . H18 H 0.5987 1.1338 0.8017 0.058 Uiso 1 1 calc R . . C19 C 0.5851(7) 0.9552(6) 0.8463(6) 0.0417(14) Uani 1 1 d . . . H19 H 0.6533 1.0077 0.9327 0.050 Uiso 1 1 calc R . . C20 C 0.5195(6) 0.8025(6) 0.7975(5) 0.0316(12) Uani 1 1 d . . . H20 H 0.5446 0.7497 0.8493 0.038 Uiso 1 1 calc R . . Cl21 Cl 0.54422(18) 0.45845(17) 0.79706(15) 0.0432(4) Uani 1 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 0.035(3) 0.014(2) 0.037(3) 0.001(2) 0.002(2) -0.002(2) C2 0.031(3) 0.011(2) 0.026(2) 0.0050(19) 0.004(2) 0.0024(19) C3 0.045(3) 0.026(3) 0.026(3) 0.009(2) 0.005(2) 0.011(2) C4 0.058(4) 0.022(3) 0.054(4) 0.020(3) 0.021(3) 0.015(3) C5 0.068(4) 0.021(3) 0.057(4) 0.018(3) 0.030(3) 0.006(3) C6 0.043(3) 0.013(2) 0.056(4) 0.009(2) 0.021(3) 0.002(2) C7 0.050(4) 0.013(2) 0.047(3) 0.006(2) 0.017(3) 0.005(2) C8 0.029(2) 0.010(2) 0.024(2) 0.0052(18) 0.008(2) -0.0027(18) O9 0.042(2) 0.0148(17) 0.0232(18) -0.0035(14) -0.0018(15) -0.0018(15) N10 0.034(2) 0.020(2) 0.025(2) 0.0025(17) -0.0001(18) 0.0090(18) C11 0.043(3) 0.029(3) 0.037(3) 0.008(2) 0.007(3) 0.018(2) C12 0.089(5) 0.026(3) 0.074(5) 0.021(3) 0.036(4) 0.025(3) S13 0.0307(7) 0.0179(6) 0.0201(6) 0.0023(5) 0.0020(5) 0.0025(5) O14 0.043(2) 0.035(2) 0.0260(19) 0.0070(16) -0.0062(16) -0.0023(17) C15 0.030(3) 0.014(2) 0.025(2) 0.0012(19) 0.004(2) 0.0001(19) C16 0.050(3) 0.031(3) 0.034(3) 0.016(2) 0.011(3) 0.013(3) C17 0.068(4) 0.037(3) 0.061(4) 0.033(3) 0.025(4) 0.016(3) C18 0.052(4) 0.020(3) 0.067(4) 0.014(3) 0.025(3) 0.000(3) C19 0.038(3) 0.021(3) 0.045(3) -0.002(2) 0.008(3) -0.005(2) C20 0.035(3) 0.023(3) 0.033(3) 0.009(2) 0.003(2) 0.005(2) Cl21 0.0403(8) 0.0463(9) 0.0458(8) 0.0201(7) 0.0014(6) 0.0166(7) _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 C6 1.505(8) . ? C1 C7 1.540(7) . ? C1 C2 1.573(7) . ? C1 H1 1.0000 . ? C2 C8 1.523(6) . ? C2 C3 1.553(7) . ? C2 S13 1.889(5) . ? C3 C4 1.558(7) . ? C3 Cl21 1.810(6) . ? C3 H3 1.0000 . ? C4 C5 1.506(9) . ? C4 C7 1.545(8) . ? C4 H4 1.0000 . ? C5 C6 1.317(9) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 H7A 0.9900 . ? C7 H7B 0.9900 . ? C8 O9 1.243(6) . ? C8 N10 1.323(6) . ? N10 C11 1.450(6) . ? N10 H10 0.8800 . ? C11 C12 1.478(8) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? S13 O14 1.488(4) . ? S13 C15 1.794(5) . ? C15 C16 1.380(7) . ? C15 C20 1.404(7) . ? C16 C17 1.400(8) . ? C16 H16 0.9500 . ? C17 C18 1.376(9) . ? C17 H17 0.9500 . ? C18 C19 1.374(9) . ? C18 H18 0.9500 . ? C19 C20 1.390(7) . ? C19 H19 0.9500 . ? C20 H20 0.9500 . ? 