Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Derek Boyd' _publ_contact_author_address ; Department of Chemistry and Chemical Engineering Queen's University Belfast Belfast BT9 5AG UNITED KINGDOM ; _publ_contact_author_email DR.BOYD@QUB.AC.UK _publ_section_title ; Enzyme-catalysed synthesis and reactions of benzene oxide/oxepine derivatives of methyl benzoates ; loop_ _publ_author_name 'D. Boyd' 'John T. G. Hamilton' 'David B. Harper' 'John S. Harrison' 'J. Malone' ; W.C.McRoberts ; 'Narain D. Sharma' #============================================================================ data_8 _database_code_depnum_ccdc_archive 'CCDC 668670' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H12 F3 N3 O5' _chemical_formula_sum 'C17 H12 F3 N3 O5' _chemical_formula_weight 395.30 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' F F 0.0171 0.0103 '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 10.584(3) _cell_length_b 10.448(3) _cell_length_c 14.677(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.310(11) _cell_angle_gamma 90.00 _cell_volume 1623.1(8) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'large blocks' _exptl_crystal_colour colourless _exptl_crystal_size_max 0.48 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.28 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.618 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 808 _exptl_absorpt_coefficient_mu 0.143 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9373 _exptl_absorpt_correction_T_max 0.9915 _exptl_absorpt_process_details 'Bruker SADABS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 SMART CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4219 _diffrn_reflns_av_R_equivalents 0.0460 _diffrn_reflns_av_sigmaI/netI 0.0451 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.39 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2371 _reflns_number_gt 1828 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _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^)+(0.1413P)^2^+1.2930P] 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 2371 _refine_ls_number_parameters 254 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0851 _refine_ls_R_factor_gt 0.0719 _refine_ls_wR_factor_ref 0.2330 _refine_ls_wR_factor_gt 0.2173 _refine_ls_goodness_of_fit_ref 1.137 _refine_ls_restrained_S_all 1.137 _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 1.0475(3) 1.1960(3) 0.9520(2) 0.0331(10) Uani 1 1 d . . . C1 C 0.9696(4) 1.1875(3) 1.1133(3) 0.0262(13) Uani 1 1 d . . . N2 N 0.9069(4) 1.3021(3) 1.1551(2) 0.0229(12) Uani 1 1 d . . . C3 C 0.8268(5) 1.2919(3) 1.2292(3) 0.0272(15) Uani 1 1 d . . . O4 O 0.8452(3) 1.2328(3) 1.29884(19) 0.0342(10) Uani 1 1 d . . . N4 N 0.7229(4) 1.3684(3) 1.2096(3) 0.0258(12) Uani 1 1 d . . . C5 C 0.7241(5) 1.4119(3) 1.1206(3) 0.0238(13) Uani 1 1 d . . . O5 O 0.6447(3) 1.4713(3) 1.0802(2) 0.0430(11) Uani 1 1 d . . . N6 N 0.8428(4) 1.3771(3) 1.0856(2) 