Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2001 data_global _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name 'Buchanan, J.' 'Charlton, Michael H.' 'Kinsman, Richard G.' 'Mahon, M.' 'Robinson, James J.' 'Williams, I. H.' _publ_contact_author_name 'Prof I H Williams' _publ_contact_author_address ; Prof I H Williams School of Chemistry University of Bath Claverton Down Bath BA2 7AY UK ; data_(Compound 3)k00gb2 _database_code_CSD 149759 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C6 H7 Br O4' _chemical_formula_weight 223.03 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' 'Br' 'Br' -0.2901 2.4595 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.0820(8) _cell_length_b 6.3290(12) _cell_length_c 11.666(2) _cell_angle_alpha 81.379(11) _cell_angle_beta 88.407(13) _cell_angle_gamma 61.999(10) _cell_volume 391.55(12) _cell_formula_units_Z 2 _cell_measurement_temperature 170(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 12 _cell_measurement_theta_max 18 _exptl_crystal_description Needle _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.892 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 220 _exptl_absorpt_coefficient_mu 5.212 _exptl_absorpt_correction_type none _exptl_special_details ; ? ; _diffrn_ambient_temperature 170(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method KappaCCD _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4088 _diffrn_reflns_av_R_equivalents 0.0669 _diffrn_reflns_av_sigmaI/netI 0.0592 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 3.54 _diffrn_reflns_theta_max 26.37 _reflns_number_total 1583 _reflns_number_gt 1467 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction 'Denzo and Scalepack (otwinowski & Minor, 1997' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' _computing_publication_material 'SHELXL-97/2 (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^)+(0.1886P)^2^+11.3423P] 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 0.020(7) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1583 _refine_ls_number_parameters 106 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0369 _refine_ls_R_factor_gt 0.0332 _refine_ls_wR_factor_ref 0.1050 _refine_ls_wR_factor_gt 0.0964 _refine_ls_goodness_of_fit_ref 0.341 _refine_ls_restrained_S_all 0.341 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.39962(7) 0.44255(7) 0.85561(3) 0.0311(2) Uani 1 1 d . . . O1 O -0.2477(6) 0.7153(6) 0.8254(3) 0.0382(7) Uani 1 1 d . . . O2 O -0.1077(5) 0.5124(5) 0.6703(2) 0.0282(6) Uani 1 1 d . . . O3 O 0.2307(5) 0.6089(5) 0.5611(2) 0.0297(6) Uani 1 1 d . . . O4 O 0.5295(6) 0.2205(5) 0.5887(3) 0.0363(7) Uani 1 1 d . . . H4 H 0.6127 0.2760 0.5483 0.050 Uiso 1 1 calc R . . C1 C -0.0949(7) 0.5576(7) 0.7798(3) 0.0248(7) Uani 1 1 d . . . C2 C 0.1608(7) 0.3423(7) 0.8114(3) 0.0233(7) Uani 1 1 d . . . C3 C 0.1527(7) 0.3104(7) 0.6818(3) 0.0232(7) Uani 1 1 d . . . C4 C 0.1647(8) 0.1437(8) 0.9039(3) 0.0299(8) Uani 1 1 d . . . H4A H 0.1445 0.1963 0.9801 0.050 Uiso 1 1 calc R . . H4B H 0.3241 -0.0038 0.9044 0.050 Uiso 1 1 calc R . . H4C H 0.0280 0.1105 0.8869 0.050 Uiso 1 1 calc R . . C5 C 0.1697(8) 0.0788(7) 0.6544(4) 0.0303(8) Uani 1 1 d . . . H5A H 0.0389 0.0505 0.6933 0.050 Uiso 1 1 calc R . . H5B H 0.3335 -0.0563 0.6817 0.041(14) Uiso 1 1 calc R . . H5C H 0.1479 0.0911 0.5703 0.033(13) Uiso 1 1 calc R . . C6 C 0.3097(7) 0.3980(7) 0.6034(3) 0.0237(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 Br1 0.0285(3) 0.0407(3) 0.0313(3) -0.00530(17) -0.00201(16) -0.0220(2) O1 0.0246(15) 0.0423(17) 0.0426(17) -0.0159(14) 0.0044(12) -0.0091(13) O2 0.0198(13) 0.0300(14) 0.0308(14) -0.0055(11) -0.0007(10) -0.0080(11) O3 0.0313(15) 0.0277(14) 0.0265(14) -0.0022(11) 0.0048(11) -0.0117(12) O4 0.0290(15) 0.0285(15) 0.0414(17) 0.0013(12) 0.0124(12) -0.0078(12) C1 0.0209(17) 0.0273(18) 0.0299(19) -0.0065(15) 0.0017(14) -0.0138(15) C2 0.0210(17) 0.0291(18) 0.0230(17) -0.0026(14) 0.0012(13) -0.0148(15) C3 0.0179(16) 0.0231(17) 0.0248(17) -0.0020(13) -0.0001(13) -0.0071(14) C4 0.034(2) 0.034(2) 0.0244(18) -0.0016(15) 0.0020(15) -0.0189(18) C5 0.031(2) 0.0276(19) 0.033(2) -0.0076(16) -0.0023(15) -0.0134(16) C6 0.0257(18) 0.0268(18) 0.0194(16) -0.0060(14) 0.0028(13) -0.0123(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 Br1 C2 1.945(4) . ? O1 C1 1.184(5) . ? O2 C1 1.362(5) . ? O2 C3 1.490(4) . ? O3 C6 1.212(5) . ? O4 C6 1.309(5) . ? C1 C2 1.518(5) . ? C2 C4 1.520(5) . ? C2 C3 1.560(5) . ? C3 C6 1.534(5) . ? C3 C5 1.503(5) . ? 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 O2 C3 92.5(3) . . ? O1 C1 O2 127.7(4) . . ? O1 C1 C2 137.5(4) . . ? O2 C1 C2 94.8(3) . . ? C4 C2 C1 114.9(3) . . ? C4 C2 C3 117.7(3) . . ? C1 C2 C3 84.1(3) . . ? C4 C2 Br1 109.9(3) . . ? C1 C2 Br1 111.6(3) . . ? C3 C2 Br1 116.4(2) . . ? O2 C3 C6 107.0(3) . . ? O2 C3 C5 112.6(3) . . ? C6 C3 C5 112.7(3) . . ? O2 C3 C2 88.1(3) . . ? C6 C3 C2 114.3(3) . . ? C5 C3 C2 119.0(3) . . ? O3 C6 O4 126.0(3) . . ? O3 C6 C3 121.9(3) . . ? O4 C6 C3 112.1(3) . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.498 _refine_diff_density_min -0.665 _refine_diff_density_rms 0.100 data_(Compound 4)k00gb1 _database_code_CSD 149760 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C6 H7 Br O4' _chemical_formula_weight 223.03 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' 'Br' 'Br' -0.2901 2.4595 '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 10.4057(9) _cell_length_b 6.4044(4) _cell_length_c 12.0468(11) _cell_angle_alpha 90.00 _cell_angle_beta 92.812(4) _cell_angle_gamma 90.00 _cell_volume 801.86(11) _cell_formula_units_Z 4 _cell_measurement_temperature 170(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 12 _cell_measurement_theta_max 18 _exptl_crystal_description needle _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.847 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 440 _exptl_absorpt_coefficient_mu 5.090 _exptl_absorpt_correction_type none _exptl_special_details ; ? ; _diffrn_ambient_temperature 170(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 '4-circle diffractometer' _diffrn_measurement_method 'scintillation counter' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8001 _diffrn_reflns_av_R_equivalents 0.0514 _diffrn_reflns_av_sigmaI/netI 0.0447 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.74 _diffrn_reflns_theta_max 27.51 _reflns_number_total 1842 _reflns_number_gt 1328 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction 'Denzo and Scalepack (otwinowski & Minor, 1997' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' _computing_publication_material 