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 C6 C1 C7 100.6(4) . . ? C6 C1 C2 104.2(4) . . ? C7 C1 C2 100.4(4) . . ? C6 C1 H1 116.4 . . ? C7 C1 H1 116.4 . . ? C2 C1 H1 116.4 . . ? C8 C2 C3 112.5(4) . . ? C8 C2 C1 113.4(4) . . ? C3 C2 C1 102.6(4) . . ? C8 C2 S13 109.5(3) . . ? C3 C2 S13 112.9(3) . . ? C1 C2 S13 105.5(3) . . ? C2 C3 C4 103.3(4) . . ? C2 C3 Cl21 115.3(4) . . ? C4 C3 Cl21 109.7(4) . . ? C2 C3 H3 109.4 . . ? C4 C3 H3 109.4 . . ? Cl21 C3 H3 109.4 . . ? C5 C4 C7 99.9(5) . . ? C5 C4 C3 104.7(4) . . ? C7 C4 C3 100.0(4) . . ? C5 C4 H4 116.5 . . ? C7 C4 H4 116.5 . . ? C3 C4 H4 116.5 . . ? C6 C5 C4 108.9(5) . . ? C6 C5 H5 125.6 . . ? C4 C5 H5 125.6 . . ? C5 C6 C1 107.5(5) . . ? C5 C6 H6 126.3 . . ? C1 C6 H6 126.3 . . ? C1 C7 C4 94.0(4) . . ? C1 C7 H7A 112.9 . . ? C4 C7 H7A 112.9 . . ? C1 C7 H7B 112.9 . . ? C4 C7 H7B 112.9 . . ? H7A C7 H7B 110.3 . . ? O9 C8 N10 124.1(4) . . ? O9 C8 C2 120.5(4) . . ? N10 C8 C2 115.3(4) . . ? C8 N10 C11 122.8(4) . . ? C8 N10 H10 118.6 . . ? C11 N10 H10 118.6 . . ? N10 C11 C12 113.8(5) . . ? N10 C11 H11A 108.8 . . ? C12 C11 H11A 108.8 . . ? N10 C11 H11B 108.8 . . ? C12 C11 H11B 108.8 . . ? H11A C11 H11B 107.7 . . ? C11 C12 H12A 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C11 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? O14 S13 C15 104.2(2) . . ? O14 S13 C2 105.2(2) . . ? C15 S13 C2 101.9(2) . . ? C16 C15 C20 120.5(5) . . ? C16 C15 S13 116.9(4) . . ? C20 C15 S13 122.4(4) . . ? C15 C16 C17 118.8(5) . . ? C15 C16 H16 120.6 . . ? C17 C16 H16 120.6 . . ? C18 C17 C16 120.6(6) . . ? C18 C17 H17 119.7 . . ? C16 C17 H17 119.7 . . ? C19 C18 C17 120.6(5) . . ? C19 C18 H18 119.7 . . ? C17 C18 H18 119.7 . . ? C18 C19 C20 119.9(6) . . ? C18 C19 H19 120.0 . . ? C20 C19 H19 120.0 . . ? C19 C20 C15 119.5(5) . . ? C19 C20 H20 120.2 . . ? C15 C20 H20 120.2 . . ? 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 C6 C1 C2 C8 -53.3(5) . . . . ? C7 C1 C2 C8 -157.2(4) . . . . ? C6 C1 C2 C3 68.4(5) . . . . ? C7 C1 C2 C3 -35.5(5) . . . . ? C6 C1 C2 S13 -173.1(3) . . . . ? C7 C1 C2 S13 82.9(4) . . . . ? C8 C2 C3 C4 121.0(4) . . . . ? C1 C2 C3 C4 -1.2(5) . . . . ? S13 C2 C3 C4 -114.3(4) . . . . ? C8 C2 C3 Cl21 -119.3(4) . . . . ? C1 C2 C3 Cl21 118.5(4) . . . . ? S13 C2 C3 Cl21 5.4(5) . . . . ? C2 C3 C4 C5 -65.7(5) . . . . ? Cl21 C3 C4 C5 170.9(4) . . . . ? C2 C3 C4 C7 37.4(5) . . . . ? Cl21 C3 C4 C7 -86.0(4) . . . . ? C7 C4 C5 C6 -32.4(6) . . . . ? C3 C4 C5 C6 70.9(6) . . . . ? C4 C5 C6 C1 -0.3(6) . . . . ? C7 C1 C6 C5 33.0(5) . . . . ? C2 C1 C6 C5 -70.8(5) . . . . ? C6 C1 C7 C4 -49.1(5) . . . . ? C2 C1 C7 C4 57.7(4) . . . . ? C5 C4 C7 C1 48.5(4) . . . . ? C3 C4 C7 C1 -58.5(5) . . . . ? C3 C2 C8 O9 13.9(6) . . . . ? C1 C2 C8 O9 129.8(5) . . . . ? S13 C2 C8 O9 -112.6(4) . . . . ? C3 C2 C8 N10 -165.5(4) . . . . ? C1 C2 C8 N10 -49.5(6) . . . . ? S13 