# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Ian Fleming' 'John E. Davies' 'Jonathan Goodman' _publ_contact_author_name 'Prof Ian Fleming' _publ_contact_author_address ; Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UNITED KINGDOM ; _publ_contact_author_email IF10000@CAM.AC.UK _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; A tricycloheptane product in cationic rearrangements ; data_if0301 _database_code_CSD 216824 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C18 H21 N O4' _chemical_formula_sum 'C18 H21 N O4' _chemical_formula_weight 315.36 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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.0666(4) _cell_length_b 7.0975(4) _cell_length_c 18.3293(13) _cell_angle_alpha 88.437(3) _cell_angle_beta 86.586(3) _cell_angle_gamma 62.907(3) _cell_volume 816.98(9) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 11494 _cell_measurement_theta_min 1.00 _cell_measurement_theta_max 24.71 _exptl_crystal_description ? _exptl_crystal_colour colourless _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.282 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 336 _exptl_absorpt_coefficient_mu 0.091 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.865 _exptl_absorpt_correction_T_max 0.999 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; Very small (40 year old!) crystal. Very poor data. Generally poor resolution, hence relatively high R values. ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_standards_number 0 _diffrn_reflns_number 7013 _diffrn_reflns_av_R_equivalents 0.0684 _diffrn_reflns_av_sigmaI/netI 0.0886 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.61 _diffrn_reflns_theta_max 24.76 _reflns_number_total 2762 _reflns_number_gt 1576 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius B.V. 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _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^)+(0.1442P)^2^+1.2150P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2762 _refine_ls_number_parameters 211 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1793 _refine_ls_R_factor_gt 0.1113 _refine_ls_wR_factor_ref 0.3102 _refine_ls_wR_factor_gt 0.2660 _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_restrained_S_all 1.037 _refine_ls_shift/su_max 0.026 _refine_ls_shift/su_mean 0.001 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 0.2000(6) 0.6023(5) 0.18277(18) 0.0517(10) Uani 1 1 d . . . O2 O 0.2072(5) 0.3467(5) 0.11160(18) 0.0497(10) Uani 1 1 d . . . O3 O 0.3115(6) 0.9174(6) -0.18646(19) 0.0640(11) Uani 1 1 d . . . O4 O 0.2948(6) 1.1593(5) -0.1146(2) 0.0574(10) Uani 1 1 d . . . N1 N 0.2941(6) 0.9905(6) -0.1256(2) 0.0444(11) Uani 1 1 d . . . C1 C 0.3664(9) 0.6231(10) 0.3411(3) 0.0709(18) Uani 1 1 d . . . C2 C 0.1791(9) 0.6074(9) 0.3123(3) 0.0581(15) Uani 1 1 d . . . C3 C -0.0194(10) 0.8203(12) 0.3308(3) 0.081(2) Uani 1 1 d . . . H3A