# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Qing-Yun Chen' 'Wei Xu' _publ_contact_author_name 'Prof Qing-Yun Chen' _publ_contact_author_address ; Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200032 CHINA ; _publ_contact_author_email CHENQY@PUB.SIOC.AC.CN _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; A Novel Approach of Cycloaddition of Difluorocarbene to ¦Á,¦Â¨Cunsaturated Aldehydes and ketones: Synthesis of gem-difluorocyclopropyl ketones and ¦Â-fluorofurans ; data_cd22375 _database_code_CSD 200171 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C17 H13 F O2' _chemical_formula_weight 268.27 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' 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 3.9188(8) _cell_length_b 30.250(6) _cell_length_c 11.013(2) _cell_angle_alpha 90.00 _cell_angle_beta 100.187(4) _cell_angle_gamma 90.00 _cell_volume 1284.9(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1465 _cell_measurement_theta_min 4.622 _cell_measurement_theta_max 44.854 _exptl_crystal_description ? _exptl_crystal_colour colourless _exptl_crystal_size_max 0.482 _exptl_crystal_size_mid 0.433 _exptl_crystal_size_min 0.126 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.387 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 560 _exptl_absorpt_coefficient_mu 0.100 _exptl_absorpt_correction_type sadabs _exptl_absorpt_correction_T_min 0.32142 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 '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 7845 _diffrn_reflns_av_R_equivalents 0.0775 _diffrn_reflns_av_sigmaI/netI 0.0769 _diffrn_reflns_limit_h_min -3 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -39 _diffrn_reflns_limit_k_max 37 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.35 _diffrn_reflns_theta_max 28.28 _reflns_number_total 3009 _reflns_number_gt 1667 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _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 '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^)+(0.0254P)^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 0.0254(17) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3009 _refine_ls_number_parameters 234 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0818 _refine_ls_R_factor_gt 0.0425 _refine_ls_wR_factor_ref 0.0905 _refine_ls_wR_factor_gt 0.0803 _refine_ls_goodness_of_fit_ref 0.823 _refine_ls_restrained_S_all 0.823 _refine_ls_shift/su_max 0.009 _refine_ls_shift/su_mean 0.002 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 0.3515(2) 0.64627(3) 0.78179(8) 0.0456(3) Uani 1 1 d . . . O2 O 0.6910(3) 0.57743(3) 1.33495(9) 0.0601(3) Uani 1 1 d . . . F F 0.7291(3) 0.54522(3) 0.72844(8) 0.0727(3) Uani 1 1 d . . . C1 C 0.5088(4) 0.60727(5) 0.82525(13) 0.0436(4) Uani 1 1 d . . . C2 C 0.5726(4) 0.58517(5) 0.72505(14) 0.0493(4) Uani 1 1 d . . . C3 C 0.4569(4) 0.60931(5) 0.61817(16) 0.0512(4) Uani 1 1 d . . . C4 C 0.3217(4) 0.64683(5) 0.65560(13) 0.0440(4) Uani 1 1 d . . . C5 C 0.1616(4) 0.68538(5) 0.59046(13) 0.0427(4) Uani 1 1 d . . . C6 C 0.1454(4) 0.72560(5) 0.64829(16) 0.0499(4) Uani 1 1 d . . . C7 C -0.0014(4) 0.76181(6) 0.58416(16) 0.0555(4) Uani 1 1 d . . . C8 C -0.1379(4) 0.75840(7) 0.46117(16) 0.0587(5) Uani 1 1 d . . . C9 C -0.1297(4) 0.71856(6) 0.40285(17) 0.0619(5) Uani 1 1 d . . . C10 C 0.0193(4) 0.68236(6) 0.46588(15) 0.0553(5) Uani 1 1 d . . . C11 C 0.5585(4) 0.59872(5) 0.95652(13) 0.0422(4) Uani 1 1 d . . . C12 C 0.7036(4) 0.55972(5) 1.00618(16) 0.0515(4) Uani 1 1 d . . . C13 C 0.7528(4) 0.55107(5) 1.13141(15) 0.0517(4) Uani 1 1 d . . . C14 C 0.6550(4) 0.58228(5) 1.20938(13) 0.0460(4) Uani 1 1 d . . . C15 C 0.5074(4) 0.62148(5) 1.16215(15) 0.0502(4) Uani 1 1 d . . . C16 C 0.4586(4) 0.62962(5) 1.03744(15) 0.0478(4) Uani 1 1 d . . . C17 C 0.8658(6) 0.53938(7) 1.38878(19) 0.0624(5) Uani 1 1 d . . . H1 H 0.468(3) 0.6016(5) 0.5370(13) 0.061(5) Uiso 1 1 d . . . H2 H 0.236(4) 0.7272(5) 0.7321(13) 0.057(5) Uiso 1 1 d . . . H3 H -0.011(4) 0.7907(5) 0.6259(13) 0.067(5) Uiso 1 1 d . . . H4 H -0.241(3) 0.7837(5) 0.4162(12) 0.053(4) Uiso 1 1 d . . . H5 H -0.229(4) 0.7152(5) 0.3168(15) 0.074(5) Uiso 1 1 d . . . H6 H 0.033(4) 0.6548(5) 0.4254(13) 0.065(5) Uiso 1 1 d . . . H7 H 0.770(4) 0.5381(5) 0.9521(13) 0.061(5) Uiso 1 1 d . . . H8 H 0.856(4) 0.5236(5) 1.1628(12) 0.055(4) Uiso 1 1 d . . . H9 H 0.438(4) 0.6428(5) 1.2198(13) 0.068(5) Uiso 1 1 d . . . H10 H 0.354(3) 0.6566(5) 1.0057(12) 0.052(4) Uiso 1 1 d . . . H11 H 1.107(6) 0.5362(6) 1.3739(17) 0.106(8) Uiso 1 1 d . . . H12 H 0.738(4) 0.5117(6) 1.3563(14) 0.074(6) Uiso 1 1 d . . . H13 H 0.876(4) 0.5412(6) 1.4789(17) 0.087(6) Uiso 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 O1 0.0528(7) 0.0399(6) 0.0449(7) -0.0008(5) 0.0108(5) 0.0030(5) O2 0.0803(8) 0.0521(8) 0.0486(7) 0.0053(5) 0.0132(6) 0.0162(6) F 0.0995(8) 0.0487(6) 0.0729(7) -0.0043(5) 0.0232(5) 0.0220(5) C1 0.0443(9) 0.0344(9) 0.0521(10) -0.0014(7) 0.0084(7) 0.0003(7) C2 0.0554(10) 0.0353(9) 0.0585(11) -0.0023(8) 0.0136(8) 0.0058(7) C3 0.0626(11) 0.0462(10) 0.0470(10) -0.0073(8) 0.0156(8) 0.0003(8) C4 0.0468(9) 0.0443(10) 0.0415(9) -0.0030(7) 0.0099(7) -0.0057(7) C5 0.0432(9) 0.0443(10) 0.0420(9) 0.0000(7) 0.0112(7) -0.0045(7) C6 0.0545(11) 0.0497(11) 0.0448(10) -0.0004(8) 0.0071(8) -0.0020(8) C7 0.0632(12) 0.0451(11) 0.0587(11) 0.0028(9) 0.0120(9) 0.0033(9) C8 0.0604(11) 0.0585(12) 0.0579(12) 0.0145(10) 0.0121(9) 0.0061(9) C9 0.0732(13) 0.0647(13) 0.0456(11) 0.0041(9) 0.0046(9) -0.0018(10) C10 0.0667(12) 0.0507(11) 0.0487(11) -0.0043(9) 0.0108(9) -0.0027(9) C11 0.0423(9) 0.0347(8) 0.0501(9) -0.0022(7) 0.0096(7) -0.0013(7) C12 0.0617(11) 0.0407(10) 0.0533(11) -0.0050(8) 0.0137(8) 0.0076(8) C13 0.0620(11) 0.0365(10) 0.0562(11) 0.0037(8) 0.0100(8) 0.0093(8) C14 0.0503(10) 0.0419(9) 0.0459(10) 0.0003(7) 0.0092(7) 0.0005(7) C15 0.0613(11) 0.0382(10) 0.0523(11) -0.0042(8) 0.0130(8) 0.0049(8) C16 0.0532(10) 0.0353(9) 0.0552(11) 0.0030(8) 0.0104(8) 0.0056(8) C17 0.0720(15) 0.0563(13) 0.0575(13) 0.0093(10) 0.0073(10) 0.0134(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 O1 C4 1.3740(16) . ? O1 C1 1.3770(16) . ? O2 C14 1.3729(17) . ? O2 C17 1.4151(19) . ? F C2 1.3525(17) . ? C1 C2 1.351(2) . ? C1 C11 1.4474(19) . ? C2 C3 1.391(2) . ? C3 C4 1.347(2) . ? C3 H1 0.932(14) . ? C4 C5 1.4523(19) . ? C5 C6 1.380(2) . ? C5 C10 1.390(2) . ? C6 C7 1.373(2) . ? C6 H2 0.929(14) . ? C7 C8 1.369(2) . ? C7 H3 0.991(16) . ? C8 C9 1.369(2) . ? C8 H4 0.960(15) . ? C9 C10 1.371(2) . ? C9 H5 0.964(16) . ? C10 H6 0.951(15) . ? C11 C12 1.380(2) . ? C11 C16 1.394(2) . ? C12 C13 1.383(2) . ? C12 H7 0.951(16) . ? C13 C14 1.375(2) . ? C13 H8 0.962(15) . ? C14 C15 1.380(2) . ? C15 C16 1.375(2) . ? C15 H9 0.976(15) . ? C16 H10 0.952(14) . ? C17 H11 0.99(2) . ? C17 H12 1.010(17) . ? C17 H13 0.988(18) . ? 