C2 C8 N10 68.1(5) . . . . ? O9 C8 N10 C11 0.5(7) . . . . ? C2 C8 N10 C11 179.8(4) . . . . ? C8 N10 C11 C12 96.4(6) . . . . ? C8 C2 S13 O14 -77.8(4) . . . . ? C3 C2 S13 O14 155.9(3) . . . . ? C1 C2 S13 O14 44.6(4) . . . . ? C8 C2 S13 C15 30.7(4) . . . . ? C3 C2 S13 C15 -95.6(4) . . . . ? C1 C2 S13 C15 153.1(3) . . . . ? O14 S13 C15 C16 -18.3(5) . . . . ? C2 S13 C15 C16 -127.6(4) . . . . ? O14 S13 C15 C20 167.4(4) . . . . ? C2 S13 C15 C20 58.1(5) . . . . ? C20 C15 C16 C17 -1.8(8) . . . . ? S13 C15 C16 C17 -176.1(4) . . . . ? C15 C16 C17 C18 2.3(9) . . . . ? C16 C17 C18 C19 -2.4(9) . . . . ? C17 C18 C19 C20 1.9(9) . . . . ? C18 C19 C20 C15 -1.3(8) . . . . ? C16 C15 C20 C19 1.3(8) . . . . ? S13 C15 C20 C19 175.4(4) . . . . ? _diffrn_measured_fraction_theta_max 0.931 _diffrn_reflns_theta_full 25.33 _diffrn_measured_fraction_theta_full 0.931 _refine_diff_density_max 0.623 _refine_diff_density_min -0.836 _refine_diff_density_rms 0.112 #===================================================================== # END of data_endo-4b #===================================================================== #===================================================================== data_exo-4b _database_code_depnum_ccdc_archive 'CCDC 784306' #TrackingRef '- Maguire_OBM.cif' #===================================================================== _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H18 Cl N O2 S' _chemical_formula_sum 'C16 H18 Cl N O2 S' _chemical_formula_weight 323.82 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' Cl Cl 0.1484 0.1585 '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/n _symmetry_space_group_name_Hall '-P 2yn' 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 9.9680(10) _cell_length_b 13.712(2) _cell_length_c 11.671(2) _cell_angle_alpha 90.00 _cell_angle_beta 99.670(10) _cell_angle_gamma 90.00 _cell_volume 1572.5(4) _cell_formula_units_Z 4 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 22 _cell_measurement_theta_min 7.71 _cell_measurement_theta_max 12.13 _exptl_crystal_description blocks _exptl_crystal_colour colourless _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.55 _exptl_crystal_size_min 0.50 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.368 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 680 _exptl_absorpt_coefficient_mu 0.379 _exptl_absorpt_correction_type None _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; An incorrect data collection strategy means only 50% of the data were collected. ; _diffrn_ambient_temperature 291(2) _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius MACH3' _diffrn_measurement_method '\w-2\q scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 0.04 _diffrn_reflns_number 3657 _diffrn_reflns_av_R_equivalents 0.0234 _diffrn_reflns_av_sigmaI/netI 0.0507 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -2 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.31 _diffrn_reflns_theta_max 27.46 _reflns_number_total 1800 _reflns_number_gt 1009 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CAD4 data collection software, Nonius BV, Delft, The Netherlands, 1988. ; _computing_cell_refinement ; CAD4 data collection software, Nonius BV, Delft, The Netherlands, 1988. ; _computing_data_reduction ; PLATON, Spek, A.L., Acta Cryst., 2009, D65, 148-155. ; _computing_structure_solution ; SHELXS-86, Sheldrick, G.M. Acta Cryst. A, 2008, 64, 112-122. ; _computing_structure_refinement ; SHELXL-93, Sheldrick, G.M. Acta Cryst. A, 2008, 64, 112-122. ; _computing_molecular_graphics ; PLATON, Spek, A.L., Acta Cryst., 2009, D65, 148-155. ; _computing_publication_material 'SHELXL-97; PLATON' _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^)+(0.0700P)^2^+0.0300P] 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 constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.009(2) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1800 _refine_ls_number_parameters 180 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0910 _refine_ls_R_factor_gt 0.0436 _refine_ls_wR_factor_ref 0.1307 _refine_ls_wR_factor_gt 0.1136 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.079 _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 C1 C 0.8204(6) 0.3653(3) 0.7122(5) 0.049(3) Uani 1 1 d . . . H1 H 0.8853 0.4194 0.7267 0.059 Uiso 1 1 calc R . . C2 C 0.8787(6) 0.2662(3) 0.6682(4) 0.040(2) Uani 1 1 d . . . C3 C 0.7430(5) 0.2118(3) 0.6175(4) 0.0380(19) Uani 1 1 d . . . H3 H 0.7399 0.2027 0.5338 0.046 Uiso 1 1 calc R . . C4 C 0.6309(6) 0.2849(3) 0.6356(5) 0.049(3) Uani 1 1 d . . . H4 H 0.5419 0.2735 0.5876 0.059 Uiso 1 1 calc R . . C5 C 0.6295(7) 0.2951(3) 0.7655(6) 0.055(3) Uani 1 1 d . . . H5 H 0.5626 0.2730 0.8059 0.066 Uiso 1 1 calc R . . C6 C 0.7436(7) 0.3421(3) 0.8092(6) 0.056(3) Uani 1 1 d . . . H6 H 0.7712 0.3580 0.8870 0.067 Uiso 1 1 calc R . . C7 C 0.7004(6) 0.3801(3) 0.6110(5) 0.057(3) Uani 1 1 d . . . H7A H 0.6463 0.4373 0.6207 0.068 Uiso 1 1 calc R . . H7B H 0.7287 0.3809 0.5354 0.068 Uiso 1 1 calc R . . C8 C 0.9639(6) 0.2844(3) 0.5772(5) 0.046(3) Uani 1 1 d . B . N9 N 1.0664(6) 0.3499(4) 0.6073(5) 0.065(3) Uani 1 1 d D . . H9 H 1.0856 0.3651 0.6798 0.078 Uiso 1 1 calc R A 1 C10 C 1.1514(11) 0.3994(8) 0.5262(11) 0.084(3) Uiso 0.65 1 d PD B 1 H10A H 1.1421 0.3632 0.4539 0.100 Uiso 0.65 1 calc PR B 1 H10B H 1.1167 