# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 loop_ _publ_author_name _publ_author_address 'Davies, Stephen G.' ;Department of Organic Chemistry Chemistry Research Laboratory University of Oxford Mansfield Road Oxford OX1 3TA UK ; 'Ling, Kenneth B.' ;Department of Organic Chemistry Chemistry Research Laboratory University of Oxford Mansfield Road Oxford OX1 3TA UK ; 'Roberts, Paul M.' ;Department of Organic Chemistry Chemistry Research Laboratory University of Oxford Mansfield Road Oxford OX1 3TA UK ; 'Russell, Angela J.' ;Department of Organic Chemistry Chemistry Research Laboratory University of Oxford Mansfield Road Oxford OX1 3TA UK ; 'Thomson, James E.' ;Department of Organic Chemistry Chemistry Research Laboratory University of Oxford Mansfield Road Oxford OX1 3TA UK ; _publ_contact_author_address ;Department of Organic Chemistry Chemistry Research Laboratory University of Oxford Mansfield Road Oxford OX1 3TA UK ; _publ_contact_author_email steve.davies@chem.ox.ac.uk _publ_contact_author_fax '+44 1865 275633' _publ_contact_author_phone '+44 1865 275695' _publ_contact_author_name 'Stephen G. Davies' # Check this file using the IUCr facility at: # http://checkcif.iucr.org/ # The content below is held in the file 'script/refcif.dat'. This is a text # file which you may edit to reflect local conditions. # Items which need looking at are represented by a '?'. # Items for which there are choices are prefixed with 'choose from'. _publ_contact_letter ; Please consider this CIF submission for publication as a Short Format Paper in Chem. Commun. The figures have been sent by mail. ; _publ_requested_category CO # choose from: FI FM FO CI CM CO AD _publ_requested_coeditor_name 'Dr Paul M. Roberts' _publ_section_title # Title of paper ; Diastereoselective Simmons-Smith cyclopropanations of allylic amines and carbamates ; data_CRYSTALS_cif _database_code_depnum_ccdc_archive 'CCDC 644843' _audit_creation_date 06-03-10 _audit_creation_method CRYSTALS_ver_12.82 _oxford_structure_analysis_title '3101429 Compound X' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 8.5766(3) _cell_length_b 7.0349(3) _cell_length_c 10.6494(5) _cell_angle_alpha 90 _cell_angle_beta 109.9188(15) _cell_angle_gamma 90 _cell_volume 604.10(4) _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/m' _symmetry_int_tables_number 11 _symmetry_space_group_name_Hall ? loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x,y+1/2,-z x,-y+1/2,z loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 2 # Given Formula = C15 H15 N1 O2 # Dc = 1.33 Fooo = 256.00 Mu = 0.88 M = 120.64 # Found Formula = C15 H15 N1 O2 # Dc = 1.33 FOOO = 256.00 Mu = 0.88 M = 120.64 _chemical_formula_sum 'C15 H15 N1 O2' _chemical_formula_moiety 'C15 H15 N1 O2' _chemical_compound_source ? _chemical_formula_weight 241.29 _cell_measurement_reflns_used 1433 _cell_measurement_theta_min 5 _cell_measurement_theta_max 27 _cell_measurement_temperature 190 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_min 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_max 0.30 _exptl_crystal_density_diffrn 1.326 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 256 _exptl_absorpt_coefficient_mu 0.088 # Sheldrick geometric approximatio 0.99 0.99 # No experimental values of Tmin/max available _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.99 _exptl_absorpt_correction_T_max 0.99 _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_radiation_monochromator graphite _diffrn_radiation_probe ? _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'COLLECT. Nonius (1997-2001).' _computing_data_reduction 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_cell_refinement 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 190 _diffrn_reflns_number 2708 _reflns_number_total 1468 _diffrn_reflns_av_R_equivalents 0.021 # Number of reflections with Friedels Law is 1468 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 1382 _diffrn_reflns_theta_min 5.304 _diffrn_reflns_theta_max 27.460 _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 26.911 _diffrn_measured_fraction_theta_full 0.982 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _reflns_limit_h_min -11 _reflns_limit_h_max 10 _reflns_limit_k_min 0 _reflns_limit_k_max 9 _reflns_limit_l_min 0 _reflns_limit_l_max 13 _oxford_diffrn_Wilson_B_factor 0.00 _oxford_diffrn_Wilson_scale 0.00 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.44 _refine_diff_density_max 0.42 _refine_ls_number_reflns 1468 _refine_ls_number_restraints 56 _refine_ls_number_parameters 130 #_refine_ls_R_factor_ref 0.1211 _refine_ls_wR_factor_ref 0.2144 _refine_ls_goodness_of_fit_ref 1.0452 #_reflns_number_all 1468 _refine_ls_R_factor_all 0.1211 _refine_ls_wR_factor_all 0.2144 # No actual I/u(I) cutoff was used for refinement. The # threshold below is used for "_gt" information ONLY: _reflns_threshold_expression I>2.00u(I) _reflns_number_gt 1206 _refine_ls_R_factor_gt 0.1044 _refine_ls_wR_factor_gt 0.2057 _refine_ls_shift/su_max 0.007654 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment noref # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; w=1/[\s^2^(F^2^) + ( 0.04P)^2^ + 1.06P] where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; _publ_section_abstract # Text of the abstract ; ? ; _publ_section_comment # Text of the paper ; ? ; _publ_section_acknowledgements # Acknowledgments ; ? ; _publ_section_figure_captions # Captions to figures ; ? ; _publ_section_exptl_refinement # Some potentially useful phrases are: ; Because the data were collected with molybdenum radiation, there were no measurable anomalous differences, as a consequence of which it was admissible to merge Friedel pairs of reflections. All hydrogen atoms were found in difference density syntheses. Hydrogen atoms were placed geometrically after each cycle. Hydrogen atoms were placed geometrically after each cycle, the preferred orientations of those groups whose conformations could not be assigned unambiguously having been previously identified by examination of a difference Fourier map. Hydrogen atoms were seen in a difference density synthesis. Those attached to carbon atoms were repositioned geometrically. Hydrogen were initially refined with soft restraints on the bonds to regularise their geometry (bond lengths to accepted values, angles either set by symmetry or to accepted values, and U[iso] dependent upon the adjacent bonded atom), after which they were refined with riding constraints only. donated by Bill Clegg: The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularise their geometry (C---H in the range 0.93-98, O---N in the range 0.86-0.89 and O---H = 0.82 \%A) and isotropic adps (U(H) in the range 1.2-1.5 times U~equiv~ of the adjacent atom), after which they were refined with riding constraints. . ; _publ_section_exptl_prep ; ? ; # End of 'script/refcif.dat' # Insert your own references if required - in alphabetical order _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo G., Guagliardi A., Burla M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. (27), 435-435 Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius (1997-2001). COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: Academic Press. Sheldrick, G.M. (1997). SHELXL-97. University of G\"ottingen, Germany. