# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 182/1415 data_CRYSTALS_cif _audit_creation_date 99-04-06 _audit_creation_method CRYSTALS_ver_12-03-99 _publ_section_title ; "A highly diastereoselective [2,3]-sigmatropic N-O rearrangement" ; # 1. SUBMISSION DETAILS _publ_contact_author_name 'Stephen G. Davies' _publ_contact_author_address ; The Dyson Perrins Laboratory South Parks Rd OXFORD OX1 3QY ; _publ_contact_author_email ' steve.davies@chemistry.ox.ac.uk ' _publ_requested_journal 'Chemical Communications' # xxx _publ_section_exptl_refinement ; The sample was one of many pieces cut from clear plate-like "crystals. Although the cut samples remained clear, the diffraction " patterns showed that they were always severely damaged by shearing parallel to the large face during the cutting. The final sample was obtained by repeatedly shaving very thin slices away from the edges of the original large crystal. The best obtainable diffraction pattern did not represent a simple single crystalline sample. Data extraction from the 90 images (180 degrees) collected on a Nonius DIP2000 diffractometer was complicated by the presence of more than one reciprocal lattice. Reflections from the strongest lattice were "used as the basis for the structure analysis, but were inevitably contaminated by data from the weaker lattice. We could not determine a valid twin law relating the two lattices - the sample was probably polycrystalline. "The weakest data showed the greatest discrepancy between Fo and Fc, " presumably because the accidental overlap of a strong component of the minor lattice on a weak component of the strong lattice had a more damaging effect than the inverse. Data with I less than 6 sigma(I) were "there for excluded from the refinement. The value of '6' is subjective, " but was chosen by looking at the residual distribution so as to preserve "as many 'fair' reflections as possible, and at the same time reject as " many 'suspect' reflections as possible. Only one of the water hydrogen atoms could be located. ; ## -----------------REFERENCES ----------------------## _publ_section_references # Add your own references - in alphabetic order ; # SIR92 # "Altomare, A., Cascarano, G., Giacovazzo G., Guagliardi A., Burla M.C., " "Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic solution of " "crystal structures by direct methods. J. Appl. Cryst. (27), 435-435 " # Chebychev Weights # "Carruthers, J.R. and Watkin, D.J. (1979), " "Acta Cryst, A35, 698-699 " # Denzo # "Otwinowski, Z. & Minor, W. (1996), Processing of X-ray " Diffraction Data Collected in Oscillation Mode. Methods Enzymol. "276, 1997, 307-326. Ed Carter, C.W. & Sweet, R.M., Academic Press. " # Extinction correction # "Larson, A.C. (1970), Crystallographic Computing, Ed Ahmed, F.R., " "Munksgaard, Copenhagen, 291-294 " # Azimutal absorption correction # # SHELXS 86 # # DIFABS # # CRYSTALS # "Watkin, D.J., Prout, C.K. Carruthers, J.R. & Betteridge, P.W. (1996) CRYSTALS " "Issue 10. Chemical Crystallography Laboratory, OXFORD, UK. " #CAMERON # "Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical " "Crystallography Laboratory, OXFORD, UK. " # RC93 # "Watkin, D.J., Prout, C.K., Lilley, P.M.deQ. (1994), RC93, Chemical " "Crystallography Laboratory, Oxford, UK. " ; #============================================================ # Diffractometer details _diffrn_measurement_device_type ; Enraf-nonius DIP2000 ; _diffrn_radiation_monochromator graphite _computing_data_collection ; "DIP2000 software 'Xpress' (MAC Science, 1989) " ; _computing_data_reduction ; "DIP2000 software 'DENZO' (Otwinowski & Minor, 1996) " ; _computing_cell_refinement ; "DIP2000 software 'DENZO' (Otwinowski & Minor, 1996) " ; # General computing #============================================================ _computing_structure_refinement ; "CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) " ; _computing_publication_material ; "CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) " ; _computing_molecular_graphics ; " CAMERON (Watkin, Prout & Pearce, 1996) " ; #============================================================ _chemical_name_systematic # IUPAC name, in full " ; syn-N-benzyl-4-phenyl-3-aminoprop-1-ene hydrochloride ; _chemical_melting_point 'not measured' # choose from 'full, fullcycle, atomblock, userblock, diagonal, sparse' " _refine_ls_matrix_type full # choose from 'heavy, direct, difmap, geom' " _atom_sites_solution_primary direct # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom # choose from 'none, undef, noref, refall, refxyz, refU, constr, mixed' " _refine_ls_hydrogen_treatment noref #**************************************************************************** _cell_length_a 6.403(1) _cell_angle_alpha 90 _cell_length_b 27.046(1) _cell_angle_beta 97.85(2) _cell_length_c 10.252(1) _cell_angle_gamma 90 _cell_volume 1758.8 _symmetry_cell_setting 'Monoclinic ' _symmetry_space_group_name_H-M 'P 1 21/n 1 ' loop_ _symmetry_equiv_pos_as_xyz " 'x,y,z'" " '-x,-y,-z'" " '-x+1/2,y+1/2,-z+1/2'" " 'x+1/2,-y+1/2,z+1/2'" 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 ' 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International_Tables_Vol_IV_Table_2.2B' 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 'International_Tables_Vol_IV_Table_2.2B' 'N ' 0.0040 0.0030 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International_Tables_Vol_IV_Table_2.2B' 'O ' 0.0080 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International_Tables_Vol_IV_Table_2.2B' 'Cl ' 0.1320 0.1590 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International_Tables_Vol_IV_Table_2.2B' _chemical_formula_sum ' C18 H24 Cl1 N1 O2 ' _chemical_formula_moiety ' C18 H24 Cl1 N1 O2 ' _chemical_compound_source ; ? ; _chemical_formula_weight 321.84 _cell_measurement_reflns_used 