0.4647 0.5083 0.100 Uiso 0.65 1 calc PR B 1 C11 C 1.2883(12) 0.4048(10) 0.5753(14) 0.115(4) Uiso 0.65 1 d PD B 1 H11A H 1.3215 0.4694 0.5651 0.172 Uiso 0.65 1 calc PR B 1 H11B H 1.3391 0.3586 0.5380 0.172 Uiso 0.65 1 calc PR B 1 H11C H 1.2988 0.3902 0.6568 0.172 Uiso 0.65 1 calc PR B 1 C10' C 1.1740(15) 0.3393(14) 0.5428(15) 0.071(4) Uiso 0.35 1 d PD B 2 H10C H 1.1688 0.2698 0.5271 0.086 Uiso 0.35 1 calc PR B 2 H10D H 1.1331 0.3690 0.4698 0.086 Uiso 0.35 1 calc PR B 2 C11' C 1.2923(15) 0.3537(16) 0.540(2) 0.100(6) Uiso 0.35 1 d PD B 2 H11D H 1.3068 0.3550 0.4611 0.149 Uiso 0.35 1 calc PR B 2 H11E H 1.3458 0.3024 0.5813 0.149 Uiso 0.35 1 calc PR B 2 H11F H 1.3189 0.4151 0.5766 0.149 Uiso 0.35 1 calc PR B 2 O12 O 0.9434(4) 0.2470(2) 0.4799(3) 0.059(2) Uani 1 1 d . . . S13 S 0.98203(14) 0.20745(7) 0.79890(10) 0.0454(6) Uani 1 1 d . . . O14 O 1.0672(4) 0.2900(2) 0.8563(3) 0.0584(17) Uani 1 1 d . . . C15 C 1.0973(3) 0.13236(19) 0.7334(3) 0.048(2) Uani 1 1 d G . . C16 C 1.0543(2) 0.0486(2) 0.6709(3) 0.063(3) Uani 1 1 d G . . H16 H 0.9628 0.0312 0.6587 0.076 Uiso 1 1 calc R . . C17 C 1.1479(3) -0.0093(2) 0.6266(3) 0.073(3) Uani 1 1 d G . . H17 H 1.1191 -0.0654 0.5847 0.087 Uiso 1 1 calc R . . C18 C 1.2847(3) 0.0165(2) 0.6448(3) 0.065(3) Uani 1 1 d G . . H18 H 1.3474 -0.0222 0.6152 0.078 Uiso 1 1 calc R . . C19 C 1.3278(2) 0.1003(3) 0.7073(3) 0.077(4) Uani 1 1 d G . . H19 H 1.4193 0.1177 0.7195 0.092 Uiso 1 1 calc R . . C20 C 1.2341(3) 0.15826(19) 0.7516(3) 0.059(3) Uani 1 1 d G . . H20 H 1.2629 0.2143 0.7935 0.071 Uiso 1 1 calc R . . Cl21 Cl 0.71665(15) 0.09518(8) 0.68160(15) 0.0592(7) Uani 1 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 0.060(5) 0.033(2) 0.055(4) -0.004(2) 0.008(5) 0.004(2) C2 0.046(4) 0.037(2) 0.035(3) 0.006(2) 0.004(4) -0.004(2) C3 0.037(3) 0.0369(19) 0.042(3) 0.000(2) 0.011(4) 0.003(2) C4 0.043(4) 0.052(3) 0.053(4) -0.001(3) 0.010(5) 0.009(3) C5 0.055(5) 0.058(3) 0.061(4) 0.005(3) 0.032(6) 0.013(3) C6 0.079(6) 0.044(3) 0.048(4) -0.007(3) 0.021(6) 0.018(3) C7 0.065(4) 0.050(3) 0.058(4) 0.015(3) 0.016(5) 0.018(3) C8 0.045(4) 0.048(2) 0.046(4) 0.005(3) 0.006(5) -0.009(3) N9 0.063(4) 0.089(3) 0.051(4) -0.009(3) 0.034(5) -0.037(3) O12 0.057(3) 0.079(2) 0.042(2) -0.006(2) 0.015(3) -0.012(2) S13 0.0504(9) 0.0483(6) 0.0358(7) 0.0009(6) 0.0020(9) 0.0021(6) O14 0.064(3) 0.0580(18) 0.049(2) -0.0173(18) -0.003(3) -0.002(2) C15 0.051(3) 0.043(2) 0.046(3) -0.004(2) -0.006(4) 0.007(2) C16 0.047(4) 0.057(3) 0.079(5) -0.017(3) -0.006(5) 0.005(3) C17 0.067(4) 0.065(3) 0.079(5) -0.017(4) -0.008(5) 0.008(3) C18 0.059(4) 0.073(4) 0.066(5) -0.003(4) 0.021(6) 0.033(3) C19 0.056(4) 0.067(3) 0.101(6) -0.001(4) -0.004(6) 