'SHELXL-97/2 (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^)+(0.0837P)^2^+0.0000P] 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 0.0055(18) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1842 _refine_ls_number_parameters 107 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0594 _refine_ls_R_factor_gt 0.0364 _refine_ls_wR_factor_ref 0.1185 _refine_ls_wR_factor_gt 0.1021 _refine_ls_goodness_of_fit_ref 0.895 _refine_ls_restrained_S_all 0.895 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.89130(3) 0.00171(4) 0.88052(3) 0.0473(2) Uani 1 1 d . . . O1 O 0.78026(18) -0.3379(3) 0.67348(16) 0.0375(5) Uani 1 1 d . . . O2 O 0.7371(3) -0.4790(3) 0.8425(2) 0.0518(7) Uani 1 1 d . . . O3 O 0.6333(2) 0.1399(3) 0.57498(19) 0.0379(5) Uani 1 1 d . . . H3 H 0.569(3) 0.159(4) 0.534(2) 0.029(8) Uiso 1 1 d . . . O4 O 0.57535(18) -0.1966(3) 0.55755(16) 0.0334(5) Uani 1 1 d . . . C1 C 0.7519(3) -0.3343(4) 0.7824(2) 0.0356(7) Uani 1 1 d . . . C2 C 0.7442(2) -0.0971(4) 0.7895(2) 0.0293(6) Uani 1 1 d . . . C3 C 0.7692(3) -0.1085(4) 0.6624(2) 0.0303(6) Uani 1 1 d . . . C4 C 0.6219(3) 0.0016(3) 0.8285(3) 0.0353(7) Uani 1 1 d . . . H4A H 0.5477 -0.0534 0.7845 0.053 Uiso 1 1 calc R . . H4B H 0.6262 0.1533 0.8191 0.053 Uiso 1 1 calc R . . H4C H 0.6127 -0.0315 0.9072 0.053 Uiso 1 1 calc R . . C5 C 0.8873(3) -0.0100(4) 0.6168(3) 0.0449(9) Uani 1 1 d . . . H5A H 0.9643 -0.0635 0.6574 0.067 Uiso 1 1 calc R . . H5B H 0.8830 0.1419 0.6257 0.067 Uiso 1 1 calc R . . H5C H 0.8912 -0.0445 0.5378 0.067 Uiso 1 1 calc R . . C6 C 0.6487(3) -0.0601(5) 0.5920(2) 0.0300(6) 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 Br1 0.0532(3) 0.0410(3) 0.0451(3) -0.00293(11) -0.02377(19) -0.00210(12) O1 0.0442(12) 0.0316(10) 0.0362(11) -0.0043(8) -0.0033(9) 0.0086(8) O2 0.077(2) 0.0270(12) 0.0509(16) 0.0086(9) 0.0000(14) 0.0019(9) O3 0.0433(13) 0.0303(11) 0.0387(12) 0.0027(9) -0.0125(10) -0.0012(9) O4 0.0354(11) 0.0320(10) 0.0320(10) 0.0033(8) -0.0059(9) -0.0058(8) C1 0.0398(17) 0.0292(15) 0.0369(16) -0.0015(12) -0.0065(12) 0.0028(11) C2 0.0350(16) 0.0265(14) 0.0260(14) 0.0003(11) -0.0038(11) 0.0000(11) C3 0.0339(16) 0.0258(14) 0.0310(15) 0.0005(10) -0.0003(12) 0.0004(11) C4 0.0438(19) 0.0319(16) 0.0304(15) 0.0018(10) 0.0040(15) 0.0030(11) C5 0.0320(18) 0.062(2) 0.041(2) 0.0065(13) 0.0050(15) -0.0038(12) C6 0.0311(15) 0.0345(14) 0.0248(14) 0.0014(12) 0.0057(12) 0.0011(13) _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 Br1 C2 1.944(3) . ? O1 C1 1.359(3) . ? O1 C3 1.479(3) . ? O2 C1 1.191(3) . ? O3 C6 1.306(4) . ? O4 C6 1.219(4) . ? C1 C2 1.524(4) . ? C2 C4 1.516(4) . ? C2 C3 1.567(3) . ? C3 C5 1.508(4) . ? C3 C6 1.512(4) . ? 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 O1 C3 92.89(18) . . ? O2 C1 O1 127.9(3) . . ? O2 C1 C2 137.2(3) . . ? O1 C1 C2 94.9(2) . . ? C4 C2 C1 118.7(2) . . ? C4 C2 C3 120.3(2) . . ? C1 C2 C3 83.52(19) . . ? C4 C2 Br1 109.83(19) . . ? C1 C2 Br1 108.30(17) . . ? C3 C2 Br1 113.73(17) . . ? O1 C3 C5 112.8(2) . . ? O1 C3 C6 108.2(2) . . ? C5 C3 C6 112.2(2) . . ? O1 C3 C2 88.53(18) . . ? C5 C3 C2 120.9(2) . . ? C6 C3 C2 111.5(2) . . ? O4 C6 O3 125.4(3) . . ? O4 C6 C3 122.2(3) . . ? O3 C6 C3 112.4(3) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.537 _refine_diff_density_min -0.666 _refine_diff_density_rms 0.097