Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Michael Shipman' 'Jerome F. Hayes' 'N. Prevost' 'Ivan Prokes' 'A. Slawin' 'Heather Twin' _publ_contact_author_name 'Dr Michael Shipman' _publ_contact_author_address ; School of Chemistry University of Exeter Stocker Road Exeter Devon EX4 4QD UNITED KINGDOM ; _publ_contact_author_email M.SHIPMAN@EXETER.AC.UK _publ_requested_journal 'Chemical Communications' _publ_section_title ; Aziridinyl Anions From Chiral, Nonracemic 2-Isopropylidine-aziridines: Surprisingly Diastereoselective Alkylation Reactions ; data_2g _database_code_CSD 207055 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C26 H27 N O' _chemical_formula_sum 'C26 H27 N O' _chemical_formula_weight 369.49 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' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2 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 16.847(3) _cell_length_b 22.696(4) _cell_length_c 5.6162(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2147.3(7) _cell_formula_units_Z 4 _cell_measurement_temperature 125(2) _cell_measurement_reflns_used 33 _cell_measurement_theta_min 12 _cell_measurement_theta_max 168 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max .15 _exptl_crystal_size_mid .05 _exptl_crystal_size_min .05 _exptl_crystal_density_meas - _exptl_crystal_density_diffrn 1.143 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 792 _exptl_absorpt_coefficient_mu 0.069 _exptl_absorpt_correction_type multiscan _exptl_absorpt_correction_T_min 0.856122 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details - _exptl_special_details ; - ; _diffrn_ambient_temperature 125(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 0.9 _diffrn_standards_number - _diffrn_standards_interval_count - _diffrn_standards_interval_time - _diffrn_standards_decay_% - _diffrn_reflns_number 9253 _diffrn_reflns_av_R_equivalents 0.1101 _diffrn_reflns_av_sigmaI/netI 0.1948 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 6 _diffrn_reflns_theta_min 1.51 _diffrn_reflns_theta_max 23.28 _reflns_number_total 3044 _reflns_number_gt 1485 _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^)+(0.0177P)^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 0.0136(7) _refine_ls_extinction_expression Fc^*^==kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 1(2) _refine_ls_number_reflns 3044 _refine_ls_number_parameters 262 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.1290 _refine_ls_R_factor_gt 0.0429 _refine_ls_wR_factor_ref 0.0660 _refine_ls_wR_factor_gt 0.0526 _refine_ls_goodness_of_fit_ref 0.738 _refine_ls_restrained_S_all 0.738 _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 N1 N 0.78877(17) 0.10466(11) 0.2451(5) 0.0235(8) Uani 1 1 d . . . C2 C 0.7426(2) 0.15896(16) 0.1711(7) 0.0247(10) Uani 1 1 d D . . H2 H 0.7454(16) 0.1683(11) 0.0046(12) 0.012(9) Uiso 1 1 d D . . C3 C 0.7045(2) 0.10398(15) 0.2329(6) 0.0222(9) Uani 1 1 d . . . C4 C 0.8321(2) 0.07197(14) 0.0509(7) 0.0252(10) Uani 1 1 d . . . H4A