0.002(3) C20 0.048(4) 0.054(3) 0.072(5) -0.010(3) -0.001(5) 0.003(3) Cl21 0.0507(9) 0.0430(6) 0.0853(12) 0.0091(7) 0.0152(12) -0.0061(6) _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 C6 1.503(11) . ? C1 C7 1.547(5) . ? C1 C2 1.596(8) . ? C1 H1 0.9800 . ? C2 C8 1.488(9) . ? C2 C3 1.570(6) . ? C2 S13 1.874(3) . ? C3 C4 1.542(8) . ? C3 Cl21 1.804(5) . ? C3 H3 0.9800 . ? C4 C5 1.524(11) . ? C4 C7 1.527(8) . ? C4 H4 0.9800 . ? C5 C6 1.332(8) . ? C5 H5 0.9300 . ? C6 H6 0.9300 . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 O12 1.232(7) . ? C8 N9 1.361(7) . ? N9 C10' 1.418(18) . ? N9 C10 1.531(14) . ? N9 H9 0.8600 . ? C10 C11 1.391(12) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C10' C11' 1.201(17) . ? C10' H10C 0.9700 . ? C10' H10D 0.9700 . ? C11' H11D 0.9600 . ? C11' H11E 0.9600 . ? C11' H11F 0.9600 . ? S13 O14 1.503(3) . ? S13 C15 1.806(3) . ? C15 C16 1.3900 . ? C15 C20 1.3900 . ? C16 C17 1.3900 . ? C16 H16 0.9300 . ? C17 C18 1.3900 . ? C17 H17 0.9300 . ? C18 C19 1.3900 . ? C18 H18 0.9300 . ? C19 C20 1.3900 . ? C19 H19 0.9300 . ? C20 H20 0.9300 . ? 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 C6 C1 C7 100.1(5) . . ? C6 C1 C2 108.8(4) . . ? C7 C1 C2 98.2(3) . . ? C6 C1 H1 115.8 . . ? C7 C1 H1 115.8 . . ? C2 C1 H1 115.8 . . ? C8 C2 C3 111.7(4) . . ? C8 C2 C1 111.7(4) . . ? C3 C2 C1 100.9(4) . . ? C8 C2 S13 110.6(4) . . ? C3 C2 S13 115.1(3) . . ? C1 C2 S13 106.5(3) . . ? C4 C3 C2 103.7(4) . . ? C4 C3 Cl21 111.1(4) . . ? C2 C3 Cl21 116.2(2) . . ? C4 C3 H3 108.5 . . ? C2 C3 H3 108.5 . . ? Cl21 C3 H3 108.5 . . ? C5 C4 C7 100.9(4) . . ? C5 C4 C3 108.9(4) . . ? C7 C4 C3 99.6(5) . . ? C5 C4 H4 115.1 . . ? C7 C4 H4 115.1 . . ? C3 C4 H4 115.1 . . ? C6 C5 C4 105.9(8) . . ? C6 C5 H5 127.0 . . ? C4 C5 H5 127.0 . . ? C5 C6 C1 108.9(5) . . ? C5 C6 H6 125.5 . . ? C1 C6 H6 125.5 . . ? C4 C7 C1 93.5(4) . . ? C4 C7 H7A 113.0 . . ? C1 C7 H7A 113.0 . . ? C4 C7 H7B 113.0 . . ? C1 C7 H7B 113.0 . . ? H7A C7 H7B 110.4 . . ? O12 C8 N9 120.9(7) . . ? O12 C8 C2 124.2(4) . . ? N9 C8 C2 114.9(5) . . ? C8 N9 C10' 113.4(9) . . ? C8 N9 C10 127.0(6) . . ? C8 N9 H9 116.5 . . ? C10' N9 H9 119.0 . . ? C10 N9 H9 116.5 . . ? C11 C10 N9 112.0(8) . . ? C11 C10 H10A 109.2 . . ? N9 C10 H10A 109.2 . . ? C11 C10 H10B 109.2 . . ? N9 C10 H10B 109.2 . . ? H10A C10 H10B 107.9 . . ? 