# Supplementary Material (ESI) for Organic and Biomolecular Chemistry # This journal is (c) the Royal Society of Chemistry 2009 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_cambridge 0177 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name _publ_author_footnote _publ_author_address E.J.L.Stoffman . ; Department of Chemistry University of Alberta Edmonton, Alberta T6G 2G2 Canada ; D.L.J.Clive . ; Department of Chemistry University of Alberta Edmonton, Alberta T6G 2G2 Canada ; _publ_contact_author_address ; Department of Chemistry University of Alberta Edmonton, Alberta T6G 2G2 Canada ; _publ_contact_author_email derrick.clive@ualberta.ca _publ_contact_author_fax 1(780)4928231 _publ_contact_author_phone 1(780)4923251 _publ_contact_author_name 'Dr. Derrick L. J. Clive' _publ_contact_letter ; To: Cambridge Crystallographic Data Centre Please accept the following CIF data for a structure we hope to publish in Organic & Biomolecular Chemistry. Please forward any questions concerning this CIF to Bob McDonald (Bob.McDonald@ualberta.ca). ; _publ_section_title ; The coumarin-indole transformation - a method for preparing 4-halo-5-hydroxyindoles from coumarins ; data_6.1 _database_code_depnum_ccdc_archive 'CCDC 724736' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H15 I O7 S' _chemical_formula_sum 'C14 H15 I O7 S' _chemical_formula_weight 454.22 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' I I -0.4742 1.8119 '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/c' _symmetry_space_group_name_Hall '-P 2ybc' 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 10.4694(5) _cell_length_b 8.8437(4) _cell_length_c 17.8168(8) _cell_angle_alpha 90.00 _cell_angle_beta 93.3313(5) _cell_angle_gamma 90.00 _cell_volume 1646.84(13) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 9955 _cell_measurement_theta_min 2.29 _cell_measurement_theta_max 27.87 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.72 _exptl_crystal_size_mid 0.36 _exptl_crystal_size_min 0.27 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.832 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 896 _exptl_absorpt_coefficient_mu 2.103 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.3131 _exptl_absorpt_correction_T_max 0.5975 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(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 'Bruker APEX-II CCD' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 14030 _diffrn_reflns_av_R_equivalents 0.0172 _diffrn_reflns_av_sigmaI/netI 0.0161 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.95 _diffrn_reflns_theta_max 27.88 _reflns_number_total 3877 _reflns_number_gt 3691 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'DIRDIF-99 (Beurskens et al., 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0232P)^2^+1.4840P] 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 0.0054(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3877 _refine_ls_number_parameters 209 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0208 _refine_ls_R_factor_gt 0.0195 _refine_ls_wR_factor_ref 0.0504 _refine_ls_wR_factor_gt 0.0494 _refine_ls_goodness_of_fit_ref 1.047 _refine_ls_restrained_S_all 1.047 _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 I I 0.250422(11) 0.670008(13) 0.096155(7) 0.02624(6) Uani 1 1 d . . . S S 0.57397(5) 0.54382(5) 0.23688(3) 0.02872(11) Uani 1 1 d . . . O1 O 0.33351(13) 0.11822(16) -0.03407(8) 0.0282(3) Uani 1 1 