# 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 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name _publ_author_address H.M.L.Davies ;Department of Chemistry State University of New York at Buffalo Buffalo, NY 14260-3000, USA ; 'Kevin Cheng' ;Department of Chemistry State University of New York at Buffalo Buffalo, NY 14260-3000, USA ; 'Justin R. Denton' '' _publ_contact_author_address ; Department of Chemistry State University of New York at Buffalo Buffalo, NY 14260-3000, USA ; _publ_contact_author_email HDAVIES@ACSU.BUFFALO.EDU _publ_contact_author_phone (716)645-6800x2233 _publ_contact_author_name 'Huw Davies' _publ_section_title ;Stereoselective construction of nitrile-substituted cyclopropanes ; data_JD-8+3'BrCyclopropaneCN _database_code_depnum_ccdc_archive 'CCDC 654356' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H12 Br N' _chemical_formula_sum 'C16 H12 Br N' _chemical_formula_weight 298.18 _chemical_absolute_configuration ad 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' 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 C2 _symmetry_space_group_name_Hall C2y loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 17.7928(19) _cell_length_b 6.6811(7) _cell_length_c 10.9352(12) _cell_angle_alpha 90.00 _cell_angle_beta 100.069(3) _cell_angle_gamma 90.00 _cell_volume 1279.9(2) _cell_formula_units_Z 4 _cell_measurement_temperature 90(1) _cell_measurement_reflns_used 6258 _cell_measurement_theta_min 2.33 _cell_measurement_theta_max 25.69 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.547 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 600 _exptl_absorpt_coefficient_mu 3.191 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4825 _exptl_absorpt_correction_T_max 0.6203 _exptl_absorpt_process_details 'SADABS 2004/1 (Bruker, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 90(1) _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_source rotating-anode _diffrn_source_type 'RIGAKU RU-2000BEH' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART APEX2' _diffrn_detector_area_resol_mean 8.33 _diffrn_measurement_method \wand\f-scans _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8021 _diffrn_reflns_av_R_equivalents 0.0287 _diffrn_reflns_av_sigmaI/netI 0.0371 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.89 _diffrn_reflns_theta_max 25.68 _reflns_number_total 2411 _reflns_number_gt 2322 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (Bruker, 2004)' _computing_cell_refinement 'Bruker Saint v7.23A (Bruker, 2005)' _computing_data_reduction 'Bruker Saint v7.23A (Bruker, 2005)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _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^)+(0.0329P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.003(9) _refine_ls_number_reflns 2411 _refine_ls_number_parameters 163 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0232 _refine_ls_R_factor_gt 0.0220 _refine_ls_wR_factor_ref 0.0605 _refine_ls_wR_factor_gt 0.0585 _refine_ls_goodness_of_fit_ref 1.084 _refine_ls_restrained_S_all 1.084 _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 C1 C 0.27060(14) -0.0732(4) 0.7840(2) 0.0183(5) Uani 1 1 d . . . H1 H 0.3030 -0.1497 0.8449 0.022 Uiso 1 1 calc R . . C2 C 0.23669(14) -0.1623(4) 