# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2005

data_global
_journal_name_full               Org.Biomol.Chem.

_journal_coden_Cambridge         0177

_publ_contact_author_name        'Blanchard Nicolas'
_publ_contact_author_address     
;
Synthese Substances Naturelles
ICMMO
batiment 410, universite d'ORSAY
ORSAY
91400
FRANCE
;

_publ_contact_author_email       NBLANCHARD@ICMO.U-PSUD.FR

_publ_section_title              
;
Intermolecular nitroso Diels-Alder cycloaddition of
alpha-acetoxynitroso derivatives in aqueous medium
;
loop_
_publ_author_name
'Nicolas Blanchard'
'Geraldine Calvet'
'Regis Guillot'

data_azo
_database_code_depnum_ccdc_archive 'CCDC 274918'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            
;
acetic acid 5-(5-acetoxy-2,2-dimethyl-(1,3)dioxan-5-yl-ONN-
azoxy)-2,2-dimethyl-(1,3)dioxan-5-yl ester
;
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C16 H26 N2 O9'
_chemical_formula_weight         390.39

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   'P b c a'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'-x-1/2, y-1/2, z'
'x, -y-1/2, z-1/2'

_cell_length_a                   10.6750(4)
_cell_length_b                   10.8521(5)
_cell_length_c                   33.5940(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3891.7(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       plate
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.260
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.060
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1664
_exptl_absorpt_coefficient_mu    0.109
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.962
_exptl_absorpt_correction_T_max  0.985
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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 ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        none
_diffrn_reflns_number            7851
_diffrn_reflns_av_R_equivalents  0.0230
_diffrn_reflns_av_sigmaI/netI    0.0367
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_theta_min         1.21
_diffrn_reflns_theta_max         27.48
_reflns_number_total             4347
_reflns_number_gt                2829
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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^)+(0.0681P)^2^+0.5549P] 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         4347
_refine_ls_number_parameters     348
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0788
_refine_ls_R_factor_gt           0.0452
_refine_ls_wR_factor_ref         0.1383
_refine_ls_wR_factor_gt          0.1168
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_restrained_S_all      1.069
_refine_ls_shift/su_max          0.149
_refine_ls_shift/su_mean         0.019