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 . . ? C11' C10' N9 146.0(18) . . ? C11' C10' H10C 100.3 . . ? N9 C10' H10C 100.3 . . ? C11' C10' H10D 100.3 . . ? N9 C10' H10D 100.3 . . ? H10C C10' H10D 104.3 . . ? C10' C11' H11D 109.5 . . ? C10' C11' H11E 109.5 . . ? H11D C11' H11E 109.5 . . ? C10' C11' H11F 109.5 . . ? H11D C11' H11F 109.5 . . ? H11E C11' H11F 109.5 . . ? O14 S13 C15 105.4(2) . . ? O14 S13 C2 103.38(17) . . ? C15 S13 C2 101.7(2) . . ? C16 C15 C20 120.0 . . ? C16 C15 S13 122.09(17) . . ? C20 C15 S13 117.85(16) . . ? C17 C16 C15 120.0 . . ? C17 C16 H16 120.0 . . ? C15 C16 H16 120.0 . . ? C16 C17 C18 120.0 . . ? C16 C17 H17 120.0 . . ? C18 C17 H17 120.0 . . ? C19 C18 C17 120.0 . . ? C19 C18 H18 120.0 . . ? C17 C18 H18 120.0 . . ? C18 C19 C20 120.0 . . ? C18 C19 H19 120.0 . . ? C20 C19 H19 120.0 . . ? C19 C20 C15 120.0 . . ? C19 C20 H20 120.0 . . ? C15 C20 H20 120.0 . . ? 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 C6 C1 C2 C8 -176.2(3) . . . . ? C7 C1 C2 C8 80.1(5) . . . . ? C6 C1 C2 C3 65.0(4) . . . . ? C7 C1 C2 C3 -38.7(6) . . . . ? C6 C1 C2 S13 -55.4(5) . . . . ? C7 C1 C2 S13 -159.1(4) . . . . ? C8 C2 C3 C4 -117.4(5) . . . . ? C1 C2 C3 C4 1.4(5) . . . . ? S13 C2 C3 C4 115.5(4) . . . . ? C8 C2 C3 Cl21 120.4(4) . . . . ? C1 C2 C3 Cl21 -120.8(4) . . . . ? S13 C2 C3 Cl21 -6.7(6) . . . . ? C2 C3 C4 C5 -68.0(6) . . . . ? Cl21 C3 C4 C5 57.5(5) . . . . ? C2 C3 C4 C7 37.1(5) . . . . ? Cl21 C3 C4 C7 162.6(3) . . . . ? C7 C4 C5 C6 -34.4(5) . . . . ? C3 C4 C5 C6 69.8(5) . . . . ? C4 C5 C6 C1 0.9(6) . . . . ? C7 C1 C6 C5 32.3(5) . . . . ? C2 C1 C6 C5 -70.0(5) . . . . ? C5 C4 C7 C1 50.5(6) . . . . ? C3 C4 C7 C1 -61.1(5) . . . . ? C6 C1 C7 C4 -49.5(5) . . . . ? C2 C1 C7 C4 61.3(6) . . . . ? C3 C2 C8 O12 -12.0(6) . . . . ? C1 C2 C8 O12 -124.2(5) . . . . ? S13 C2 C8 O12 117.5(4) . . . . ? C3 C2 C8 N9 165.6(4) . . . . ? C1 C2 C8 N9 53.5(5) . . . . ? S13 C2 C8 N9 -64.9(5) . . . . ? O12 C8 N9 C10' -24.9(11) . . . . ? C2 C8 N9 C10' 157.3(9) . . . . ? O12 C8 N9 C10 11.4(10) . . . . ? C2 C8 N9 C10 -166.3(7) . . . . ? C8 N9 C10 C11 -138.9(9) . . . . ? C10' N9 C10 C11 -62.2(13) . . . . ? C8 N9 C10' C11' -157(4) . . . . ? C10 N9 C10' C11' 81(4) . . . . ? C8 C2 S13 O14 74.9(4) . . . . ? C3 C2 S13 O14 -157.4(4) . . . . ? C1 C2 S13 O14 -46.6(5) . . . . ? C8 C2 S13 C15 -34.3(3) . . . . ? C3 C2 S13 C15 93.4(4) . . . . ? C1 C2 S13 C15 -155.7(4) . . . . ? O14 S13 C15 C16 -179.4(2) . . . . ? C2 S13 C15 C16 -71.8(2) . . . . ? O14 S13 C15 C20 3.5(2) . . . . ? C2 S13 C15 C20 111.1(2) . . . . ? C20 C15 C16 C17 0.0 . . . . ? S13 C15 C16 C17 -177.0(2) . . . . ? C15 C16 C17 C18 0.0 . . . . ? C16 C17 C18 C19 0.0 . . . . ? C17 C18 C19 C20 0.0 . . . . ? C18 C19 C20 C15 0.0 . . . . ? C16 C15 C20 C19 0.0 . . . . ? S13 C15 C20 C19 177.2(2) . . . . ? _diffrn_measured_fraction_theta_max 0.501 _diffrn_reflns_theta_full 27.46 _diffrn_measured_fraction_theta_full 0.501 _refine_diff_density_max 0.187 _refine_diff_density_min -0.211 _refine_diff_density_rms 0.036