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens N1 N 0.1574(4) 0.2500 0.3577(3) 0.0544 1.0000 Uani S T . . . . C1 C 0.2856(5) 0.2500 0.3046(4) 0.0461 1.0000 Uani S T . . . . C2 C 0.4429(4) 0.2500 0.4211(4) 0.0373 1.0000 Uani S T . . . . C3 C 0.6059(5) 0.2500 0.4278(5) 0.0516 1.0000 Uani S T . . . . C4 C 0.7271(5) 0.2500 0.5535(5) 0.0569 1.0000 Uani S T . . . . C5 C 0.6859(5) 0.2500 0.6676(5) 0.0562 1.0000 Uani S T . . . . C6 C 0.5213(5) 0.2500 0.6609(4) 0.0572 1.0000 Uani S T . . . . C7 C 0.4016(4) 0.2500 0.5356(4) 0.0420 1.0000 Uani S T . . . . C8 C 0.2189(5) 0.2500 0.4960(4) 0.0576 1.0000 Uani S T . . . . O1 O 0.2702(4) 0.2500 0.1882(3) 0.0701 1.0000 Uani S T . . . . O2 O 0.1353(4) 0.2500 0.5676(3) 0.0883 1.0000 Uani S T . . . . C9 C -0.0236(6) 0.2063(10) 0.2855(5) 0.0467 0.5000 Uani . U . 1 -1 . C10 C -0.1019(8) 0.3973(13) 0.2540(9) 0.0651 0.5000 Uani . U . 1 -1 . C11 C -0.2549(19) 0.455(2) 0.1398(13) 0.0776 0.5000 Uani . U . 1 -1 . C12 C -0.3279(8) 0.2909(18) 0.0490(6) 0.0782 0.5000 Uani . U . 1 -1 . C13 C -0.2561(19) 0.088(2) 0.1022(12) 0.0830 0.5000 Uani . U . 1 -1 . C14 C -0.0635(10) 0.0691(16) 0.1780(10) 0.0769 0.5000 Uani . U . 1 -1 . C15 C -0.0996(12) 0.4943(19) 0.1367(11) 0.0957 0.5000 Uani . U . 1 -1 . H31 H 0.6360 0.2500 0.3450 0.0640 1.0000 Uiso . . . . . . H41 H 0.8467 0.2500 0.5613 0.0676 1.0000 Uiso . . . . . . H51 H 0.7760 0.2500 0.7569 0.0637 1.0000 Uiso . . . . . . H61 H 0.4908 0.2500 0.7436 0.0675 1.0000 Uiso . . . . . . H91 H -0.0714 0.1307 0.3432 0.0545 0.5000 Uiso . . . 1 -1 . H101 H -0.0678 0.4130 0.3530 0.0738 0.5000 Uiso . . . 1 -1 . H111 H -0.3574 0.5296 0.1316 0.0850 0.5000 Uiso . . . 1 -1 . H121 H -0.4499 0.2887 0.0327 0.0851 0.5000 Uiso . . . 1 -1 . H122 H -0.3086 0.3134 -0.0373 0.0851 0.5000 Uiso . . . 1 -1 . H131 H -0.3129 0.0450 0.1650 0.0867 0.5000 Uiso . . . 1 -1 . H132 H -0.2853 0.0013 0.0234 0.0867 0.5000 Uiso . . . 1 -1 . H141 H -0.0355 -0.0622 0.2144 0.0831 0.5000 Uiso . . . 1 -1 . H142 H -0.0010 0.0985 0.1163 0.0831 0.5000 Uiso . . . 1 -1 . H151 H -0.0610 0.6296 0.1445 0.1068 0.5000 Uiso . . . 1 -1 . H152 H -0.0595 0.4258 0.0715 0.1068 0.5000 Uiso . . . 1 -1 . 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 0.0243(16) 0.096(3) 0.0401(18) 0.0000 0.0071(13) 0.0000 C1 0.039(2) 0.057(3) 0.041(2) 0.0000 0.0121(17) 0.0000 C2 0.0300(18) 0.040(2) 0.043(2) 0.0000 0.0132(15) 0.0000 C3 0.034(2) 0.068(3) 0.058(3) 0.0000 0.0224(19) 0.0000 C4 0.0252(18) 0.066(3) 0.078(3) 0.0000 0.016(2) 0.0000 C5 0.033(2) 0.071(3) 0.056(3) 0.0000 0.0029(18) 0.0000 C6 0.039(2) 0.092(4) 0.038(2) 0.0000 0.0092(17) 0.0000 C7 0.0271(18) 0.057(3) 0.043(2) 0.0000 0.0130(15) 0.0000 C8 0.0271(19) 0.101(4) 0.044(2) 0.0000 0.0120(17) 0.0000 O1 0.0530(19) 0.120(3) 0.0393(17) 0.0000 0.0179(14) 0.0000 O2 0.0336(16) 0.190(5) 0.0455(18) 0.0000 0.0186(14) 0.0000 C9 0.025(2) 0.072(5) 0.039(2) -0.005(3) 0.0062(18) 0.000(3) C10 0.037(3) 0.077(4) 0.071(4) 0.014(3) 0.005(3) 0.005(3) C11 0.043(3) 0.101(6) 0.069(5) -0.004(4) -0.007(3) 0.008(4) C12 0.045(3) 0.112(8) 0.056(3) -0.008(4) -0.011(2) 0.012(4) C13 0.043(3) 0.100(7) 0.074(6) -0.018(5) -0.022(5) -0.001(5) C14 0.039(3) 0.099(6) 0.070(5) -0.037(4) -0.011(3) -0.006(4) C15 0.058(4) 0.113(6) 0.096(5) 0.047(4) 0.001(4) -0.008(5) _refine_ls_extinction_method None _oxford_refine_ls_scale 3.03(12) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag N1 . C9 4_555 1.510(6) yes N1 . C1 . 