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
O4A O 0.38008(11) -0.06116(12) 0.21269(4) 0.0500(3) Uani 1 1 d . . .
O2B O 0.65332(11) 0.32917(12) 0.12462(4) 0.0461(3) Uani 1 1 d . . .
O5B O 0.86640(11) 0.24554(12) 0.07706(4) 0.0487(3) Uani 1 1 d . . .
O5A O 0.53478(11) -0.13762(12) 0.17037(4) 0.0497(3) Uani 1 1 d . . .
O3B O 0.67811(13) 0.23148(12) 0.18328(4) 0.0538(4) Uani 1 1 d . . .
O2A O 0.27458(11) 0.04202(13) 0.13761(4) 0.0504(3) Uani 1 1 d . . .
N1A N 0.47262(13) 0.13583(15) 0.12851(4) 0.0483(4) Uani 1 1 d . . .
O4B O 0.69962(12) 0.32600(12) 0.04104(4) 0.0542(4) Uani 1 1 d . . .
N1B N 0.58237(13) 0.11120(14) 0.11866(4) 0.0467(4) Uani 1 1 d . . .
O3A O 0.32293(15) 0.00712(18) 0.07367(4) 0.0780(5) Uani 1 1 d . . .
O1A O 0.41631(12) 0.23755(13) 0.12772(5) 0.0668(4) Uani 1 1 d . . .
C1A C 0.40252(16) 0.02855(17) 0.14826(5) 0.0437(4) Uani 1 1 d . . .
C4A C 0.4115(2) 0.05017(19) 0.19309(6) 0.0494(5) Uani 1 1 d . . .
C1B C 0.65623(16) 0.21527(16) 0.10218(5) 0.0432(4) Uani 1 1 d . . .
C2B C 0.66571(16) 0.32506(18) 0.16469(5) 0.0446(4) Uani 1 1 d . . .
C3B C 0.6611(2) 0.4518(2) 0.18158(7) 0.0573(5) Uani 1 1 d . . .
C5A C 0.45326(18) -0.10008(19) 0.13938(6) 0.0463(4) Uani 1 1 d . . .
C5B C 0.78964(17) 0.16544(19) 0.09947(6) 0.0476(5) Uani 1 1 d . . .
C6B C 0.82253(17) 0.27356(18) 0.03814(5) 0.0486(5) Uani 1 1 d . . .
C2A C 0.2461(2) 0.0300(2) 0.09819(7) 0.0572(5) Uani 1 1 d . . .
C4B C 0.61162(18) 0.2484(2) 0.06064(6) 0.0504(5) Uani 1 1 d . . .
C6A C 0.47356(17) -0.15465(18) 0.20793(6) 0.0504(5) Uani 1 1 d . . .
C8B C 0.8281(3) 0.1635(3) 0.01094(9) 0.0702(7) Uani 1 1 d . . .
C7B C 0.9062(2) 0.3774(2) 0.02432(8) 0.0644(6) Uani 1 1 d . . .
C7A C 0.4053(3) -0.2758(3) 0.21004(10) 0.0797(8) Uani 1 1 d . . .
C8A C 0.5748(2) -0.1415(3) 0.23931(8) 0.0733(7) Uani 1 1 d . . .
C3A C 0.1091(3) 0.0473(4) 0.09165(12) 0.0853(9) Uani 1 1 d . . .
H4B2 H 0.5413(18) 0.2978(18) 0.0611(6) 0.048(5) Uiso 1 1 d . . .
H4B1 H 0.606(2) 0.171(2) 0.0423(7) 0.077(7) Uiso 1 1 d . . .
H5B1 H 0.8267(18) 0.1629(18) 0.1253(7) 0.051(5) Uiso 1 1 d . . .
H5B2 H 0.7857(17) 0.0798(19) 0.0865(6) 0.050(5) Uiso 1 1 d . . .
H7B2 H 0.873(2) 0.398(2) -0.0017(8) 0.078(7) Uiso 1 1 d . . .
H8B1 H 0.916(2) 0.133(2) 0.0079(7) 0.075(7) Uiso 1 1 d . . .
H7B1 H 1.000(3) 0.349(2) 0.0225(7) 0.095(8) Uiso 1 1 d . . .
H7B3 H 0.898(2) 0.447(3) 0.0446(8) 0.091(8) Uiso 1 1 d . . .
H3B3 H 0.584(2) 0.493(2) 0.1697(6) 0.071(7) Uiso 1 1 d . . .
H3B1 H 0.741(3) 0.501(2) 0.1714(7) 0.088(8) Uiso 1 1 d . . .
H8B2 H 0.782(2) 0.097(3) 0.0190(8) 0.088(9) Uiso 1 1 d . . .
H8B3 H 0.795(2) 0.185(2) -0.0133(9) 0.079(8) Uiso 1 1 d . . .
H3B2 H 0.661(2) 0.454(2) 0.2092(8) 0.073(7) Uiso 1 1 d . . .
H4A2 H 0.4949(19) 0.0772(17) 0.2002(5) 0.050(5) Uiso 1 1 d . . .
H4A1 H 0.352(2) 0.117(2) 0.2009(6) 0.059(6) Uiso 1 1 d . . .
H8A3 H 0.641(3) -0.201(3) 0.2321(8) 0.104(9) Uiso 1 1 d . . .
H7A1 H 0.363(2) -0.285(2) 0.2360(8) 0.078(7) Uiso 1 1 d . . .
H8A2 H 0.539(2) -0.159(2) 0.2645(8) 0.081(8) Uiso 1 1 d . . .
H7A2 H 0.462(3) -0.340(3) 0.2083(9) 0.111(11) Uiso 1 1 d . . .
H7A3 H 0.341(3) -0.279(3) 0.1866(9) 0.095(9) Uiso 1 1 d . . .
H8A1 H 0.617(3) -0.054(3) 0.2368(9) 0.108(10) Uiso 1 1 d . . .
H5A1 H 0.3842(18) -0.1544(18) 0.1361(5) 0.047(5) Uiso 1 1 d . . .
H5A2 H 0.5007(19) -0.1013(16) 0.1154(6) 0.050(5) Uiso 1 1 d . . .
H3A3 H 0.084(4) 0.124(4) 0.0975(12) 0.153(16) Uiso 1 1 d . . .
H3A2 H 0.103(3) 0.044(3) 0.0616(14) 0.149(14) Uiso 1 1 d . . .
H3A1 H 0.062(4) -0.008(5) 0.0999(13) 0.18(2) Uiso 1 1 d . . .

