# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Junji Ichikawa' 'Jun Mihara' 'Kotaro Sakoda' _publ_contact_author_name 'Junji Ichikawa' _publ_contact_author_address ; Department of Chemistry, Graduate School of Science The University of Tokyo Hongo, Bunkyo-ku Tokyo 113-0033 JAPAN ; _publ_contact_author_email JUNJI@CHEM.S.U-TOKYO.AC.JP _publ_requested_journal 'Chemical Communications' _publ_section_title ; Heck-Type 5-endo-trig Cyclization Promoted by Vinylic Fluorines: Synthesis of 5-Fluoro-3H-Pyrroles ; #CC2005ichikawaXray.cif data_cn1109 _database_code_depnum_ccdc_archive 'CCDC 278998' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H13 F2 N O' _chemical_formula_weight 225.23 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' F F 0.0171 0.0103 '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' _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 7.5652(18) _cell_length_b 6.3060(15) _cell_length_c 23.707(6) _cell_angle_alpha 90.00 _cell_angle_beta 97.4505(10) _cell_angle_gamma 90.00 _cell_volume 1121.4(5) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 3177 _cell_measurement_theta_min 3.0267 _cell_measurement_theta_max 27.4835 _exptl_crystal_description Block _exptl_crystal_colour Colorless _exptl_crystal_size_max 0.70 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.334 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 472 _exptl_absorpt_coefficient_mu 0.107 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.9286 _exptl_absorpt_correction_T_max 0.9736 _exptl_absorpt_process_details ; Private communication (R. Jacobson, 1998) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 120(2) _diffrn_source_power 2.0000 _diffrn_source_voltage 50.0000 _diffrn_source_current 40.0000 _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector CCD _diffrn_measurement_device ; Mercury CCD (2x2 bin mode) ; _diffrn_measurement_device_type ? _diffrn_measurement_method dtintegrate.ref _diffrn_detector_area_resol_mean 14.5666 _diffrn_standards_number ? _diffrn_reflns_number 6907 _diffrn_reflns_av_R_equivalents 0.0158 _diffrn_reflns_av_sigmaI/netI 0.0138 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 3.03 _diffrn_reflns_theta_max 27.48 _reflns_number_total 2186 _reflns_number_gt 2157 _reflns_threshold_expression >2sigma(I) _diffrn_reflns_reduction_process 'Lp corrections applied' _diffrn_measurement_details ; scan: Number of images: 600 Slice: -70.0000 - 110.0000 Image width: 0.3000 Exp time: 19.0000 Rotation axis: Omega Omega: 0.0000 Chi: 45.0000 Phi: 0.0000 XTD: 45.2006 2theta: 19.8837 scan: Number of images: 600 Slice: -70.0000 - 110.0000 Image width: 0.3000 Exp time: 19.0000 Rotation axis: Omega Omega: 0.0000 Chi: 45.0000 Phi: 90.0000 XTD: 45.2006 2theta: 19.8837 ; _diffrn_measurement_device_details ; AFC8: Eulerian 3-circle ; _diffrn_orient_matrix_UB_11 -0.0048 _diffrn_orient_matrix_UB_12 0.1018 _diffrn_orient_matrix_UB_13 -0.0859 _diffrn_orient_matrix_UB_21 0.1514 _diffrn_orient_matrix_UB_22 0.0343 _diffrn_orient_matrix_UB_23 0.0323 _diffrn_orient_matrix_UB_31 0.0123 _diffrn_orient_matrix_UB_32 -0.0214 _diffrn_orient_matrix_UB_33 -0.0346 _diffrn_orient_matrix_type d*Trek _computing_data_collection 