1.397(5) yes N1 . C8 . 1.385(5) yes N1 . C9 . 1.510(6) yes C1 . C2 . 1.489(5) yes C1 . O1 . 1.200(5) yes C2 . C3 . 1.375(5) yes C2 . C7 . 1.381(5) yes C3 . C4 . 1.387(6) yes C3 . H31 . 1.000 no C4 . C5 . 1.377(7) yes C4 . H41 . 1.000 no C5 . C6 . 1.390(6) yes C5 . H51 . 1.000 no C6 . C7 . 1.379(6) yes C6 . H61 . 1.000 no C7 . C8 . 1.478(5) yes C8 . O2 . 1.210(5) yes C9 . C10 . 1.489(11) yes C9 . C14 . 1.446(11) yes C9 . H91 . 1.000 no C10 . C11 . 1.510(16) yes C10 . C15 . 1.429(12) yes C10 . H101 . 1.000 no C11 . C12 . 1.502(14) yes C11 . C15 . 1.37(2) yes C11 . H111 . 1.000 no C12 . C13 . 1.579(17) yes C12 . H121 . 1.000 no C12 . H122 . 1.000 no C13 . C14 . 1.578(16) yes C13 . H131 . 1.000 no C13 . H132 . 0.999 no C14 . H141 . 0.999 no C14 . H142 . 1.001 no C15 . H151 . 1.002 no C15 . H152 . 0.998 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C9 4_555 N1 . C1 . 127.4(3) yes C9 4_555 N1 . C8 . 119.6(3) yes C1 . N1 . C8 . 111.3(3) yes C9 4_555 N1 . C9 . 23.5(5) yes C1 . N1 . C9 . 127.4(3) yes C8 . N1 . C9 . 119.6(3) yes N1 . C1 . C2 . 106.1(3) yes N1 . C1 . O1 . 126.4(4) yes C2 . C1 . O1 . 127.6(4) yes C1 . C2 . C3 . 131.3(4) yes C1 . C2 . C7 . 107.7(3) yes C3 . C2 . C7 . 121.0(4) yes C2 . C3 . C4 . 117.7(4) yes C2 . C3 . H31 . 121.1 no C4 . C3 . H31 . 121.1 no C3 . C4 . C5 . 121.2(4) yes C3 . C4 . H41 . 119.4 no C5 . C4 . H41 . 119.4 no C4 . C5 . C6 . 121.1(4) yes C4 . C5 . H51 . 119.5 no C6 . C5 . H51 . 119.4 no C5 . C6 . C7 . 117.3(4) yes C5 . C6 . H61 . 121.4 no C7 . C6 . H61 . 121.4 no C2 . C7 . C6 . 121.6(3) yes C2 . C7 . C8 . 108.3(3) yes C6 . C7 . C8 . 130.1(4) yes C7 . C8 . N1 . 106.6(3) yes C7 . C8 . O2 . 128.2(4) yes N1 . C8 . O2 . 125.2(4) yes N1 . C9 . C10 . 103.7(5) yes N1 . C9 . C14 . 117.6(5) yes C10 . C9 . C14 . 117.2(6) yes N1 . C9 . H91 . 111.2 no C10 . C9 . H91 . 111.7 no C14 . C9 . H91 . 95.5 no C9 . C10 . C11 . 128.9(8) yes C9 . C10 . C15 . 119.2(9) yes C11 . C10 . C15 . 55.5(8) yes C9 . C10 . H101 . 85.1 no C11 . C10 . H101 . 132.9 no C15 . C10 . H101 . 141.5 no C10 . C11 . C12 . 111.5(11) yes C10 . C11 . C15 . 59.3(8) yes C12 . C11 . C15 . 109.5(12) yes C10 . C11 . H111 . 135.1 no C12 . C11 . H111 . 100.6 no C15 . C11 . H111 . 136.6 no C11 . C12 . C13 . 116.0(5) yes C11 . C12 . H121 . 107.8 no C13 . C12 . H121 . 107.8 no C11 . C12 . H122 . 107.8 no C13 . C12 . H122 . 107.8 no H121 . C12 . H122 . 109.5 no C12 . C13 . C14 . 118.3(11) yes C12 . C13 . H131 . 107.2 no C14 . C13 . H131 . 107.2 no C12 . C13 . H132 . 107.2 no C14 . C13 . H132 . 107.3 no H131 . C13 . H132 . 109.5 no C13 . C14 . C9 . 105.8(9) yes C13 . C14 . H141 . 110.4 no C9 . C14 . H141 . 110.5 no C13 . C14 . H142 . 110.3 no C9 . C14 . H142 . 110.3 no H141 . C14 . H142 . 109.5 no C10 . C15 . C11 . 65.2(8) yes C10 . C15 . H151 . 118.9 no C11 . C15 . H151 . 118.9 no C10 . C15 . H152 . 119.2 no C11 . C15 . H152 . 119.3 no H151 . C15 . H152 . 109.5 no