H -0.0425 0.9290 0.2927 0.097 Uiso 1 1 calc R . . H3B H -0.1502 0.8032 0.3401 0.097 Uiso 1 1 calc R . . C4 C 0.0589(12) 0.8661(14) 0.4000(4) 0.104(3) Uani 1 1 d . . . H4 H -0.0359 1.0022 0.4256 0.124 Uiso 1 1 calc R . . C5 C 0.1198(16) 0.6566(13) 0.4451(4) 0.109(3) Uani 1 1 d . . . H5A H 0.2072 0.6461 0.4867 0.130 Uiso 1 1 calc R . . H5B H -0.0069 0.6397 0.4627 0.130 Uiso 1 1 calc R . . C6 C 0.2399(19) 0.5117(14) 0.3878(4) 0.127(4) Uani 1 1 d . . . H6 H 0.3065 0.3552 0.3958 0.152 Uiso 1 1 calc R . . C7 C 0.2825(11) 0.8261(10) 0.3799(4) 0.0769(19) Uani 1 1 d . . . C8 C 0.5805(12) 0.4909(16) 0.3146(6) 0.150(5) Uani 1 1 d . . . H8A H 0.6223 0.5658 0.2763 0.225 Uiso 1 1 calc R . . H8B H 0.5897 0.3603 0.2945 0.225 Uiso 1 1 calc R . . H8C H 0.6760 0.4561 0.3549 0.225 Uiso 1 1 calc R . . C9 C 0.275(2) 0.9940(16) 0.3183(5) 0.145(4) Uani 1 1 d . . . H9A H 0.1876 0.9932 0.2790 0.217 Uiso 1 1 calc R . . H9B H 0.4200 0.9557 0.2984 0.217 Uiso 1 1 calc R . . H9C H 0.2136 1.1357 0.3399 0.217 Uiso 1 1 calc R . . C10 C 0.4036(12) 0.8471(13) 0.4408(4) 0.096(2) Uani 1 1 d . . . H10A H 0.4463 0.7234 0.4729 0.143 Uiso 1 1 calc R . . H10B H 0.3132 0.9755 0.4688 0.143 Uiso 1 1 calc R . . H10C H 0.5308 0.8560 0.4204 0.143 Uiso 1 1 calc R . . C11 C 0.1856(10) 0.4856(9) 0.2469(3) 0.0590(15) Uani 1 1 d . . . H11A H 0.3104 0.3440 0.2471 0.071 Uiso 1 1 calc R . . H11B H 0.0552 0.4665 0.2469 0.071 Uiso 1 1 calc R . . C12 C 0.2105(7) 0.5147(7) 0.1180(3) 0.0396(12) Uani 1 1 d . . . C13 C 0.2288(6) 0.6444(6) 0.0556(2) 0.0358(11) Uani 1 1 d . . . C14 C 0.2240(7) 0.5795(7) -0.0154(3) 0.0377(12) Uani 1 1 d . . . H14 H 0.2063 0.4566 -0.0226 0.045 Uiso 1 1 calc R . . C15 C 0.2448(7) 0.6923(7) -0.0750(3) 0.0399(12) Uani 1 1 d . . . H15 H 0.2408 0.6497 -0.1233 0.048 Uiso 1 1 calc R . . C16 C 0.2719(6) 0.8704(6) -0.0622(2) 0.0359(11) Uani 1 1 d . . . C17 C 0.2757(7) 0.9394(7) 0.0065(3) 0.0367(11) Uani 1 1 d . . . H17 H 0.2925 1.0632 0.0130 0.044 Uiso 1 1 calc R . . C18 C 0.2549(6) 0.8267(7) 0.0655(3) 0.0388(12) Uani 1 1 d . . . H18 H 0.2582 0.8720 0.1135 0.047 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 O1 0.066(2) 0.052(2) 0.046(2) -0.0162(17) 0.0055(17) -0.0351(19) O2 0.058(2) 0.045(2) 0.052(2) -0.0086(16) -0.0031(16) -0.0271(17) O3 0.087(3) 0.060(2) 0.045(2) -0.0082(19) -0.0029(19) -0.032(2) O4 0.070(3) 0.048(2) 0.061(2) -0.0084(18) 0.0051(19) -0.0339(19) N1 0.035(2) 0.038(2) 0.054(3) -0.015(2) 0.0030(18) -0.0112(18) C1 0.062(4) 0.070(4) 0.074(4) -0.030(3) 0.001(3) -0.023(3) C2 0.063(4) 0.069(4) 0.046(3) -0.006(3) -0.005(3) -0.033(3) C3 0.059(4) 0.114(5) 0.064(4) -0.028(4) 0.010(3) -0.033(4) C4 0.091(6) 0.115(6) 0.091(6) -0.055(5) 0.018(4) -0.035(5) C5 0.165(9) 0.116(7) 0.063(5) -0.006(5) 0.004(5) -0.081(6) C6 0.260(12) 0.109(6) 0.056(4) -0.012(4) 0.016(6) -0.125(8) C7 0.075(4) 0.081(4) 0.080(5) -0.031(4) 0.007(3) -0.040(4) C8 0.065(5) 0.163(9) 0.182(10) -0.112(8) -0.005(5) -0.012(5) C9 