H 0.7993 0.0731 -0.0975 0.030 Uiso 1 1 calc R . . C5 C 0.8427(2) 0.00891(16) 0.1259(7) 0.0246(10) Uani 1 1 d . . . C6 C 0.8841(2) -0.00469(16) 0.3347(7) 0.0306(11) Uani 1 1 d . . . H6A H 0.9060 0.0260 0.4293 0.037 Uiso 1 1 calc R . . C7 C 0.8932(2) -0.06314(17) 0.4035(8) 0.0362(11) Uani 1 1 d . . . H7A H 0.9213 -0.0723 0.5455 0.043 Uiso 1 1 calc R . . C8 C 0.8617(2) -0.10810(17) 0.2671(8) 0.0388(12) Uani 1 1 d . . . H8A H 0.8677 -0.1480 0.3148 0.047 Uiso 1 1 calc R . . C9 C 0.8215(2) -0.09434(16) 0.0617(8) 0.0401(12) Uani 1 1 d . . . H9A H 0.8003 -0.1250 -0.0341 0.048 Uiso 1 1 calc R . . C10 C 0.8116(2) -0.03657(15) -0.0070(7) 0.0321(12) Uani 1 1 d . . . H10A H 0.7828 -0.0279 -0.1482 0.038 Uiso 1 1 calc R . . C11 C 0.9107(2) 0.10390(14) 0.0046(7) 0.0400(12) Uani 1 1 d . . . H11A H 0.8999 0.1444 -0.0463 0.060 Uiso 1 1 calc R . . H11B H 0.9402 0.0832 -0.1205 0.060 Uiso 1 1 calc R . . H11C H 0.9423 0.1045 0.1511 0.060 Uiso 1 1 calc R . . C12 C 0.7439(2) 0.21007(14) 0.3486(6) 0.0193(10) Uani 1 1 d . . . O12 O 0.77338(14) 0.18683(9) 0.5708(4) 0.0257(7) Uani 1 1 d D . . H12O H 0.7994(16) 0.1498(7) 0.526(6) 0.055(13) Uiso 1 1 d D . . C13 C 0.6589(2) 0.23126(15) 0.3809(7) 0.0221(10) Uani 1 1 d . . . C14 C 0.6144(2) 0.21741(16) 0.5780(7) 0.0324(11) Uani 1 1 d . . . H14A H 0.6373 0.1941 0.7005 0.039 Uiso 1 1 calc R . . C15 C 0.5365(2) 0.23679(15) 0.6023(8) 0.0348(11) Uani 1 1 d . . . H15A H 0.5070 0.2273 0.7412 0.042 Uiso 1 1 calc R . . C16 C 0.5022(2) 0.26999(17) 0.4232(8) 0.0415(12) Uani 1 1 d . . . H16A H 0.4488 0.2832 0.4375 0.050 Uiso 1 1 calc R . . C17 C 0.5465(2) 0.28378(15) 0.2227(8) 0.0347(11) Uani 1 1 d . . . H17A H 0.5236 0.3066 0.0984 0.042 Uiso 1 1 calc R . . C18 C 0.6236(2) 0.26439(15) 0.2043(7) 0.0309(11) Uani 1 1 d . . . H18A H 0.6535 0.2741 0.0662 0.037 Uiso 1 1 calc R . . C19 C 0.7959(2) 0.26208(15) 0.2769(7) 0.0199(9) Uani 1 1 d . . . C20 C 0.8011(2) 0.30820(15) 0.4386(7) 0.0275(10) Uani 1 1 d . . . H20A H 0.7748 0.3048 0.5876 0.033 Uiso 1 1 calc R . . C21 C 0.8434(2) 0.35882(16) 0.3892(7) 0.0295(11) Uani 1 1 d . . . H21A H 0.8455 0.3898 0.5026 0.035 Uiso 1 1 calc R . . C22 C 0.8828(2) 0.36425(16) 0.1749(7) 0.0309(11) Uani 1 1 d . . . H22A H 0.9120 0.3990 0.1394 0.037 Uiso 1 1 calc R . . C23 C 0.8792(2) 0.31887(16) 0.0133(7) 0.0264(10) Uani 1 1 d . . . H23A H 0.9069 0.3221 -0.1334 0.032 Uiso 1 1 calc R . . C24 C 0.83530(19) 0.26806(16) 0.0617(7) 0.0268(10) Uani 1 1 d . . . H24A H 0.8324 0.2375 -0.0535 0.032 Uiso 1 1 calc R . . C25 C 0.6418(2) 0.07104(15) 0.2726(7) 0.0302(11) Uani 1 1 d . . . C26 C 0.6475(2) 0.00855(15) 0.3611(7) 0.0457(13) Uani 1 1 d . . . H26A H 0.7035 -0.0023 0.3802 0.069 Uiso 1 1 calc R . . H26B H 0.6224 -0.0180 0.2459 0.069 Uiso 1 1 calc R . . H26C H 0.6204 0.0052 0.5148 0.069 Uiso 1 1 calc R . . C27 C 0.5590(2) 0.09442(14) 0.2337(8) 0.0514(14) Uani 1 1 d . . . H27A H 0.5619 0.1348 0.1722 0.077 Uiso 1 1 calc R . . H27B H 0.5300 0.0943 0.3851 0.077 Uiso 1 1 calc R . . H27C H 0.5312 0.0694 0.1186 0.077 