# 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 ω and φ 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 F² against ALL reflections.  The weighted R-factor wR and
goodness of fit S are based on F², conventional R-factors R are based
on F, with F set to zero for negative F². The threshold expression of
F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement.  R-factors based
on F² 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/[σ²(Fo²)+(0.1442P)²+1.2150P] where P=(Fo²+2Fc²)/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 . .


_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