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 C4 O1 C1 108.35(11) . . ? C14 O2 C17 117.70(13) . . ? C2 C1 O1 106.03(12) . . ? C2 C1 C11 135.71(15) . . ? O1 C1 C11 118.23(13) . . ? C1 C2 F 124.62(14) . . ? C1 C2 C3 110.59(14) . . ? F C2 C3 124.79(14) . . ? C4 C3 C2 105.68(14) . . ? C4 C3 H1 126.2(9) . . ? C2 C3 H1 128.1(9) . . ? C3 C4 O1 109.35(14) . . ? C3 C4 C5 133.16(14) . . ? O1 C4 C5 117.49(13) . . ? C6 C5 C10 118.07(15) . . ? C6 C5 C4 122.08(13) . . ? C10 C5 C4 119.85(14) . . ? C7 C6 C5 121.00(16) . . ? C7 C6 H2 121.4(9) . . ? C5 C6 H2 117.6(9) . . ? C8 C7 C6 120.24(18) . . ? C8 C7 H3 119.0(8) . . ? C6 C7 H3 120.8(9) . . ? C9 C8 C7 119.53(17) . . ? C9 C8 H4 120.1(8) . . ? C7 C8 H4 120.4(9) . . ? C8 C9 C10 120.61(17) . . ? C8 C9 H5 121.1(10) . . ? C10 C9 H5 118.3(10) . . ? C9 C10 C5 120.53(17) . . ? C9 C10 H6 121.1(9) . . ? C5 C10 H6 118.4(9) . . ? C12 C11 C16 117.54(14) . . ? C12 C11 C1 121.45(14) . . ? C16 C11 C1 121.01(14) . . ? C11 C12 C13 122.12(16) . . ? C11 C12 H7 118.6(9) . . ? C13 C12 H7 119.3(9) . . ? C14 C13 C12 119.19(15) . . ? C14 C13 H8 121.0(9) . . ? C12 C13 H8 119.8(9) . . ? O2 C14 C13 124.42(14) . . ? O2 C14 C15 115.66(14) . . ? C13 C14 C15 119.92(15) . . ? C16 C15 C14 120.36(16) . . ? C16 C15 H9 121.7(9) . . ? C14 C15 H9 118.0(9) . . ? C15 C16 C11 120.86(15) . . ? C15 C16 H10 119.7(8) . . ? C11 C16 H10 119.4(8) . . ? O2 C17 H11 114.5(12) . . ? O2 C17 H12 110.7(10) . . ? H11 C17 H12 106.9(15) . . ? O2 C17 H13 107.8(10) . . ? H11 C17 H13 107.6(15) . . ? H12 C17 H13 109.3(14) . . ? 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 C4 O1 C1 C2 0.31(15) . . . . ? C4 O1 C1 C11 -178.21(12) . . . . ? O1 C1 C2 F 179.33(13) . . . . ? C11 C1 C2 F -2.5(3) . . . . ? O1 C1 C2 C3 -0.32(18) . . . . ? C11 C1 C2 C3 177.81(16) . . . . ? C1 C2 C3 C4 0.20(19) . . . . ? F C2 C3 C4 -179.45(14) . . . . ? C2 C3 C4 O1 0.00(17) . . . . ? C2 C3 C4 C5 179.72(15) . . . . ? C1 O1 C4 C3 -0.20(16) . . . . ? C1 O1 C4 C5 -179.97(12) . . . . ? C3 C4 C5 C6 -158.01(17) . . . . ? O1 C4 C5 C6 21.7(2) . . . . ? C3 C4 C5 C10 21.9(3) . . . . ? O1 C4 C5 C10 -158.42(13) . . . . ? C10 C5 C6 C7 -1.2(2) . . . . ? C4 C5 C6 C7 178.73(15) . . . . ? C5 C6 C7 C8 0.6(3) . . . . ? C6 C7 C8 C9 0.6(3) . . . . ? C7 C8 C9 C10 -1.2(3) . . . . ? C8 C9 C10 C5 0.6(3) . . . . ? C6 C5 C10 C9 0.5(2) . . . . ? C4 C5 C10 C9 -179.35(15) . . . . ? C2 C1 C11 C12 -0.2(3) . . . . ? O1 C1 C11 C12 177.80(14) . . . . ? C2 C1 C11 C16 -179.66(18) . . . . ? O1 C1 C11 C16 -1.7(2) . . . . ? C16 C11 C12 C13 -0.5(2) . . . . ? C1 C11 C12 C13 180.00(14) . . . . ? C11 C12 C13 C14 -0.1(3) . . . . ? C17 O2 C14 C13 5.4(2) . . . . ? C17 O2 C14 C15 -175.09(16) . . . . ? C12 C13 C14 O2 -179.97(14) . . . . ? C12 C13 C14 C15 0.5(2) . . . . ? O2 C14 C15 C16 -179.82(14) . . . . ? C13 C14 C15 C16 -0.2(2) . . . . ? C14 C15 C16 C11 -0.4(2) . . . . ? C12 C11 C16 C15 0.7(2) . . . . ? C1 C11 C16 C15 -179.75(14) . . . . ? _diffrn_measured_fraction_theta_max 0.941 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.941 _refine_diff_density_max 0.136 _refine_diff_density_min -0.122 _refine_diff_density_rms 0.032