11145 _cell_measurement_theta_min 0 _cell_measurement_theta_max 27 _cell_measurement_temperature 180 _cell_formula_units_Z 4 _exptl_crystal_description ' plate ' _exptl_crystal_colour ' colourless ' _exptl_crystal_size_min 0.20 _exptl_crystal_size_mid 0.80 _exptl_crystal_size_max 0.80 _exptl_crystal_density_diffrn 1.21 _exptl_crystal_density_meas 'not measured' _exptl_crystal_F_000 684.67 _exptl_absorpt_coefficient_mu 0.22 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8 _exptl_absorpt_correction_T_max 0.9 _diffrn_ambient_temperature 180 _diffrn_reflns_number 3109 _reflns_number_total 3109 _diffrn_reflns_av_R_equivalents 0.08 # Number of reflections with Friedels Law is 3109 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 3673 _diffrn_measured_fraction_theta_max 0.846 _reflns_number_gt 2050 _diffrn_reflns_theta_min 0.00 _diffrn_reflns_theta_max 26.57 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _reflns_limit_h_min -7 _reflns_limit_h_max 7 _reflns_limit_k_min -33 _reflns_limit_k_max 33 _reflns_limit_l_min 0 _reflns_limit_l_max 12 _refine_diff_density_min -0.69 _refine_diff_density_max 0.81 _reflns_threshold_expression >6.00\s(I) _refine_ls_number_reflns 2050 _refine_ls_number_parameters 199 _refine_ls_R_factor_gt 0.1129 _refine_ls_wR_factor_ref 0.1610 _refine_ls_goodness_of_fit_ref 1.6847 _refine_ls_shift/su_max 0.000142 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme sigma _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71069 _diffrn_measurement_method \w # Uequiv = arithmetic mean of Ui # i.e. Ueqiv = (U1+U2+U3)/3 loop_ _atom_site_label _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 Cl1 0.2132(4) 0.4327(1) 0.3984(3) 0.0312 1.0000 Uani O2 0.7553(11) 0.3458(3) 0.5415(7) 0.0284 1.0000 Uani C3 0.5534(16) 0.3282(4) 0.565(1) 0.0225 1.0000 Uani C4 0.5032(16) 0.3586(4) 0.684(1) 0.0227 1.0000 Uani N5 0.5244(14) 0.4116(3) 0.6482(8) 0.0228 1.0000 Uani C6 0.4588(17) 0.4490(4) 0.744(1) 0.0271 1.0000 Uani C7 0.5582(17) 0.4413(4) 0.886(1) 0.0255 1.0000 Uani C8 0.7717(17) 0.4486(4) 0.921(1) 0.0307 1.0000 Uani C9 0.8599(17) 0.4464(4) 1.0568(11) 0.0310 1.0000 Uani C10 0.7305(19) 0.4368(4) 1.149(1) 0.0306 1.0000 Uani C11 0.5147(18) 0.4283(4) 1.112(1) 0.0319 1.0000 Uani C12 0.4321(16) 0.4311(4) 0.980(1) 0.0262 1.0000 Uani C13 0.2816(17) 0.3469(4) 0.713(1) 0.0293 1.0000 Uani C14 0.242(2) 0.3250(5) 0.8200(12) 0.0476 1.0000 Uani C15 0.5615(17) 0.2742(3) 0.5919(9) 0.0233 1.0000 Uani C16 0.3810(18) 0.2430(4) 0.5510(11) 0.0326 1.0000 Uani C17 0.381(2) 0.1952(5) 0.5776(12) 0.0444 1.0000 Uani C18 0.559(2) 0.1729(4) 0.6449(11) 0.0352 1.0000 Uani C19 0.735(2) 0.2002(4) 0.6832(11) 0.0381 1.0000 Uani C20 0.7358(19) 0.2514(4) 0.6575(11) 0.0356 1.0000 Uani C21 0.809(2) 0.3332(4) 0.4148(11) 0.0369 1.0000 Uani O22 0.9057(13) 0.4542(3) 0.6130(8) 0.0395 1.0000 Uani H51 0.4368 0.4176 0.5618 1.0000 1.0000 Uiso H52 0.6762 0.4177 0.6407 1.0000 1.0000 