# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'C. Braddock' _publ_contact_author_address ; Department of Chemistry Imperial College South Kensington LONDON SW7 2AY UNITED KINGDOM ; _publ_contact_author_email C.BRADDOCK@IMPERIAL.AC.UK _publ_section_title ; The Stereochemical Course of Bromoetherification of Enynes ; loop_ _publ_author_name 'C. Braddock' 'Roshni Bhuva' 'Yolanda Perez-Fuertes' 'Rebecca Pouwer' 'Craig Roberts' ; A.Ruggiero ; 'Elaine Stokes' 'A. White' data_Compound_21 _database_code_depnum_ccdc_archive 'CCDC 625183' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H16 Br N O3 S' _chemical_formula_sum 'C14 H16 Br N O3 S' _chemical_formula_weight 358.25 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 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' N N 0.0311 0.0180 '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' S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.6763 1.2805 '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)/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 17.481(2) _cell_length_b 10.1393(16) _cell_length_c 8.799(2) _cell_angle_alpha 90.00 _cell_angle_beta 98.488(13) _cell_angle_gamma 90.00 _cell_volume 1542.5(5) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 13706 _cell_measurement_theta_min 2.5535 _cell_measurement_theta_max 70.7181 _exptl_crystal_description needles _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.543 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 728 _exptl_absorpt_coefficient_mu 4.959 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.60598 _exptl_absorpt_correction_T_max 1.11543 _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.30.2 (release 11-05-2006 CrysAlis171 .NET) (compiled May 11 2006,17:41:17) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 1.54248 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'Enhance Ultra (Cu) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'OD Xcalibur PX Ultra' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 8.2556 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 34903 _diffrn_reflns_av_R_equivalents 0.0497 _diffrn_reflns_av_sigmaI/netI 0.0200 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.56 _diffrn_reflns_theta_max 71.06 _reflns_number_total 2968 _reflns_number_gt 2449 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD, Oxford Diffraction Ltd' _computing_cell_refinement 'CrysAlis RED, Oxford Diffraction Ltd' _computing_data_reduction 'CrysAlis RED, Oxford Diffraction Ltd' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0345P)^2^+3.7805P] 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 0.00149(19) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2968 _refine_ls_number_parameters 220 _refine_ls_number_restraints 64 _refine_ls_R_factor_all 0.0686 _refine_ls_R_factor_gt 0.0588 _refine_ls_wR_factor_ref 0.1442 _refine_ls_wR_factor_gt 0.1411 _refine_ls_goodness_of_fit_ref 1.116 _refine_ls_restrained_S_all 1.116 _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 O1 O 