0.6729(2) 0.0210(7) Uani 1 1 d . . . H2 H 0.2468 -0.2992 0.6586 0.025 Uiso 1 1 calc R . . C3 C 0.18860(14) -0.0555(4) 0.5828(2) 0.0189(5) Uani 1 1 d . . . H3 H 0.1656 -0.1168 0.5070 0.023 Uiso 1 1 calc R . . C4 C 0.17511(14) 0.1439(4) 0.6069(2) 0.0183(5) Uani 1 1 d . . . C5 C 0.20784(13) 0.2362(4) 0.7166(2) 0.0169(5) Uani 1 1 d . . . H5 H 0.1967 0.3725 0.7308 0.020 Uiso 1 1 calc R . . C6 C 0.25708(13) 0.1295(4) 0.8063(2) 0.0170(5) Uani 1 1 d . . . C7 C 0.29086(14) 0.2363(4) 0.9216(2) 0.0156(5) Uani 1 1 d . . . H7 H 0.2564 0.3382 0.9498 0.019 Uiso 1 1 calc R . . C8 C 0.34787(14) 0.1469(4) 1.0245(2) 0.0169(5) Uani 1 1 d . . . H8A H 0.3625 0.0054 1.0156 0.020 Uiso 1 1 calc R . . H8B H 0.3449 0.1878 1.1106 0.020 Uiso 1 1 calc R . . C9 C 0.37709(11) 0.2992(6) 0.94218(19) 0.0154(4) Uani 1 1 d . . . C10 C 0.39032(13) 0.4990(4) 0.9952(2) 0.0169(6) Uani 1 1 d . . . C11 C 0.42689(13) 0.2494(3) 0.8488(2) 0.0158(6) Uani 1 1 d . . . C12 C 0.44324(14) 0.3972(4) 0.7675(2) 0.0201(5) Uani 1 1 d . . . H12 H 0.4220 0.5272 0.7706 0.024 Uiso 1 1 calc R . . C13 C 0.49034(16) 0.3562(4) 0.6819(3) 0.0219(6) Uani 1 1 d . . . H13 H 0.5020 0.4590 0.6281 0.026 Uiso 1 1 calc R . . C14 C 0.52041(15) 0.1667(5) 0.6745(3) 0.0207(6) Uani 1 1 d . . . H14 H 0.5519 0.1386 0.6148 0.025 Uiso 1 1 calc R . . C15 C 0.50462(14) 0.0186(4) 0.7541(2) 0.0203(6) Uani 1 1 d . . . H15 H 0.5257 -0.1112 0.7494 0.024 Uiso 1 1 calc R . . C16 C 0.45807(14) 0.0575(4) 0.8413(2) 0.0166(5) Uani 1 1 d . . . H16 H 0.4474 -0.0455 0.8956 0.020 Uiso 1 1 calc R . . N1 N 0.39939(13) 0.6560(4) 1.0358(2) 0.0229(5) Uani 1 1 d . . . Br1 Br 0.109184(11) 0.29737(6) 0.486601(18) 0.02178(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 C1 0.0191(12) 0.0140(13) 0.0209(13) 0.0019(11) 0.0007(10) 0.0016(10) C2 0.0225(12) 0.0143(19) 0.0264(13) -0.0018(10) 0.0043(10) -0.0023(10) C3 0.0193(12) 0.0190(13) 0.0183(13) -0.0042(11) 0.0030(10) -0.0043(11) C4 0.0146(11) 0.0194(13) 0.0202(13) 0.0014(11) 0.0011(10) 0.0001(10) C5 0.0166(11) 0.0127(13) 0.0206(13) -0.0003(9) 0.0016(10) 0.0003(9) C6 0.0158(12) 0.0142(13) 0.0214(13) 0.0001(11) 0.0048(10) -0.0013(10) C7 0.0170(11) 0.0122(12) 0.0174(12) -0.0001(9) 0.0021(10) 0.0006(9) C8 0.0201(12) 0.0120(11) 0.0173(13) 0.0022(11) -0.0008(10) -0.0006(10) C9 0.0173(9) 0.0108(9) 0.0166(10) 0.0002(16) -0.0012(8) -0.0005(16) C10 0.0180(14) 0.0162(15) 0.0153(12) 0.0029(11) -0.0008(10) 0.0039(10) C11 0.0157(10) 0.0141(16) 0.0154(11) -0.0025(9) -0.0029(9) -0.0006(9) C12 0.0219(13) 0.0138(13) 0.0229(14) 0.0010(11) -0.0010(11) 0.0015(11) C13 0.0251(14) 0.0207(17) 0.0202(13) 0.0046(10) 0.0044(11) -0.0010(10) C14 0.0193(13) 0.0265(16) 0.0164(13) -0.0035(12) 0.0034(10) -0.0010(11) C15 0.0197(13) 0.0144(12) 0.0243(14) -0.0048(11) -0.0032(11) 0.0008(10) C16 0.0179(12) 0.0106(13) 0.0198(13) 0.0012(10) -0.0011(10) -0.0001(9) N1 0.0285(12) 0.0126(12) 0.0267(12) -0.0032(10) 0.0020(10) 0.0010(9) Br1 0.02147(13) 0.02113(13) 0.02032(13) -0.00131(14) -0.00305(8) 0.00395(14) _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 C1 C2 1.393(4) . ? C1 C6 1.404(4) . ? C1 H1 0.9500 . ? C2 C3 1.384(4) . ? C2 H2 0.9500 . ? C3 C4 1.387(4) . ? C3 H3 0.9500 . ? C4 C5 1.384(4) . ? C4 Br1 1.902(3) . ? C5 C6 1.392(4) . ? C5 H5 0.9500 . ? C6 C7 