0.0232(12) Uani 1 1 d . . . C7 C 0.8468(4) 1.3129(3) 0.9930(3) 0.0293(14) Uani 1 1 d . . . H7 H 0.7957 1.3604 0.9465 0.035 Uiso 1 1 calc R . . C8 C 0.9863(4) 1.3156(3) 0.9717(3) 0.0295(14) Uani 1 1 d . . . H8 H 1.0227 1.3958 0.9455 0.035 Uiso 1 1 calc R . . C9 C 1.0594(4) 1.2469(3) 1.0417(3) 0.0270(14) Uani 1 1 d . . . C10 C 0.8664(5) 1.1104(3) 1.0660(3) 0.0305(13) Uani 1 1 d . . . H10 H 0.8498 1.0230 1.0791 0.037 Uiso 1 1 calc R . . C11 C 0.8018(4) 1.1773(3) 1.0046(3) 0.0285(13) Uani 1 1 d . . . H11 H 0.7331 1.1425 0.9709 0.034 Uiso 1 1 calc R . . C12 C 1.0422(4) 1.1069(3) 1.1834(3) 0.0270(13) Uani 1 1 d . . . F1 F 1.1223(3) 1.0319(2) 1.13757(18) 0.0380(9) Uani 1 1 d . . . F2 F 0.9687(3) 1.0287(2) 1.23161(18) 0.0394(9) Uani 1 1 d . . . F3 F 1.1100(3) 1.1763(2) 1.24166(16) 0.0392(9) Uani 1 1 d . . . C13 C 1.1905(5) 1.2886(4) 1.0692(3) 0.0317(14) Uani 1 1 d . . . O2 O 1.2835(4) 1.2324(3) 1.0494(3) 0.0479(12) Uani 1 1 d . . . O3 O 1.1870(3) 1.3929(3) 1.1198(2) 0.0363(10) Uani 1 1 d . . . C14 C 1.3086(5) 1.4348(5) 1.1564(4) 0.0475(17) Uani 1 1 d . . . H14A H 1.3668 1.4516 1.1060 0.071 Uiso 1 1 calc R . . H14B H 1.3438 1.3676 1.1956 0.071 Uiso 1 1 calc R . . H14C H 1.2969 1.5132 1.1920 0.071 Uiso 1 1 calc R . . C15 C 0.6228(5) 1.3895(3) 1.2730(3) 0.0293(17) Uani 1 1 d . . . C16 C 0.5625(5) 1.2850(4) 1.3121(4) 0.0313(17) Uani 1 1 d . . . H16 H 0.5854 1.2005 1.2948 0.038 Uiso 1 1 calc R . . C17 C 0.4697(6) 1.3041(4) 1.3761(4) 0.0378(18) Uani 1 1 d . . . H17 H 0.4294 1.2325 1.4032 0.045 Uiso 1 1 calc R . . C18 C 0.4343(5) 1.4276(4) 1.4012(3) 0.0371(15) Uani 1 1 d . . . H18 H 0.3698 1.4410 1.4450 0.044 Uiso 1 1 calc R . . C19 C 0.4955(6) 1.5313(4) 1.3608(4) 0.0373(18) Uani 1 1 d . . . H19 H 0.4727 1.6159 1.3777 0.045 Uiso 1 1 calc R . . C20 C 0.5880(6) 1.5129(4) 1.2972(4) 0.0332(17) Uani 1 1 d . . . H20 H 0.6282 1.5844 1.2698 0.040 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 0.038(2) 0.0405(14) 0.0204(16) -0.0071(11) -0.0023(18) 0.0086(13) C1 0.028(3) 0.0297(17) 0.020(2) -0.0022(14) -0.005(3) 0.0048(15) N2 0.023(3) 0.0335(15) 0.012(2) 0.0005(12) 0.003(2) 0.0056(13) C3 0.026(3) 0.0306(17) 0.025(3) 0.0010(15) -0.007(3) -0.0029(16) O4 0.034(2) 0.0501(16) 0.0187(16) 0.0055(12) -0.0024(19) 0.0076(13) N4 0.023(3) 0.0403(17) 0.014(2) -0.0025(14) 0.003(2) 0.0061(15) C5 0.024(3) 0.0315(17) 0.016(2) 0.0034(14) 0.007(3) -0.0008(16) O5 0.044(3) 0.0576(18) 0.0277(18) 0.0063(13) -0.005(2) 0.0209(15) N6 0.023(3) 0.0351(15) 0.0114(19) 0.0006(12) 0.005(2) 0.0042(14) C7 0.034(3) 0.0371(19) 0.017(2) -0.0007(14) -0.006(3) 0.0028(16) C8 0.033(4) 0.0352(18) 0.020(2) -0.0020(14) -0.001(3) 0.0013(17) C9 0.033(3) 0.0298(17) 0.018(2) -0.0032(14) 0.000(3) 0.0002(16) C10 0.035(3) 0.0321(17) 0.024(2) -0.0051(15) -0.003(3) -0.0003(16) C11 0.027(3) 0.0374(18) 0.021(2) -0.0057(15) -0.001(3) -0.0013(16) C12 0.025(3) 0.0341(18) 0.022(2) 0.0016(15) 0.001(3) 0.0065(17) F1 0.035(2) 0.0467(13) 