0.5941(2) 0.2656(4) 0.7705(4) 0.0716(10) Uani 1 1 d . . . C2 C 0.6470(3) 0.1927(5) 0.6945(5) 0.0639(13) Uani 1 1 d D A . H2A H 0.6283 0.1913 0.5815 0.077 Uiso 1 1 calc R . . C3 C 0.7269(3) 0.2541(5) 0.7241(5) 0.0587(12) Uani 1 1 d . . . H3A H 0.7470 0.2518 0.8354 0.070 Uiso 1 1 calc R . . H3B H 0.7630 0.2042 0.6689 0.070 Uiso 1 1 calc R . . N4 N 0.7211(2) 0.3908(4) 0.6699(4) 0.0533(9) Uani 1 1 d . . . C5 C 0.6657(3) 0.4674(5) 0.7455(6) 0.0631(12) Uani 1 1 d . . . H5A H 0.6613 0.5582 0.7038 0.076 Uiso 1 1 calc R . . H5B H 0.6837 0.4725 0.8574 0.076 Uiso 1 1 calc R . . C6 C 0.5880(3) 0.3991(7) 0.7155(7) 0.0762(16) Uani 1 1 d . . . H6A H 0.5502 0.4477 0.7679 0.091 Uiso 1 1 calc R . . H6B H 0.5689 0.3994 0.6039 0.091 Uiso 1 1 calc R . . C7 C 0.6469(4) 0.0564(7) 0.7566(6) 0.0840(18) Uani 1 1 d D . . H7A H 0.6418 0.0464 0.8620 0.101 Uiso 0.710(4) 1 calc PR A 1 H7B H 0.6732 0.0377 0.8579 0.101 Uiso 0.150(3) 1 d PR B 2 H7C H 0.6424 0.0456 0.8621 0.101 Uiso 0.140(5) 1 d PR C 3 C8 C 0.6531(6) -0.0492(7) 0.6778(10) 0.061(2) Uani 0.710(4) 1 d PDU A 1 C9 C 0.6575(5) -0.1544(8) 0.5901(8) 0.064(2) Uani 0.710(4) 1 d PDU A 1 H9A H 0.7065 -0.1930 0.5838 0.077 Uiso 0.710(4) 1 calc PR A 1 Br Br 0.56846(18) -0.2275(3) 0.4791(2) 0.0794(6) Uani 0.710(4) 1 d PDU A 1 C8' C 0.6102(17) -0.0380(19) 0.675(3) 0.073(8) Uiso 0.150(3) 1 d PDU A 2 C9' C 0.5696(13) -0.128(3) 0.588(4) 0.083(8) Uiso 0.150(3) 1 d PDU A 2 H9'A H 0.5148 -0.1318 0.5801 0.100 Uiso 0.150(3) 1 calc PR B 2 Br' Br 0.6224(5) -0.2465(6) 0.4803(10) 0.130(3) Uani 0.150(3) 1 d PDU A 2 C8" C 0.652(2) -0.048(2) 0.674(5) 0.065(9) Uiso 0.140(5) 1 d PDU A 3 C9" C 0.6531(16) -0.1623(17) 0.600(2) 0.066(9) Uiso 0.140(5) 1 d PDU A 3 H9"A H 0.7009 -0.1993 0.5820 0.080 Uiso 0.140(5) 1 calc PR C 3 Br" Br 0.5605(8) -0.2495(13) 0.5330(19) 0.097(4) Uani 0.140(5) 1 d PDU A 3 S10 S 0.80272(7) 0.46737(12) 0.65390(12) 0.0531(3) Uani 1 1 d . . . O11 O 0.84719(19) 0.3772(3) 0.5778(3) 0.0617(9) Uani 1 1 d . . . O12 O 0.7825(2) 0.5934(3) 0.5872(3) 0.0625(9) Uani 1 1 d . . . C13 C 0.8502(2) 0.4922(5) 0.8430(5) 0.0496(10) Uani 1 1 d . . . C14 C 0.8932(3) 0.3898(5) 0.9183(5) 0.0572(11) Uani 1 1 d . . . H14A H 0.9005 0.3095 0.8667 0.069 Uiso 1 1 calc R . . C15 C 0.9252(3) 0.4082(5) 1.0707(5) 0.0606(12) Uani 1 1 d . . . H15A H 0.9552 0.3393 1.1230 0.073 Uiso 1 1 calc R . . C16 C 0.9150(3) 0.5224(5) 1.1480(5) 0.0548(11) Uani 1 1 d . . . C17 C 0.8732(3) 0.6238(5) 1.0704(5) 0.0606(12) Uani 1 1 d . . . H17A H 0.8669 0.7045 1.1218 0.073 Uiso 1 1 calc R . . C18 C 0.8403(3) 0.6086(5) 0.9177(5) 0.0552(11) Uani 1 1 d . . . H18A H 0.8112 0.6783 0.8653 0.066 Uiso 1 1 calc R . . C19 C 0.9491(3) 0.5372(6) 1.3153(5) 0.0716(15) Uani 1 1 d . . . H19A H 0.9095 0.5169 1.3799 0.107 Uiso 1 1 calc R . . H19B H 0.9671 0.6280 1.3347 0.107 Uiso 1 1 calc R . . H19C H 0.9927 0.4763 1.3398 0.107 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 O1 0.067(2) 0.088(3) 0.062(2) -0.0118(19) 0.0179(17) -0.018(2) C2 0.075(3) 0.074(3) 0.043(2) -0.005(2) 0.010(2) -0.020(3) C3 0.067(3) 0.065(3) 