1.482(4) . ? C7 C8 1.501(3) . ? C7 C9 1.569(3) . ? C7 H7 1.0000 . ? C8 C9 1.510(4) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 C10 1.458(5) . ? C9 C11 1.502(3) . ? C10 N1 1.140(4) . ? C11 C12 1.394(3) . ? C11 C16 1.405(3) . ? C12 C13 1.389(4) . ? C12 H12 0.9500 . ? C13 C14 1.382(4) . ? C13 H13 0.9500 . ? C14 C15 1.378(4) . ? C14 H14 0.9500 . ? C15 C16 1.393(4) . ? C15 H15 0.9500 . ? C16 H16 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 C2 C1 C6 120.2(2) . . ? C2 C1 H1 119.9 . . ? C6 C1 H1 119.9 . . ? C3 C2 C1 121.4(2) . . ? C3 C2 H2 119.3 . . ? C1 C2 H2 119.3 . . ? C2 C3 C4 117.7(2) . . ? C2 C3 H3 121.1 . . ? C4 C3 H3 121.1 . . ? C5 C4 C3 122.2(2) . . ? C5 C4 Br1 118.3(2) . . ? C3 C4 Br1 119.5(2) . . ? C4 C5 C6 120.0(2) . . ? C4 C5 H5 120.0 . . ? C6 C5 H5 120.0 . . ? C5 C6 C1 118.5(2) . . ? C5 C6 C7 117.7(2) . . ? C1 C6 C7 123.8(2) . . ? C6 C7 C8 124.5(2) . . ? C6 C7 C9 119.5(2) . . ? C8 C7 C9 58.89(17) . . ? C6 C7 H7 114.2 . . ? C8 C7 H7 114.2 . . ? C9 C7 H7 114.2 . . ? C7 C8 C9 62.80(15) . . ? C7 C8 H8A 117.5 . . ? C9 C8 H8A 117.5 . . ? C7 C8 H8B 117.5 . . ? C9 C8 H8B 117.5 . . ? H8A C8 H8B 114.6 . . ? C10 C9 C11 113.6(2) . . ? C10 C9 C8 115.4(2) . . ? C11 C9 C8 124.2(3) . . ? C10 C9 C7 112.8(2) . . ? C11 C9 C7 121.5(2) . . ? C8 C9 C7 58.32(16) . . ? N1 C10 C9 178.8(3) . . ? C12 C11 C16 118.7(2) . . ? C12 C11 C9 119.4(2) . . ? C16 C11 C9 121.9(2) . . ? C13 C12 C11 120.6(2) . . ? C13 C12 H12 119.7 . . ? C11 C12 H12 119.7 . . ? C14 C13 C12 120.3(2) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? C15 C14 C13 119.8(2) . . ? C15 C14 H14 120.1 . . ? C13 C14 H14 120.1 . . ? C14 C15 C16 120.6(3) . . ? C14 C15 H15 119.7 . . ? C16 C15 H15 119.7 . . ? C15 C16 C11 119.9(2) . . ? C15 C16 H16 120.0 . . ? C11 C16 H16 120.0 . . ? 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 C6 C1 C2 C3 -0.7(4) . . . . ? C1 C2 C3 C4 -0.1(4) . . . . ? C2 C3 C4 C5 -0.1(4) . . . . ? C2 C3 C4 Br1 -179.76(18) . . . . ? C3 C4 C5 C6 1.1(4) . . . . ? Br1 C4 C5 C6 -179.26(17) . . . . ? C4 C5 C6 C1 -1.8(4) . . . . ? C4 C5 C6 C7 179.6(2) . . . . ? C2 C1 C6 C5 1.6(4) . . . . ? C2 C1 C6 C7 -179.9(2) . . . . ? C5 C6 C7 C8 -176.8(2) . . . . ? C1 C6 C7 C8 4.7(4) . . . . ? C5 C6 C7 C9 -106.2(3) . . . . ? C1 C6 C7 C9 75.3(3) . . . . ? C6 C7 C8 C9 106.4(3) . . . . ? C7 C8 C9 C10 102.2(2) . . . . ? C7 C8 C9 C11 -108.8(2) . . . . ? C6 C7 C9 C10 138.6(2) . . . . ? C8 C7 C9 C10 -106.7(2) . . . . ? C6 C7 C9 C11 -1.5(4) . . . . ? C8 C7 C9 C11 113.3(3) . . . . ? C6 C7 C9 C8 -114.8(3) . . . . ? C11 C9 C10 N1 120(14) . . . . ? C8 C9 C10 N1 -88(14) . . . . ? C7 C9 C10 N1 -23(14) . . . . ? C10 C9 C11 C12 -38.1(3) . . . . ? C8 C9 C11 C12 172.5(2) . . . . ? C7 C9 C11 C12 101.7(3) . . . . ? C10 C9 C11 C16 141.6(2) . . . . ? C8 C9 C11 C16 -7.9(4) . . . . ? C7 C9 C11 C16 -78.7(3) . . . . ? C16 C11 C12 C13 -0.9(4) . . . . ? C9 C11 C12 C13 178.7(2) . . . . ? C11 C12 C13 C14 1.3(4) . . . . ? C12 C13 C14 C15 -1.1(4) . . . . ? C13 C14 C15 C16 0.5(4) . . . . ? C14 C15 C16 C11 -0.1(4) . . . . ? C12 C11 C16 C15 0.3(4) . . . . ? C9 C11 C16 C15 -179.3(2) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.68 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.967 _refine_diff_density_min -0.472 _refine_diff_density_rms 0.069