0.250(13) 0.135(8) 0.104(7) 0.008(6) -0.007(7) -0.136(9) C10 0.103(5) 0.121(6) 0.078(5) -0.052(4) 0.011(4) -0.063(5) C11 0.083(4) 0.066(3) 0.043(3) -0.002(3) 0.002(3) -0.047(3) C12 0.028(2) 0.040(3) 0.050(3) -0.010(2) -0.002(2) -0.015(2) C13 0.023(2) 0.034(2) 0.047(3) -0.013(2) 0.003(2) -0.0098(19) C14 0.027(2) 0.033(2) 0.048(3) -0.016(2) -0.001(2) -0.0086(19) C15 0.030(3) 0.039(3) 0.043(3) -0.013(2) -0.002(2) -0.009(2) C16 0.028(2) 0.030(2) 0.045(3) -0.007(2) 0.001(2) -0.0089(19) C17 0.034(3) 0.031(2) 0.047(3) -0.010(2) 0.001(2) -0.015(2) C18 0.029(2) 0.037(2) 0.049(3) -0.020(2) -0.003(2) -0.013(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 O1 C12 1.337(5) . ? O1 C11 1.444(6) . ? O2 C12 1.212(5) . ? O3 N1 1.219(5) . ? O4 N1 1.223(5) . ? N1 C16 1.466(6) . ? C1 C8 1.431(9) . ? C1 C7 1.470(8) . ? C1 C2 1.505(8) . ? C1 C6 1.635(10) . ? C2 C11 1.483(7) . ? C2 C6 1.522(10) . ? C2 C3 1.552(8) . ? C3 C4 1.513(9) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 C7 1.497(10) . ? C4 C5 1.572(12) . ? C4 H4 1.0000 . ? C5 C6 1.427(10) . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C6 H6 1.0000 . ? C7 C10 1.496(9) . ? C7 C9 1.604(11) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 C13 1.486(7) . ? C13 C14 1.400(6) . ? C13 C18 1.406(6) . ? C14 C15 1.376(7) . ? C14 H14 0.9500 . ? C15 C16 1.390(6) . ? C15 H15 0.9500 . ? C16 C17 1.369(6) . ? C17 C18 1.369(7) . ? C17 H17 0.9500 . ? C18 H18 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 C12 O1 C11 116.6(4) . . ? O3 N1 O4 123.3(5) . . ? O3 N1 C16 118.6(4) . . ? O4 N1 C16 118.1(4) . . ? C8 C1 C7 128.3(6) . . ? C8 C1 C2 122.2(5) . . ? C7 C1 C2 107.1(5) . . ? C8 C1 C6 117.9(8) . . ? C7 C1 C6 100.1(5) . . ? C2 C1 C6 57.8(5) . . ? C11 C2 C1 125.5(5) . . ? C11 C2 C6 124.3(5) . . ? C1 C2 C6 65.4(5) . . ? C11 C2 C3 120.0(5) . . ? C1 C2 C3 106.5(5) . . ? C6 C2 C3 101.8(6) . . ? C4 C3 C2 96.9(5) . . ? C4 C3 H3A 112.4 . . ? C2 C3 H3A 112.4 . . ? C4 C3 H3B 112.4 . . ? C2 C3 H3B 112.4 . . ? H3A C3 H3B 109.9 . . ? C7 C4 C3 104.6(5) . . ? C7 C4 C5 96.2(7) . . ? C3 C4 C5 102.3(7) . . ? C7 C4 H4 116.9 . . ? C3 C4 H4 116.9 . . ? C5 C4 H4 116.9 . . ? C6 C5 C4 97.3(6) . . ? C6 C5 H5A 112.3 . . ? C4 C5 H5A 112.3 . . ? C6 C5 H5B 112.3 . . ? C4 C5 H5B 112.3 . . ? H5A C5 H5B 109.9 . . ? C5 C6 C2 112.5(8) . . ? C5 C6 C1 105.8(6) . . ? C2 C6 C1 56.8(4) . . ? C5 C6 H6 121.4 . . ? C2 C6 H6 121.4 . . ? C1 C6 H6 121.4 . . ? C1 C7 C10 119.0(6) . . ? C1 C7 C4 101.4(5) . . ? C10 C7 C4 115.7(6) . . ? C1 C7 C9 104.9(6) . . ? C10 C7 C9 106.8(6) . . ? C4 C7 C9 108.3(8) . . ? C1 C8 H8A 109.5 . . ? C1 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C1 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 H10A 109.5 . . ? C7 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? O1 C11 C2 108.1(4) . . ? O1 C11 H11A 110.1 . . ? C2 C11 H11A 110.1 . . ? O1 C11 H11B 110.1 . . ? C2 C11 H11B 110.1 . . ? H11A C11 H11B 108.4 . . ? O2 