0.045(2) -0.005(2) 0.010(2) -0.010(2) N4 0.059(2) 0.060(2) 0.0418(18) -0.0047(17) 0.0098(16) -0.0093(18) C5 0.064(3) 0.070(3) 0.056(3) -0.009(2) 0.013(2) -0.004(3) C6 0.060(3) 0.098(5) 0.072(3) -0.011(3) 0.013(3) -0.006(3) C7 0.101(4) 0.101(5) 0.051(3) -0.002(3) 0.015(3) -0.037(4) C8 0.062(4) 0.074(5) 0.048(4) 0.008(3) 0.009(3) -0.014(4) C9 0.055(4) 0.085(5) 0.054(4) 0.010(4) 0.015(3) -0.004(4) Br 0.0838(11) 0.0791(12) 0.0728(9) -0.0165(8) 0.0028(8) -0.0228(9) Br' 0.098(5) 0.096(4) 0.220(8) 0.066(5) 0.097(5) 0.030(3) Br" 0.073(5) 0.073(4) 0.134(10) 0.009(6) -0.019(6) -0.008(3) S10 0.0617(7) 0.0577(7) 0.0412(5) -0.0023(5) 0.0122(5) -0.0067(5) O11 0.071(2) 0.068(2) 0.0508(17) -0.0092(15) 0.0234(15) -0.0078(17) O12 0.079(2) 0.061(2) 0.0474(17) 0.0042(15) 0.0072(15) -0.0083(17) C13 0.050(2) 0.056(3) 0.044(2) -0.0017(19) 0.0090(18) -0.005(2) C14 0.062(3) 0.054(3) 0.057(3) -0.002(2) 0.011(2) -0.006(2) C15 0.052(3) 0.072(3) 0.058(3) 0.014(2) 0.007(2) -0.006(2) C16 0.050(2) 0.070(3) 0.045(2) 0.002(2) 0.0086(19) -0.007(2) C17 0.062(3) 0.072(3) 0.049(2) -0.014(2) 0.012(2) -0.004(2) C18 0.060(3) 0.054(3) 0.051(2) 0.000(2) 0.008(2) 0.002(2) C19 0.071(3) 0.095(4) 0.047(2) 0.000(3) 0.004(2) -0.009(3) _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 O1 C2 1.425(6) . ? O1 C6 1.436(7) . ? C2 C7 1.486(8) . ? C2 C3 1.517(7) . ? C3 N4 1.464(6) . ? N4 C5 1.474(6) . ? N4 S10 1.649(4) . ? C5 C6 1.513(7) . ? C7 C8 1.289(9) . ? C7 C8" 1.295(17) . ? C7 C8' 1.305(14) . ? C8 C9 1.326(10) . ? C9 Br 1.865(8) . ? C8' C9' 1.332(17) . ? C9' Br' 1.855(18) . ? C8" C9" 1.330(16) . ? C9" Br" 1.864(18) . ? S10 O12 1.429(4) . ? S10 O11 1.429(3) . ? S10 C13 1.764(4) . ? C13 C18 1.375(6) . ? C13 C14 1.391(6) . ? C14 C15 1.388(6) . ? C15 C16 1.368(7) . ? C16 C17 1.383(7) . ? C16 C19 1.512(6) . ? C17 C18 1.389(6) . ? 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 C2 O1 C6 110.7(4) . . ? O1 C2 C7 105.9(4) . . ? O1 C2 C3 110.6(4) . . ? C7 C2 C3 111.7(5) . . ? N4 C3 C2 108.3(4) . . ? C3 N4 C5 111.7(4) . . ? C3 N4 S10 117.0(3) . . ? C5 N4 S10 115.2(3) . . ? N4 C5 C6 108.3(4) . . ? O1 C6 C5 110.6(5) . . ? C8 C7 C8" 2(2) . . ? C8 C7 C8' 33.9(13) . . ? C8" C7 C8' 33(2) . . ? C8 C7 C2 124.8(6) . . ? C8" C7 C2 123.4(19) . . ? C8' C7 C2 120.6(14) . . ? C7 C8 C9 176.8(9) . . ? C8 C9 Br 120.6(6) . . ? C7 C8' C9' 176(3) . . ? C8' C9' Br' 118.4(18) . . ? C7 C8" C9" 174(4) . . ? C8" C9" Br" 119.6(19) . . ? O12 S10 O11 119.9(2) . . ? O12 S10 N4 107.0(2) . . ? O11 S10 N4 106.1(2) . . ? O12 S10 C13 108.2(2) . . ? O11 S10 C13 108.7(2) . . ? N4 S10 C13 106.20(19) . . ? C18 C13 C14 120.7(4) . . ? C18 C13 S10 120.0(4) . . ? C14 C13 S10 119.2(4) . . ? C15 C14 C13 118.2(5) . . ? C16 C15 C14 122.1(5) . . ? C15 C16 C17 118.8(4) . . ? C15 C16 C19 120.5(5) . . ? C17 C16 C19 120.7(5) . . ? C16 C17 C18 120.6(5) . . ? C13 C18 C17 119.6(5) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 71.06 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.352 _refine_diff_density_min -0.537 _refine_diff_density_rms 0.067 #===END