0.0321(15) -0.0013(10) -0.0021(17) 0.0158(11) F2 0.041(2) 0.0447(13) 0.0329(16) 0.0145(10) 0.0000(18) 0.0020(11) F3 0.039(2) 0.0502(13) 0.0280(14) -0.0011(10) -0.0144(16) 0.0049(11) C13 0.029(4) 0.0390(19) 0.027(3) 0.0039(17) 0.001(3) 0.0019(19) O2 0.026(3) 0.064(2) 0.054(3) -0.0106(17) 0.007(2) 0.0042(18) O3 0.032(2) 0.0431(15) 0.0342(18) -0.0059(12) -0.0097(19) -0.0017(12) C14 0.040(4) 0.055(2) 0.047(3) 0.000(2) -0.020(3) -0.007(2) C15 0.033(4) 0.0318(17) 0.022(3) -0.0018(15) -0.010(3) 0.0018(17) C16 0.030(4) 0.039(2) 0.024(3) -0.0034(16) -0.002(3) 0.0027(18) C17 0.036(4) 0.048(2) 0.029(3) 0.0020(19) -0.004(4) -0.001(2) C18 0.026(4) 0.061(3) 0.024(2) -0.0008(19) 0.000(3) 0.007(2) C19 0.040(4) 0.044(2) 0.027(3) -0.0050(18) -0.001(4) 0.011(2) C20 0.036(4) 0.0349(19) 0.029(3) 0.0013(17) -0.007(3) 0.0011(19) _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 C9 1.425(5) . ? O1 C8 1.438(5) . ? C1 N2 1.501(5) . ? C1 C10 1.522(5) . ? C1 C12 1.533(4) . ? C1 C9 1.550(7) . ? N2 C3 1.386(6) . ? N2 N6 1.451(4) . ? C3 O4 1.209(5) . ? C3 N4 1.389(5) . ? N4 C5 1.384(6) . ? N4 C15 1.431(7) . ? C5 O5 1.198(5) . ? C5 N6 1.408(6) . ? N6 C7 1.517(5) . ? C7 C11 1.505(5) . ? C7 C8 1.511(7) . ? C8 C9 1.471(5) . ? C9 C13 1.508(6) . ? C10 C11 1.326(5) . ? C12 F3 1.328(4) . ? C12 F2 1.333(6) . ? C12 F1 1.338(5) . ? C13 O2 1.184(6) . ? C13 O3 1.318(5) . ? O3 C14 1.460(5) . ? C15 C20 1.388(6) . ? C15 C16 1.390(7) . ? C16 C17 1.377(8) . ? C17 C18 1.395(7) . ? C18 C19 1.396(8) . ? C19 C20 1.370(8) . ? 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 C9 O1 C8 61.8(2) . . ? N2 C1 C10 106.9(3) . . ? N2 C1 C12 112.6(3) . . ? C10 C1 C12 111.8(3) . . ? N2 C1 C9 103.4(3) . . ? C10 C1 C9 110.1(3) . . ? C12 C1 C9 111.6(3) . . ? C3 N2 N6 107.9(3) . . ? C3 N2 C1 122.2(3) . . ? N6 N2 C1 110.5(3) . . ? O4 C3 N2 127.3(4) . . ? O4 C3 N4 126.3(5) . . ? N2 C3 N4 106.3(4) . . ? C5 N4 C3 111.9(5) . . ? C5 N4 C15 125.0(4) . . ? C3 N4 C15 122.9(4) . . ? O5 C5 N4 128.8(5) . . ? O5 C5 N6 125.4(4) . . ? N4 C5 N6 105.8(3) . . ? C5 N6 N2 107.4(3) . . ? C5 N6 C7 118.0(3) . . ? N2 N6 C7 112.1(3) . . ? C11 C7 C8 110.6(3) . . ? C11 C7 N6 107.7(3) . . ? C8 C7 N6 102.0(3) . . ? O1 C8 C9 58.6(2) . . ? O1 C8 C7 117.9(3) . . ? C9 C8 C7 111.0(4) . . ? O1 C9 C8 59.5(2) . . ? O1 C9 C13 115.6(4) . . ? C8 C9 C13 121.7(4) . . ? O1 C9 C1 115.2(3) . . ? C8 C9 C1 110.3(4) . . ? C13 C9 C1 120.1(3) . . ? C11 C10 C1 113.4(3) . . ? C10 C11 C7 114.3(3) . . ? F3 C12 F2 107.9(3) . . ? F3 C12 F1 107.6(3) . . ? F2 C12 F1 106.3(3) . . ? F3 C12 C1 113.5(3) . . ? F2 C12 C1 113.6(4) . . ? F1 C12 C1 107.5(3) . . ? O2 C13 O3 125.0(4) . . ? O2 C13 C9 123.8(4) . . ? O3 C13 C9 111.1(4) . . ? C13 O3 C14 115.3(4) . . ? C20 C15 C16 120.1(6) . . ? C20 C15 N4 120.5(4) . . ? C16 C15 N4 119.3(4) . . ? C17 C16 C15 119.9(4) . . ? C16 C17 C18 120.6(5) . . ? C17 C18 C19 118.7(6) . . ? C20 C19 C18 121.1(4) . . ? C19 C20 C15 119.7(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 