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 N1 0.023(2) 0.0183(17) 0.029(2) -0.0029(17) -0.0018(17) -0.0006(16) C2 0.027(3) 0.027(3) 0.020(3) 0.002(2) 0.000(2) 0.004(2) C3 0.018(3) 0.028(2) 0.021(2) 0.000(2) -0.003(2) 0.002(2) C4 0.030(3) 0.023(2) 0.022(3) -0.003(2) 0.005(2) -0.003(2) C5 0.019(2) 0.027(2) 0.028(3) 0.003(2) 0.003(2) 0.001(2) C6 0.033(3) 0.023(2) 0.036(3) -0.004(2) -0.001(2) 0.001(2) C7 0.030(3) 0.037(3) 0.042(3) 0.009(3) 0.000(2) 0.005(2) C8 0.040(3) 0.020(3) 0.056(4) 0.004(3) 0.009(3) 0.008(2) C9 0.050(3) 0.022(3) 0.049(3) -0.004(3) -0.004(3) 0.003(2) C10 0.034(3) 0.019(2) 0.044(3) -0.009(2) -0.011(2) 0.003(2) C11 0.029(3) 0.030(2) 0.061(3) -0.004(3) 0.018(2) 0.001(2) C12 0.022(3) 0.019(2) 0.017(3) -0.0018(19) -0.005(2) -0.0019(19) O12 0.0349(17) 0.0209(15) 0.0213(17) 0.0024(14) -0.0051(14) 0.0028(13) C13 0.024(3) 0.026(2) 0.017(3) 0.001(2) -0.001(2) -0.006(2) C14 0.032(3) 0.039(3) 0.025(3) 0.004(2) -0.004(3) -0.003(2) C15 0.032(3) 0.039(3) 0.034(3) -0.001(2) 0.014(3) -0.007(2) C16 0.029(3) 0.043(3) 0.052(3) -0.015(3) 0.005(3) 0.005(2) C17 0.031(3) 0.034(3) 0.038(3) 0.002(2) -0.001(3) 0.008(2) C18 0.033(3) 0.029(3) 0.031(3) 0.004(2) 0.003(2) 0.000(2) C19 0.017(2) 0.019(2) 0.024(3) 0.001(2) -0.002(2) 0.0048(19) C20 0.033(3) 0.022(2) 0.027(3) 0.002(2) -0.003(2) -0.003(2) C21 0.037(3) 0.025(2) 0.026(3) -0.003(2) -0.003(2) -0.003(2) C22 0.033(3) 0.021(3) 0.039(3) 0.003(2) -0.005(2) 0.000(2) C23 0.022(2) 0.030(2) 0.027(3) 0.005(2) -0.002(2) 0.000(2) C24 0.022(2) 0.031(2) 0.028(3) 0.000(2) -0.004(2) -0.001(2) C25 0.025(3) 0.023(2) 0.043(3) 0.001(2) -0.001(2) 0.001(2) C26 0.037(3) 0.036(3) 0.064(4) 0.015(3) 0.008(2) -0.011(2) C27 0.025(3) 0.039(3) 0.091(4) 0.006(3) -0.006(3) -0.009(2) _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 N1 C3 1.421(4) . ? N1 C4 1.507(4) . ? N1 C2 1.516(4) . ? C2 C3 1.445(5) . ? C2 C12 1.530(4) . ? C3 C25 1.313(4) . ? C4 C5 1.503(4) . ? C4 C11 1.532(4) . ? C5 C10 1.377(4) . ? C5 C6 1.399(4) . ? C6 C7 1.390(5) . ? C7 C8 1.382(5) . ? C8 C9 1.374(5) . ? C9 C10 1.377(4) . ? C12 O12 1.443(4) . ? C12 C13 1.522(4) . ? C12 C19 1.525(4) . ? C13 C14 1.373(4) . ? C13 C18 1.379(5) . ? C14 C15 1.390(4) . ? C15 C16 1.384(5) . ? C16 C17 1.387(5) . ? C17 C18 1.376(4) . ? C19 C24 1.386(5) . ? C19 C20 1.388(4) . ? C20 C21 1.380(4) . ? C21 C22 1.380(5) . ? C22 C23 1.374(4) . ? C23 C24 1.396(4) . ? C25 C26 1.506(4) . ? C25 C27 1.509(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 C3 N1 C4 116.3(3) . . ? C3 N1 C2 58.9(2) . . ? C4 N1 C2 116.7(3) . . ? C3 C2 N1 57.3(2) . . ? C3 C2 C12 120.3(3) . . ? N1 C2 C12 115.5(3) . . ? C25 C3 N1 143.3(4) . . ? C25 C3 C2 152.8(4) . . ? N1 C3 C2 63.8(2) . . ? C5 C4 N1 108.9(3) . . ? C5 C4 C11 113.3(3) . . ? N1 C4 C11 108.0(3) . . ? C10 C5 C6 118.6(3) . . ? C10 C5 C4 121.1(3) . . ? C6 C5 C4 120.3(3) . . ? C7 C6 C5 119.9(4) . . ? C8 C7 C6 120.5(4) . . ? C9 C8 C7 119.1(4) . . ? C8 C9 C10 120.8(4) . . ? C9 C10 C5 121.0(4) . . ? O12 C12 C13 109.7(3) . . ? O12 C12 C19 108.2(3) . . ? C13 C12 C19 