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
O4A 0.0467(7) 0.0598(8) 0.0435(8) 0.0018(6) 0.0117(6) 0.0032(6)
O2B 0.0548(7) 0.0486(7) 0.0349(7) 0.0029(5) 0.0006(6) -0.0013(6)
O5B 0.0493(7) 0.0548(7) 0.0420(8) 0.0063(6) 0.0004(6) -0.0046(6)
O5A 0.0442(6) 0.0641(8) 0.0408(7) 0.0048(6) 0.0094(5) 0.0084(6)
O3B 0.0663(8) 0.0542(8) 0.0407(7) 0.0063(6) -0.0047(6) -0.0075(7)
O2A 0.0394(7) 0.0616(8) 0.0502(8) -0.0021(6) -0.0001(6) 0.0004(6)
N1A 0.0444(8) 0.0555(10) 0.0449(9) -0.0010(7) -0.0005(7) 0.0057(7)
O4B 0.0584(8) 0.0615(8) 0.0427(8) 0.0087(6) 0.0012(6) 0.0015(6)
N1B 0.0451(8) 0.0528(9) 0.0424(9) -0.0015(7) 0.0012(7) 0.0043(7)
O3A 0.0641(10) 0.1215(15) 0.0485(9) -0.0048(9) -0.0047(8) 0.0078(9)
O1A 0.0500(7) 0.0500(8) 0.1004(13) 0.0126(7) 0.0144(7) 0.0147(7)
C1A 0.0387(8) 0.0517(10) 0.0407(10) 0.0016(8) 0.0025(7) -0.0028(8)
C4A 0.0527(11) 0.0526(11) 0.0429(11) -0.0040(9) 0.0017(9) 0.0036(9)
C1B 0.0480(9) 0.0459(10) 0.0355(10) 0.0027(8) -0.0003(8) -0.0058(8)
C2B 0.0428(9) 0.0541(11) 0.0370(10) 0.0036(9) 0.0014(8) -0.0054(8)
C3B 0.0734(15) 0.0543(12) 0.0443(13) -0.0009(10) 0.0018(11) 0.0015(11)
C5A 0.0441(9) 0.0557(11) 0.0392(11) -0.0047(9) 0.0059(9) 0.0006(9)
C5B 0.0492(10) 0.0535(12) 0.0401(12) 0.0062(9) 0.0000(9) -0.0006(8)
C6B 0.0526(10) 0.0566(11) 0.0368(10) 0.0044(8) 0.0040(8) -0.0005(9)
C2A 0.0538(11) 0.0631(13) 0.0547(13) 0.0027(10) -0.0087(10) -0.0008(10)
C4B 0.0468(10) 0.0663(13) 0.0381(11) 0.0031(10) -0.0041(8) 0.0003(10)
C6A 0.0516(10) 0.0562(12) 0.0434(11) 0.0040(8) 0.0138(8) 0.0073(9)
C8B 0.0839(18) 0.0718(17) 0.0550(16) -0.0113(12) 0.0074(14) -0.0083(14)
C7B 0.0725(15) 0.0679(15) 0.0526(15) 0.0085(12) 0.0094(12) -0.0087(12)
C7A 0.103(2) 0.0616(16) 0.075(2) 0.0059(13) 0.0317(18) -0.0075(15)
C8A 0.0601(13) 0.113(2) 0.0471(14) 0.0106(14) 0.0038(11) 0.0208(15)
C3A 0.0550(14) 0.100(2) 0.101(3) -0.0049(19) -0.0242(14) 0.0047(15)