C10 C1 N2 C3 69.9(4) . . . . ? C12 C1 N2 C3 -53.3(5) . . . . ? C9 C1 N2 C3 -173.9(3) . . . . ? C10 C1 N2 N6 -58.6(4) . . . . ? C12 C1 N2 N6 178.3(3) . . . . ? C9 C1 N2 N6 57.6(4) . . . . ? N6 N2 C3 O4 177.2(3) . . . . ? C1 N2 C3 O4 47.6(5) . . . . ? N6 N2 C3 N4 -5.7(3) . . . . ? C1 N2 C3 N4 -135.2(3) . . . . ? O4 C3 N4 C5 -173.8(3) . . . . ? N2 C3 N4 C5 9.1(4) . . . . ? O4 C3 N4 C15 1.5(6) . . . . ? N2 C3 N4 C15 -175.6(3) . . . . ? C3 N4 C5 O5 173.9(4) . . . . ? C15 N4 C5 O5 -1.2(6) . . . . ? C3 N4 C5 N6 -8.7(4) . . . . ? C15 N4 C5 N6 176.2(3) . . . . ? O5 C5 N6 N2 -177.7(4) . . . . ? N4 C5 N6 N2 4.7(3) . . . . ? O5 C5 N6 C7 -50.0(5) . . . . ? N4 C5 N6 C7 132.5(3) . . . . ? C3 N2 N6 C5 0.6(3) . . . . ? C1 N2 N6 C5 136.4(3) . . . . ? C3 N2 N6 C7 -130.6(4) . . . . ? C1 N2 N6 C7 5.3(5) . . . . ? C5 N6 C7 C11 -74.5(4) . . . . ? N2 N6 C7 C11 51.0(4) . . . . ? C5 N6 C7 C8 169.0(3) . . . . ? N2 N6 C7 C8 -65.5(4) . . . . ? C9 O1 C8 C7 -98.7(4) . . . . ? C11 C7 C8 O1 9.5(4) . . . . ? N6 C7 C8 O1 123.8(3) . . . . ? C11 C7 C8 C9 -55.2(4) . . . . ? N6 C7 C8 C9 59.2(3) . . . . ? C8 O1 C9 C13 -113.3(4) . . . . ? C8 O1 C9 C1 99.7(4) . . . . ? C7 C8 C9 O1 110.7(4) . . . . ? O1 C8 C9 C13 103.0(5) . . . . ? C7 C8 C9 C13 -146.3(4) . . . . ? O1 C8 C9 C1 -108.0(3) . . . . ? C7 C8 C9 C1 2.6(4) . . . . ? N2 C1 C9 O1 -127.8(3) . . . . ? C10 C1 C9 O1 -13.9(4) . . . . ? C12 C1 C9 O1 110.9(3) . . . . ? N2 C1 C9 C8 -62.8(3) . . . . ? C10 C1 C9 C8 51.1(4) . . . . ? C12 C1 C9 C8 175.8(3) . . . . ? N2 C1 C9 C13 86.8(4) . . . . ? C10 C1 C9 C13 -159.3(3) . . . . ? C12 C1 C9 C13 -34.6(4) . . . . ? N2 C1 C10 C11 56.5(5) . . . . ? C12 C1 C10 C11 -179.8(4) . . . . ? C9 C1 C10 C11 -55.2(5) . . . . ? C1 C10 C11 C7 1.8(6) . . . . ? C8 C7 C11 C10 54.6(5) . . . . ? N6 C7 C11 C10 -56.1(5) . . . . ? N2 C1 C12 F3 -43.6(5) . . . . ? C10 C1 C12 F3 -163.9(4) . . . . ? C9 C1 C12 F3 72.2(4) . . . . ? N2 C1 C12 F2 80.3(4) . . . . ? C10 C1 C12 F2 -40.1(5) . . . . ? C9 C1 C12 F2 -163.9(3) . . . . ? N2 C1 C12 F1 -162.4(4) . . . . ? C10 C1 C12 F1 77.2(5) . . . . ? C9 C1 C12 F1 -46.6(4) . . . . ? O1 C9 C13 O2 -38.9(6) . . . . ? C8 C9 C13 O2 -107.5(5) . . . . ? C1 C9 C13 O2 106.4(6) . . . . ? O1 C9 C13 O3 142.7(3) . . . . ? C8 C9 C13 O3 74.1(5) . . . . ? C1 C9 C13 O3 -71.9(4) . . . . ? O2 C13 O3 C14 -3.3(7) . . . . ? C9 C13 O3 C14 175.0(4) . . . . ? C5 N4 C15 C20 -60.1(5) . . . . ? C3 N4 C15 C20 125.2(4) . . . . ? C5 N4 C15 C16 121.5(4) . . . . ? C3 N4 C15 C16 -53.1(5) . . . . ? C20 C15 C16 C17 -1.0(5) . . . . ? N4 C15 C16 C17 177.3(3) . . . . ? C15 C16 C17 C18 0.8(5) . . . . ? C16 C17 C18 C19 -0.5(5) . . . . ? C17 C18 C19 C20 0.4(5) . . . . ? C18 C19 C20 C15 -0.7(5) . . . . ? C16 C15 C20 C19 1.0(5) . . . . ? N4 C15 C20 C19 -177.3(3) . . . . ? _diffrn_measured_fraction_theta_max 0.828 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.828 _refine_diff_density_max 0.419 _refine_diff_density_min -0.668 _refine_diff_density_rms 0.085