109.2(3) . . ? O12 C12 C2 106.9(3) . . ? C13 C12 C2 107.7(3) . . ? C19 C12 C2 115.0(3) . . ? C14 C13 C18 118.0(3) . . ? C14 C13 C12 122.5(4) . . ? C18 C13 C12 119.4(4) . . ? C13 C14 C15 121.4(4) . . ? C16 C15 C14 119.7(4) . . ? C15 C16 C17 119.2(4) . . ? C18 C17 C16 119.8(4) . . ? C17 C18 C13 121.8(4) . . ? C24 C19 C20 117.8(3) . . ? C24 C19 C12 125.6(3) . . ? C20 C19 C12 116.6(3) . . ? C21 C20 C19 121.9(4) . . ? C22 C21 C20 119.8(4) . . ? C23 C22 C21 119.2(4) . . ? C22 C23 C24 120.9(4) . . ? C19 C24 C23 120.3(4) . . ? C3 C25 C26 122.8(3) . . ? C3 C25 C27 121.3(3) . . ? C26 C25 C27 115.9(3) . . ? 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 N1 C2 C3 106.0(3) . . . . ? C3 N1 C2 C12 111.0(4) . . . . ? C4 N1 C2 C12 -143.1(3) . . . . ? C4 N1 C3 C25 76.8(6) . . . . ? C2 N1 C3 C25 -176.5(7) . . . . ? C4 N1 C3 C2 -106.7(3) . . . . ? N1 C2 C3 C25 175.4(9) . . . . ? C12 C2 C3 C25 72.9(9) . . . . ? C12 C2 C3 N1 -102.6(4) . . . . ? C3 N1 C4 C5 -88.6(3) . . . . ? C2 N1 C4 C5 -155.2(3) . . . . ? C3 N1 C4 C11 148.1(3) . . . . ? C2 N1 C4 C11 81.5(4) . . . . ? N1 C4 C5 C10 120.4(3) . . . . ? C11 C4 C5 C10 -119.5(4) . . . . ? N1 C4 C5 C6 -59.1(4) . . . . ? C11 C4 C5 C6 61.0(4) . . . . ? C10 C5 C6 C7 0.1(5) . . . . ? C4 C5 C6 C7 179.6(3) . . . . ? C5 C6 C7 C8 0.1(6) . . . . ? C6 C7 C8 C9 0.3(6) . . . . ? C7 C8 C9 C10 -0.9(6) . . . . ? C8 C9 C10 C5 1.1(6) . . . . ? C6 C5 C10 C9 -0.7(5) . . . . ? C4 C5 C10 C9 179.9(4) . . . . ? C3 C2 C12 O12 51.2(4) . . . . ? N1 C2 C12 O12 -14.3(4) . . . . ? C3 C2 C12 C13 -66.6(4) . . . . ? N1 C2 C12 C13 -132.1(3) . . . . ? C3 C2 C12 C19 171.4(3) . . . . ? N1 C2 C12 C19 105.9(3) . . . . ? O12 C12 C13 C14 -13.0(4) . . . . ? C19 C12 C13 C14 -131.5(4) . . . . ? C2 C12 C13 C14 103.0(4) . . . . ? O12 C12 C13 C18 168.7(3) . . . . ? C19 C12 C13 C18 50.3(4) . . . . ? C2 C12 C13 C18 -75.3(4) . . . . ? C18 C13 C14 C15 -1.0(5) . . . . ? C12 C13 C14 C15 -179.3(3) . . . . ? C13 C14 C15 C16 1.0(6) . . . . ? C14 C15 C16 C17 -0.5(6) . . . . ? C15 C16 C17 C18 0.0(6) . . . . ? C16 C17 C18 C13 0.0(6) . . . . ? C14 C13 C18 C17 0.5(5) . . . . ? C12 C13 C18 C17 178.8(3) . . . . ? O12 C12 C19 C24 125.0(4) . . . . ? C13 C12 C19 C24 -115.7(4) . . . . ? C2 C12 C19 C24 5.5(5) . . . . ? O12 C12 C19 C20 -57.8(4) . . . . ? C13 C12 C19 C20 61.5(4) . . . . ? C2 C12 C19 C20 -177.3(3) . . . . ? C24 C19 C20 C21 0.4(5) . . . . ? C12 C19 C20 C21 -177.0(3) . . . . ? C19 C20 C21 C22 -0.7(5) . . . . ? C20 C21 C22 C23 0.0(5) . . . . ? C21 C22 C23 C24 1.1(5) . . . . ? C20 C19 C24 C23 0.6(5) . . . . ? C12 C19 C24 C23 177.8(3) . . . . ? C22 C23 C24 C19 -1.4(5) . . . . ? N1 C3 C25 C26 -1.5(8) . . . . ? C2 C3 C25 C26 -174.7(7) . . . . ? N1 C3 C25 C27 177.8(4) . . . . ? C2 C3 C25 C27 4.7(10) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O12 H12O N1 0.9799(11) 1.89(3) 2.625(4) 129(3) . _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 23.28 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.144 _refine_diff_density_min -0.140 _refine_diff_density_rms 0.035