'CrystalClear (Rigaku Corp., 2000)' _computing_cell_refinement 'CrystalClear (Rigaku Corp., 2000)' _computing_data_reduction 'CrystalClear (Rigaku Corp., 2000)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-3 for Windows (Farrugia, 1997)' _computing_publication_material ? _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^)+(0.2000P)^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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2186 _refine_ls_number_parameters 149 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0994 _refine_ls_R_factor_gt 0.0986 _refine_ls_wR_factor_ref 0.3643 _refine_ls_wR_factor_gt 0.3630 _refine_ls_goodness_of_fit_ref 1.895 _refine_ls_restrained_S_all 1.895 _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 0.1187(2) 0.6483(3) 0.46208(8) 0.0260(6) Uani 1 1 d . . . H1 H 0.1548 0.5645 0.4886 0.039 Uiso 1 1 calc R . . N1 N -0.0697(3) 0.6569(3) 0.45540(8) 0.0213(6) Uani 1 1 d . . . C1 C -0.1355(3) 0.7876(4) 0.41747(10) 0.0202(6) Uani 1 1 d . . . C2 C -0.0247(3) 0.9172(4) 0.38222(10) 0.0211(6) Uani 1 1 d . . . C3 C 0.0180(4) 0.8373(4) 0.33082(11) 0.0262(7) Uani 1 1 d . . . H2 H -0.0202 0.6993 0.3187 0.031 Uiso 1 1 calc R . . C4 C 0.1165(4) 0.9597(5) 0.29740(11) 0.0338(8) Uani 1 1 d . . . H3 H 0.1456 0.9050 0.2624 0.041 Uiso 1 1 calc R . . C5 C 0.1724(4) 1.1618(5) 0.31499(13) 0.0337(8) Uani 1 1 d . . . H4 H 0.2377 1.2462 0.2917 0.040 Uiso 1 1 calc R . . C6 C 0.1330(4) 1.2397(4) 0.36630(13) 0.0321(7) Uani 1 1 d . . . H5 H 0.1729 1.3770 0.3785 0.039 Uiso 1 1 calc R . . C7 C 0.0350(3) 1.1183(5) 0.40029(11) 0.0275(7) Uani 1 1 d . . . H6 H 0.0088 1.1724 0.4357 0.033 Uiso 1 1 calc R . . C8 C -0.3393(3) 0.8126(4) 0.40909(10) 0.0247(7) Uani 1 1 d . . . C9 C -0.3833(4) 1.0427(5) 0.42386(16) 0.0408(8) Uani 1 1 d . . . H7 H -0.3323 1.1399 0.3980 0.061 Uiso 1 1 calc R . . H8 H -0.3327 1.0734 0.4632 0.061 Uiso 1 1 calc R . . H9 H -0.5129 1.0612 0.4198 0.061 Uiso 1 1 calc R . . C10 C -0.4277(4) 0.6627(5) 0.44798(12) 0.0305(7) Uani 1 1 d . . . H10 H -0.5575 0.6793 0.4407 0.046 Uiso 1 1 calc R . . H11 H -0.3864 0.6972 0.4878 0.046 Uiso 1 1 calc R . . H12 H -0.3958 0.5159 0.4403 0.046 Uiso 1 1 calc R . . C11 C -0.4570(11) 0.6202(8) 0.32211(19) 0.089(2) Uani 1 1 d . . . C12 C -0.4090(4) 0.7803(6) 0.34668(13) 0.0406(8) Uani 1 1 d . . . H13 H -0.4156 0.9046 0.3239 0.049 Uiso 1 1 calc R . . F1 F -0.3129(11) 0.4536(9) 0.3344(3) 0.162(2) Uani 1 1 d . . . F2 F -0.5288(4) 0.5965(5) 0.26713(9) 0.0722(9) 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 O1 0.0208(10) 0.0305(11) 0.0263(10) 0.0081(7) 0.0019(7) 0.0027(7) N1 0.0207(10) 0.0227(12) 0.0205(11) 0.0018(8) 0.0023(8) 0.0016(7) C1 0.0231(12) 0.0198(12) 0.0180(11) -0.0013(8) 0.0036(9) 0.0008(9) C2 0.0227(11) 0.0219(13) 0.0181(12) 0.0018(9) 0.0011(9) 0.0006(8) C3 0.0325(13) 0.0241(14) 0.0226(13) -0.0008(10) 0.0053(10) -0.0002(10) C4 0.0406(15) 0.0402(16) 0.0218(13) 0.0025(11) 0.0089(11) -0.0002(13) C5 0.0336(14) 0.0357(16) 0.0324(15) 0.0099(11) 0.0064(11) -0.0022(11) C6 0.0359(14) 0.0246(14) 0.0356(15) 0.0026(11) 0.0040(12) -0.0004(11) C7 0.0292(13) 0.0279(14) 0.0252(13) -0.0027(10) 0.0034(10) -0.0010(10) C8 0.0210(12) 0.0283(13) 0.0240(13) 0.0024(9) 