d . . . O2 O 0.17443(16) -0.0156(2) -0.08474(10) 0.0471(4) Uani 1 1 d . . . O3 O 0.13650(15) -0.00108(16) 0.09416(9) 0.0381(3) Uani 1 1 d . . . O4 O 0.06259(14) 0.22977(15) 0.12096(8) 0.0295(3) Uani 1 1 d . . . O5 O 0.53043(12) 0.57652(14) 0.14995(7) 0.0237(3) Uani 1 1 d . . . O6 O 0.63714(16) 0.68062(16) 0.25977(10) 0.0403(4) Uani 1 1 d . . . O7 O 0.64287(16) 0.40463(17) 0.24190(9) 0.0404(4) Uani 1 1 d . . . C1 C 0.20580(19) 0.0874(2) -0.04439(11) 0.0300(4) Uani 1 1 d . . . C2 C 0.11744(17) 0.1890(2) -0.00280(11) 0.0246(4) Uani 1 1 d . . . H2 H 0.0305 0.1836 -0.0290 0.030 Uiso 1 1 calc R . . C3 C 0.16241(17) 0.3546(2) -0.00423(10) 0.0220(3) Uani 1 1 d . . . H3 H 0.1078 0.4156 0.0287 0.026 Uiso 1 1 calc R . . C4 C 0.29862(16) 0.3574(2) 0.02921(10) 0.0203(3) Uani 1 1 d . . . C5 C 0.35213(16) 0.47173(19) 0.07572(9) 0.0199(3) Uani 1 1 d . . . C6 C 0.47787(16) 0.45810(19) 0.10516(9) 0.0207(3) Uani 1 1 d . . . C7 C 0.55331(17) 0.33634(19) 0.08732(11) 0.0234(4) Uani 1 1 d . . . H7 H 0.6396 0.3305 0.1067 0.028 Uiso 1 1 calc R . . C8 C 0.50244(17) 0.2232(2) 0.04108(10) 0.0239(3) Uani 1 1 d . . . H8 H 0.5530 0.1388 0.0283 0.029 Uiso 1 1 calc R . . C9 C 0.37685(17) 0.2354(2) 0.01382(10) 0.0219(3) Uani 1 1 d . . . C10 C 0.10809(17) 0.1263(2) 0.07629(11) 0.0255(4) Uani 1 1 d . . . C11 C 0.0415(2) 0.1814(2) 0.19776(12) 0.0349(5) Uani 1 1 d . . . H11A H 0.1186 0.1303 0.2203 0.042 Uiso 1 1 calc R . . H11B H -0.0315 0.1102 0.1980 0.042 Uiso 1 1 calc R . . C12 C 0.0138(4) 0.3193(3) 0.24046(16) 0.0620(8) Uani 1 1 d . . . H12A H -0.0019 0.2921 0.2924 0.074 Uiso 1 1 calc R . . H12B H -0.0622 0.3692 0.2172 0.074 Uiso 1 1 calc R . . H12C H 0.0870 0.3882 0.2401 0.074 Uiso 1 1 calc R . . C13 C 0.15071(19) 0.4208(3) -0.08379(11) 0.0313(4) Uani 1 1 d . . . H13A H 0.0611 0.4175 -0.1029 0.038 Uiso 1 1 calc R . . H13B H 0.2030 0.3614 -0.1168 0.038 Uiso 1 1 calc R . . H13C H 0.1805 0.5258 -0.0826 0.038 Uiso 1 1 calc R . . C14 C 0.4286(2) 0.5259(3) 0.27941(12) 0.0386(5) Uani 1 1 d . . . H14A H 0.4450 0.5059 0.3332 0.046 Uiso 1 1 calc R . . H14B H 0.3796 0.4420 0.2562 0.046 Uiso 1 1 calc R . . H14C H 0.3796 0.6198 0.2727 0.046 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 I 0.02309(8) 0.01933(8) 0.03599(8) -0.00563(4) -0.00094(5) 0.00491(4) S 0.0344(2) 0.0192(2) 0.0311(2) -0.00225(17) -0.01015(18) -0.00030(18) O1 0.0236(6) 0.0258(7) 0.0350(7) -0.0130(6) 0.0007(5) 0.0034(5) O2 0.0357(8) 0.0441(9) 0.0609(11) -0.0322(8) -0.0035(7) 0.0006(7) O3 0.0386(8) 0.0224(7) 0.0534(9) 0.0018(6) 0.0036(7) 0.0076(6) O4 0.0376(8) 0.0215(6) 0.0299(7) 0.0007(5) 0.0065(6) 0.0026(6) O5 0.0241(6) 0.0174(6) 0.0288(6) 0.0009(5) -0.0042(5) -0.0025(5) O6 0.0405(9) 0.0272(8) 0.0508(9) -0.0072(6) -0.0185(7) -0.0043(6) O7 0.0524(10) 0.0262(7) 0.0403(8) -0.0007(6) -0.0168(7) 0.0103(7) C1 0.0259(9) 0.0284(10) 0.0354(10) -0.0099(8) -0.0009(7) 0.0009(7) C2 0.0195(8) 0.0222(8) 0.0317(9) -0.0068(7) -0.0016(7) 0.0005(6) C3 0.0193(8) 0.0203(8) 0.0260(8) -0.0031(7) -0.0009(6) 0.0016(6) C4 0.0189(8) 0.0189(8) 0.0231(8) 0.0006(6) 0.0012(6) 0.0016(6) C5 0.0203(8) 0.0162(7) 0.0233(8) 0.0012(6) 0.0016(6) 0.0024(6) C6 0.0216(8) 0.0178(8) 0.0226(8) 0.0009(6) -0.0002(6) -0.0021(6) C7 0.0176(8) 0.0227(9) 0.0298(9) 0.0021(7) 0.0003(7) 0.0014(6) C8 0.0215(8) 0.0204(8) 0.0303(9) -0.0005(7) 0.0044(7) 0.0048(7) C9 0.0224(8) 0.0193(8) 0.0241(8) -0.0040(6) 0.0021(6) 0.0003(6) C10 0.0194(8) 0.0198(8) 0.0370(10) -0.0035(7) 0.0001(7) -0.0010(7) C11 0.0386(11) 