Uiso H9 0.9760 0.4423 0.6556 1.0000 1.0000 Uiso H31 0.4394 0.3325 0.4870 0.0600 1.0000 Uiso H41 0.6018 0.3506 0.7658 0.0600 1.0000 Uiso H61 0.4979 0.4829 0.7144 0.0600 1.0000 Uiso H62 0.3010 0.4475 0.7399 0.0600 1.0000 Uiso H81 0.8649 0.4551 0.8508 0.0600 1.0000 Uiso H91 1.0152 0.4520 1.0837 0.0600 1.0000 Uiso H101 0.7908 0.4359 1.2453 0.0600 1.0000 Uiso H111 0.4216 0.4195 1.1811 0.0600 1.0000 Uiso H121 0.2755 0.4260 0.9522 0.0600 1.0000 Uiso H131 0.1580 0.3571 0.6458 0.0600 1.0000 Uiso H141 0.3622 0.3143 0.8892 0.0575 1.0000 Uiso H142 0.0938 0.3176 0.8364 0.0575 1.0000 Uiso H161 0.2503 0.2585 0.5005 0.0600 1.0000 Uiso H171 0.2499 0.1750 0.5490 0.0533 1.0000 Uiso H181 0.5586 0.1367 0.6659 0.0600 1.0000 Uiso H191 0.8662 0.1837 0.7298 0.0600 1.0000 Uiso H201 0.8649 0.2717 0.6886 0.0600 1.0000 Uiso H211 0.9512 0.3465 0.4040 0.0600 1.0000 Uiso H212 0.7018 0.3479 0.3436 0.0600 1.0000 Uiso H213 0.8086 0.2964 0.4033 0.0600 1.0000 Uiso 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 Cl1 0.0334(14) 0.0361(15) 0.0237(12) 0.0023(11) 0.0026(11) 0.0020(11) O2 0.034(4) 0.024(4) 0.029(4) -0.007(3) 0.010(3) -0.007(3) C3 0.025(5) 0.018(5) 0.025(5) 0.002(4) 0.005(4) 0.002(4) C4 0.030(6) 0.016(5) 0.022(5) 0.003(4) 0.005(4) 0.002(4) N5 0.038(5) 0.007(4) 0.024(4) 0.001(3) 0.005(4) 0.006(3) C6 0.030(6) 0.026(6) 0.024(5) -0.012(4) 0.002(5) 0.002(4) C7 0.031(6) 0.018(5) 0.028(5) -0.003(4) 0.007(5) 0.007(4) C8 0.025(6) 0.039(7) 0.028(6) -0.003(5) 0.005(5) -0.008(5) C9 0.030(6) 0.019(5) 0.041(6) 0.001(4) -0.007(5) 0.005(4) C10 0.049(7) 0.015(5) 0.027(5) 0.004(4) 0.004(5) 0.009(5) C11 0.044(7) 0.021(6) 0.033(6) -0.007(4) 0.011(5) -0.007(5) C12 0.030(6) 0.013(5) 0.035(6) -0.008(4) 0.003(5) -0.003(4) C13 0.030(6) 0.029(6) 0.030(6) -0.016(4) 0.010(5) -0.010(4) C14 0.067(9) 0.035(7) 0.045(7) -0.016(6) 0.024(7) -0.027(6) C15 0.034(6) 0.013(5) 0.022(5) -0.004(4) 0.001(5) -0.002(4) C16 0.034(6) 0.026(6) 0.036(6) -0.003(5) 0.001(5) 0.000(5) C17 0.052(8) 0.048(8) 0.036(7) 0.000(6) 0.016(6) -0.017(6) C18 0.063(8) 0.009(5) 0.035(6) -0.004(4) 0.012(6) 0.006(5) C19 0.059(8) 0.017(6) 0.036(6) 0.006(4) -0.004(6) -0.001(5) C20 0.038(7) 0.033(7) 0.034(6) -0.007(5) -0.004(5) -0.005(5) C21 0.055(8) 0.025(6) 0.034(6) -0.007(5) 0.019(6) -0.006(5) O22 0.050(5) 0.025(4) 0.048(5) -0.001(3) 0.023(4) -0.004(4) _refine_ls_extinction_coef 64.496 _refine_ls_extinction_method 'Larson 1970 Crystallographic Computing eq 22' 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 O2 . C3 . 1.429(12) yes O2 . C21 . 1.430(12) yes C3 . C4 . 1.537(13) yes C3 . C15 . 1.486(14) yes C3 . H31 . 1.01(1) no C4 . N5 . 1.491(12) yes C4 . C13 . 1.523(14) yes C4 . H41 . 1.00(1) no N5 . C6 . 1.507(12) yes N5 . H51 . 0.995(8) no N5 . H52 . 0.999(9) no C6 . C7 . 1.520(14) yes C6 . H61 . 1.007(11) no C6 . H62 . 1.007(11) no C7 . C8 . 1.381(15) yes C7 . C12 . 1.370(14) yes C8 . C9 . 1.426(15) yes C8 . H81 . 1.01(1) no C9 . C10 . 