0.0000(9) 0.0019(9) C9 0.0279(14) 0.0315(15) 0.063(2) 0.0010(15) 0.0074(14) 0.0081(11) C10 0.0224(12) 0.0364(16) 0.0330(14) 0.0073(11) 0.0046(11) 0.0000(10) C11 0.169(6) 0.049(2) 0.037(2) -0.0043(18) -0.027(3) 0.001(3) C12 0.0372(15) 0.0511(19) 0.0296(15) 0.0082(14) -0.0101(12) -0.0047(14) F1 0.241(7) 0.101(3) 0.146(4) -0.014(3) 0.029(4) 0.026(4) F2 0.094(2) 0.087(2) 0.0315(12) -0.0163(12) -0.0080(11) -0.0158(16) _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 N1 1.414(3) . ? O1 H1 0.8400 . ? N1 C1 1.273(3) . ? C1 C2 1.500(3) . ? C1 C8 1.536(3) . ? C2 C3 1.395(4) . ? C2 C7 1.395(4) . ? C3 C4 1.389(4) . ? C3 H2 0.9500 . ? C4 C5 1.390(4) . ? C4 H3 0.9500 . ? C5 C6 1.380(4) . ? C5 H4 0.9500 . ? C6 C7 1.393(4) . ? C6 H5 0.9500 . ? C7 H6 0.9500 . ? C8 C12 1.519(4) . ? C8 C10 1.533(4) . ? C8 C9 1.539(4) . ? C9 H7 0.9800 . ? C9 H8 0.9800 . ? C9 H9 0.9800 . ? C10 H10 0.9800 . ? C10 H11 0.9800 . ? C10 H12 0.9800 . ? C11 C12 1.198(6) . ? C11 F2 1.354(5) . ? C11 F1 1.515(9) . ? C12 H13 0.9500 . ? 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 N1 O1 H1 109.5 . . ? C1 N1 O1 113.60(19) . . ? N1 C1 C2 123.4(2) . . ? N1 C1 C8 116.9(2) . . ? C2 C1 C8 119.7(2) . . ? C3 C2 C7 119.6(2) . . ? C3 C2 C1 120.0(2) . . ? C7 C2 C1 120.4(2) . . ? C4 C3 C2 120.0(2) . . ? C4 C3 H2 120.0 . . ? C2 C3 H2 120.0 . . ? C3 C4 C5 120.2(3) . . ? C3 C4 H3 119.9 . . ? C5 C4 H3 119.9 . . ? C6 C5 C4 119.9(3) . . ? C6 C5 H4 120.0 . . ? C4 C5 H4 120.0 . . ? C5 C6 C7 120.4(3) . . ? C5 C6 H5 119.8 . . ? C7 C6 H5 119.8 . . ? C6 C7 C2 119.8(2) . . ? C6 C7 H6 120.1 . . ? C2 C7 H6 120.1 . . ? C12 C8 C10 112.3(2) . . ? C12 C8 C1 109.2(2) . . ? C10 C8 C1 111.6(2) . . ? C12 C8 C9 106.9(3) . . ? C10 C8 C9 108.7(2) . . ? C1 C8 C9 108.1(2) . . ? C8 C9 H7 109.5 . . ? C8 C9 H8 109.5 . . ? H7 C9 H8 109.5 . . ? C8 C9 H9 109.5 . . ? H7 C9 H9 109.5 . . ? H8 C9 H9 109.5 . . ? C8 C10 H10 109.5 . . ? C8 C10 H11 109.5 . . ? H10 C10 H11 109.5 . . ? C8 C10 H12 109.5 . . ? H10 C10 H12 109.5 . . ? H11 C10 H12 109.5 . . ? C12 C11 F2 128.3(4) . . ? C12 C11 F1 109.0(6) . . ? F2 C11 F1 107.3(5) . . ? C11 C12 C8 129.2(4) . . ? C11 C12 H13 115.4 . . ? C8 C12 H13 115.4 . . ? 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 O1 N1 C1 C2 1.2(3) . . . . ? O1 N1 C1 C8 -177.81(19) . . . . ? N1 C1 C2 C3 89.6(3) . . . . ? C8 C1 C2 C3 -91.4(3) . . . . ? N1 C1 C2 C7 -91.0(3) . . . . ? C8 C1 C2 C7 88.1(3) . . . . ? C7 C2 C3 C4 -1.3(4) . . . . ? C1 C2 C3 C4 178.2(2) . . . . ? C2 C3 C4 C5 -0.1(4) . . . . ? C3 C4 C5 C6 1.2(5) . . . . ? C4 C5 C6 C7 -1.0(5) . . . . ? C5 C6 C7 C2 -0.4(4) . . . . ? C3 C2 C7 C6 1.5(4) . . . . ? C1 C2 C7 C6 -178.0(2) . . . . ? N1 C1 C8 C12 -127.1(3) . . . . ? C2 C1 C8 C12 53.9(3) . . . . ? N1 C1 C8 C10 -2.3(3) . . . . ? C2 C1 C8 C10 178.6(2) . . . . ? N1 C1 C8 C9 117.1(3) . . . . ? C2 C1 C8 C9 -62.0(3) . . . . ? F2 C11 C12 C8 175.6(5) . . . . ? F1 C11 C12 C8 -52.0(8) . . . . ? C10 C8 C12 C11 -34.0(7) . . . . ? C1 C8 C12 C11 90.4(6) . . . . ? C9 C8 C12 C11 -153.0(6) . . . . ? _diffrn_measured_fraction_theta_max 0.849 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.849 _refine_diff_density_max 0.667 _refine_diff_density_min -1.338 _refine_diff_density_rms 0.125