0.0339(11) 0.0324(10) 0.0073(8) 0.0036(8) 0.0005(8) C12 0.100(3) 0.0496(16) 0.0375(13) 0.0003(11) 0.0161(14) 0.0171(15) C13 0.0240(9) 0.0404(11) 0.0290(9) 0.0048(8) -0.0035(7) -0.0005(8) C14 0.0540(13) 0.0299(10) 0.0324(10) -0.0053(8) 0.0066(9) -0.0067(10) _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 I C5 2.0943(16) . ? S O6 1.4269(15) . ? S O7 1.4270(15) . ? S O5 1.6150(13) . ? S C14 1.747(2) . ? O1 C1 1.366(2) . ? O1 C9 1.401(2) . ? O2 C1 1.194(2) . ? O3 C10 1.203(2) . ? O4 C10 1.320(2) . ? O4 C11 1.463(2) . ? O5 C6 1.409(2) . ? C1 C2 1.514(3) . ? C2 C10 1.523(3) . ? C2 C3 1.539(2) . ? C3 C4 1.513(2) . ? C3 C13 1.532(3) . ? C4 C9 1.392(2) . ? C4 C5 1.403(2) . ? C5 C6 1.394(2) . ? C6 C7 1.383(2) . ? C7 C8 1.383(3) . ? C8 C9 1.379(3) . ? C11 C12 1.475(3) . ? 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 O6 S O7 119.29(10) . . ? O6 S O5 102.86(9) . . ? O7 S O5 109.15(8) . . ? O6 S C14 110.73(11) . . ? O7 S C14 110.17(11) . . ? O5 S C14 103.17(9) . . ? C1 O1 C9 120.62(14) . . ? C10 O4 C11 116.16(15) . . ? C6 O5 S 119.29(11) . . ? O2 C1 O1 117.77(18) . . ? O2 C1 C2 126.34(18) . . ? O1 C1 C2 115.89(16) . . ? C1 C2 C10 108.10(16) . . ? C1 C2 C3 111.13(15) . . ? C10 C2 C3 113.45(15) . . ? C4 C3 C13 112.37(15) . . ? C4 C3 C2 106.95(14) . . ? C13 C3 C2 111.77(15) . . ? C9 C4 C5 117.11(16) . . ? C9 C4 C3 117.47(15) . . ? C5 C4 C3 125.40(15) . . ? C6 C5 C4 119.73(15) . . ? C6 C5 I 119.06(12) . . ? C4 C5 I 121.08(12) . . ? C7 C6 C5 121.36(16) . . ? C7 C6 O5 119.95(15) . . ? C5 C6 O5 118.56(15) . . ? C8 C7 C6 119.66(16) . . ? C9 C8 C7 118.65(16) . . ? C8 C9 C4 123.45(16) . . ? C8 C9 O1 115.15(15) . . ? C4 C9 O1 121.34(16) . . ? O3 C10 O4 125.58(19) . . ? O3 C10 C2 123.90(18) . . ? O4 C10 C2 110.51(15) . . ? O4 C11 C12 106.61(18) . . ? 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 O6 S O5 C6 172.21(13) . . . . ? O7 S O5 C6 44.58(15) . . . . ? C14 S O5 C6 -72.55(14) . . . . ? C9 O1 C1 O2 -178.6(2) . . . . ? C9 O1 C1 C2 1.4(3) . . . . ? O2 C1 C2 C10 94.9(3) . . . . ? O1 C1 C2 C10 -85.1(2) . . . . ? O2 C1 C2 C3 -140.0(2) . . . . ? O1 C1 C2 C3 40.0(2) . . . . ? C1 C2 C3 C4 -56.59(19) . . . . ? C10 C2 C3 C4 65.46(18) . . . . ? C1 C2 C3 C13 66.8(2) . . . . ? C10 C2 C3 C13 -171.15(15) . . . . ? C13 C3 C4 C9 -86.8(2) . . . . ? C2 C3 C4 C9 36.2(2) . . . . ? C13 C3 C4 C5 94.4(2) . . . . ? C2 C3 C4 C5 -142.55(17) . . . . ? C9 C4 C5 C6 -1.1(2) . . . . ? C3 C4 C5 C6 177.66(16) . . . . ? C9 C4 C5 I 174.84(12) . . . . ? C3 C4 C5 I -6.4(2) . . . . ? C4 C5 C6 C7 2.4(3) . . . . ? I C5 C6 C7 -173.60(13) . . . . ? C4 C5 C6 O5 178.21(15) . . . . ? I C5 C6 O5 2.2(2) . . . . ? S O5 C6 C7 -66.90(19) . . . . ? S O5 C6 C5 117.21(15) . . . . ? C5 C6 C7 C8 -1.9(3) . . . . ? O5 C6 C7 C8 -177.64(16) . . . . ? C6 C7 C8 C9 0.1(3) . . . . ? C7 C8 C9 C4 1.3(3) . . . . ? C7 C8 C9 O1 178.49(16) . . . . ? C5 C4 C9 C8 -0.7(3) . . . . ? C3 C4 C9 C8 -179.57(17) . . . . ? C5 C4 C9 O1 -177.81(16) . . . . ? C3 C4 C9 O1 3.4(3) . . . . ? C1 O1 C9 C8 157.67(18) . . . . ? C1 O1 C9 C4 -25.0(3) . . . . ? C11 O4 C10 O3 -2.3(3) . . . . ? C11 O4 C10 C2 176.47(16) . . . . ? C1 C2 C10 O3 -18.5(3) . . . . ? C3 C2 C10 O3 -142.25(19) . . . . ? C1 C2 C10 O4 162.71(15) . . . . ? C3 C2 C10 O4 39.0(2) . . . . ? C10 O4 C11 C12 170.0(2) . . . . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 27.88 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 1.206 _refine_diff_density_min -0.747 _refine_diff_density_rms 0.067