C12 O1 123.2(5) . . ? O2 C12 C13 124.2(4) . . ? O1 C12 C13 112.6(4) . . ? C14 C13 C18 119.2(5) . . ? C14 C13 C12 118.5(4) . . ? C18 C13 C12 122.3(4) . . ? C15 C14 C13 120.6(4) . . ? C15 C14 H14 119.7 . . ? C13 C14 H14 119.7 . . ? C14 C15 C16 117.9(4) . . ? C14 C15 H15 121.1 . . ? C16 C15 H15 121.1 . . ? C17 C16 C15 123.1(5) . . ? C17 C16 N1 119.0(4) . . ? C15 C16 N1 117.9(4) . . ? C18 C17 C16 118.8(4) . . ? C18 C17 H17 120.6 . . ? C16 C17 H17 120.6 . . ? C17 C18 C13 120.5(4) . . ? C17 C18 H18 119.8 . . ? C13 C18 H18 119.8 . . ? 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 C8 C1 C2 C11 -10.9(11) . . . . ? C7 C1 C2 C11 152.8(6) . . . . ? C6 C1 C2 C11 -115.8(7) . . . . ? C8 C1 C2 C6 105.0(9) . . . . ? C7 C1 C2 C6 -91.4(6) . . . . ? C8 C1 C2 C3 -159.3(8) . . . . ? C7 C1 C2 C3 4.3(7) . . . . ? C6 C1 C2 C3 95.7(6) . . . . ? C11 C2 C3 C4 178.8(6) . . . . ? C1 C2 C3 C4 -30.6(7) . . . . ? C6 C2 C3 C4 37.0(7) . . . . ? C2 C3 C4 C7 46.8(8) . . . . ? C2 C3 C4 C5 -53.0(7) . . . . ? C7 C4 C5 C6 -58.5(7) . . . . ? C3 C4 C5 C6 47.9(8) . . . . ? C4 C5 C6 C2 -23.2(9) . . . . ? C4 C5 C6 C1 36.8(9) . . . . ? C11 C2 C6 C5 -147.9(7) . . . . ? C1 C2 C6 C5 94.6(7) . . . . ? C3 C2 C6 C5 -8.3(9) . . . . ? C11 C2 C6 C1 117.5(6) . . . . ? C3 C2 C6 C1 -102.9(5) . . . . ? C8 C1 C6 C5 140.9(8) . . . . ? C7 C1 C6 C5 -2.9(9) . . . . ? C2 C1 C6 C5 -106.9(9) . . . . ? C8 C1 C6 C2 -112.2(7) . . . . ? C7 C1 C6 C2 103.9(5) . . . . ? C8 C1 C7 C10 -45.0(12) . . . . ? C2 C1 C7 C10 152.6(6) . . . . ? C6 C1 C7 C10 93.4(7) . . . . ? C8 C1 C7 C4 -173.1(9) . . . . ? C2 C1 C7 C4 24.5(7) . . . . ? C6 C1 C7 C4 -34.8(7) . . . . ? C8 C1 C7 C9 74.3(11) . . . . ? C2 C1 C7 C9 -88.1(7) . . . . ? C6 C1 C7 C9 -147.3(7) . . . . ? C3 C4 C7 C1 -46.1(8) . . . . ? C5 C4 C7 C1 58.3(6) . . . . ? C3 C4 C7 C10 -176.3(6) . . . . ? C5 C4 C7 C10 -71.8(7) . . . . ? C3 C4 C7 C9 63.9(8) . . . . ? C5 C4 C7 C9 168.4(5) . . . . ? C12 O1 C11 C2 179.1(4) . . . . ? C1 C2 C11 O1 -75.5(7) . . . . ? C6 C2 C11 O1 -157.9(7) . . . . ? C3 C2 C11 O1 69.2(7) . . . . ? C11 O1 C12 O2 0.4(7) . . . . ? C11 O1 C12 C13 -179.0(4) . . . . ? O2 C12 C13 C14 5.7(6) . . . . ? O1 C12 C13 C14 -175.0(4) . . . . ? O2 C12 C13 C18 -173.0(4) . . . . ? O1 C12 C13 C18 6.3(6) . . . . ? C18 C13 C14 C15 0.0(6) . . . . ? C12 C13 C14 C15 -178.7(4) . . . . ? C13 C14 C15 C16 0.4(6) . . . . ? C14 C15 C16 C17 -0.9(6) . . . . ? C14 C15 C16 N1 180.0(4) . . . . ? O3 N1 C16 C17 172.9(4) . . . . ? O4 N1 C16 C17 -6.9(6) . . . . ? O3 N1 C16 C15 -8.0(6) . . . . ? O4 N1 C16 C15 172.2(4) . . . . ? C15 C16 C17 C18 0.9(6) . . . . ? N1 C16 C17 C18 -180.0(4) . . . . ? C16 C17 C18 C13 -0.4(6) . . . . ? C14 C13 C18 C17 -0.1(6) . . . . ? C12 C13 C18 C17 178.6(4) . . . . ? _diffrn_measured_fraction_theta_max 0.982 _diffrn_reflns_theta_full 24.76 _diffrn_measured_fraction_theta_full 0.982 _refine_diff_density_max 0.804 _refine_diff_density_min -0.342 _refine_diff_density_rms 0.089