1.367(15) yes C9 . H91 . 1.007(11) no C10 . C11 . 1.401(16) yes C10 . H101 . 1.008(11) no C11 . C12 . 1.392(15) yes C11 . H111 . 1.01(1) no C12 . H121 . 1.01(1) no C13 . C14 . 1.305(16) yes C13 . H131 . 1.012(12) no C14 . H141 . 1.017(16) no C14 . H142 . 1.004(13) no C15 . C16 . 1.445(15) yes C15 . C20 . 1.369(15) yes C16 . C17 . 1.321(18) yes C16 . H161 . 1.013(11) no C17 . C18 . 1.385(18) yes C17 . H171 . 1.013(13) no C18 . C19 . 1.359(17) yes C18 . H181 . 1.00(1) no C19 . C20 . 1.409(16) yes C19 . H191 . 1.012(12) no C20 . H201 . 1.008(11) no C21 . H211 . 0.997(12) no C21 . H212 . 1.014(13) no C21 . H213 . 1.003(11) no O22 . H9 . 0.666(9) 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 C3 . O2 . C21 . 114.2(8) yes O2 . C3 . C4 . 104.3(8) yes O2 . C3 . C15 . 110.4(8) yes C4 . C3 . C15 . 112.6(8) yes O2 . C3 . H31 . 113.6(8) no C4 . C3 . H31 . 111.0(9) no C15 . C3 . H31 . 105.2(9) no C3 . C4 . N5 . 106.6(7) yes C3 . C4 . C13 . 110.3(8) yes N5 . C4 . C13 . 111.4(8) yes C3 . C4 . H41 . 111.9(9) no N5 . C4 . H41 . 110.1(9) no C13 . C4 . H41 . 106.7(9) no C4 . N5 . C6 . 116.4(8) yes C4 . N5 . H51 . 108.3(7) no C6 . N5 . H51 . 107.3(7) no C4 . N5 . H52 . 107.4(7) no C6 . N5 . H52 . 107.5(8) no H51 . N5 . H52 . 109.9(8) no N5 . C6 . C7 . 114.4(8) yes N5 . C6 . H61 . 108.4(9) no C7 . C6 . H61 . 108.7(9) no N5 . C6 . H62 . 108.4(8) no C7 . C6 . H62 . 108.6(9) no H61 . C6 . H62 . 108.3(10) no C6 . C7 . C8 . 120.4(9) yes C6 . C7 . C12 . 119.5(9) yes C8 . C7 . C12 . 119.9(9) yes C7 . C8 . C9 . 120.0(10) yes C7 . C8 . H81 . 119.5(10) no C9 . C8 . H81 . 120.5(10) no C8 . C9 . C10 . 119.1(10) yes C8 . C9 . H91 . 120.4(11) no C10 . C9 . H91 . 120.5(10) no C9 . C10 . C11 . 120.9(9) yes C9 . C10 . H101 . 119.7(11) no C11 . C10 . H101 . 119.5(10) no C10 . C11 . C12 . 118.9(9) yes C10 . C11 . H111 . 120.3(10) no C12 . C11 . H111 . 120.8(11) no C7 . C12 . C11 . 121.2(9) yes C7 . C12 . H121 . 119.1(10) no C11 . C12 . H121 . 119.6(10) no C4 . C13 . C14 . 123.7(12) yes C4 . C13 . H131 . 118.3(10) no C14 . C13 . H131 . 118.0(11) no C13 . C14 . H141 . 119.9(13) no C13 . C14 . H142 . 122.0(15) no H141 . C14 . H142 . 118.0(12) no C3 . C15 . C16 . 120.9(9) yes C3 . C15 . C20 . 122.7(9) yes C16 . C15 . C20 . 116.4(9) yes C15 . C16 . C17 . 122.2(11) yes C15 . C16 . H161 . 118.6(10) no C17 . C16 . H161 . 119.2(11) no C16 . C17 . C18 . 120.4(12) yes C16 . C17 . H171 . 119.4(14) no C18 . C17 . H171 . 120.1(13) no C17 . C18 . C19 . 120.0(10) yes C17 . C18 . H181 . 120.4(12) no C19 . C18 . H181 . 119.6(12) no C18 . C19 . C20 . 120.2(11) yes C18 . C19 . H191 . 120.0(10) no C20 . C19 . H191 . 119.8(11) no C15 . C20 . C19 . 120.7(10) yes C15 . C20 . H201 . 119.2(11) no C19 . C20 . H201 . 120.1(12) no O2 . C21 . H211 . 110.6(10) no O2 . C21 . H212 . 109.6(10) no H211 . C21 . H212 . 108.6(10) no O2 . C21 . H213 . 110.2(9) no H211 . C21 . H213 . 109.5(11) no H212 . C21 . H213 . 108.1(11) no