_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
O4A C4A 1.416(2) . ?
O4A C6A 1.432(2) . ?
O2B C2B 1.353(2) . ?
O2B C1B 1.448(2) . ?
O5B C5B 1.412(2) . ?
O5B C6B 1.422(2) . ?
O5A C5A 1.417(2) . ?
O5A C6A 1.433(2) . ?
O3B C2B 1.200(2) . ?
O2A C2A 1.365(2) . ?
O2A C1A 1.419(2) . ?
N1A N1B 1.247(2) . ?
N1A O1A 1.2572(19) . ?
N1A C1A 1.535(2) . ?
O4B C4B 1.423(2) . ?
O4B C6B 1.434(2) . ?
N1B C1B 1.485(2) . ?
O3A C2A 1.188(3) . ?
C1A C5A 1.527(3) . ?
C1A C4A 1.527(3) . ?
C1B C4B 1.518(3) . ?
C1B C5B 1.526(3) . ?
C2B C3B 1.488(3) . ?
C6B C8B 1.505(3) . ?
C6B C7B 1.511(3) . ?
C2A C3A 1.492(3) . ?
C6A C7A 1.505(3) . ?
C6A C8A 1.516(3) . ?

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
C4A O4A C6A 112.79(14) . . ?
C2B O2B C1B 119.18(13) . . ?
C5B O5B C6B 115.52(14) . . ?
C5A O5A C6A 113.83(14) . . ?
C2A O2A C1A 116.65(14) . . ?
N1B N1A O1A 129.20(16) . . ?
N1B N1A C1A 114.23(15) . . ?
O1A N1A C1A 116.24(13) . . ?
C4B O4B C6B 113.61(15) . . ?
N1A N1B C1B 115.79(15) . . ?
O2A C1A C5A 112.73(15) . . ?
O2A C1A C4A 107.05(14) . . ?
C5A C1A C4A 108.10(15) . . ?
O2A C1A N1A 106.39(14) . . ?
C5A C1A N1A 115.86(14) . . ?
C4A C1A N1A 106.20(15) . . ?
O4A C4A C1A 108.21(15) . . ?
O2B C1B N1B 116.35(14) . . ?
O2B C1B C4B 105.66(15) . . ?
N1B C1B C4B 110.87(14) . . ?
O2B C1B C5B 110.71(15) . . ?
N1B C1B C5B 104.37(14) . . ?
C4B C1B C5B 108.77(16) . . ?
O3B C2B O2B 123.82(17) . . ?
O3B C2B C3B 125.96(18) . . ?
O2B C2B C3B 110.22(17) . . ?
O5A C5A C1A 109.72(15) . . ?
O5B C5B C1B 110.81(15) . . ?
O5B C6B O4B 108.90(14) . . ?
O5B C6B C8B 112.05(19) . . ?
O4B C6B C8B 113.11(18) . . ?
O5B C6B C7B 104.32(17) . . ?
O4B C6B C7B 105.41(17) . . ?
C8B C6B C7B 112.47(19) . . ?
O3A C2A O2A 122.62(19) . . ?
O3A C2A C3A 126.9(2) . . ?
O2A C2A C3A 110.4(2) . . ?
O4B C4B C1B 111.00(15) . . ?
O4A C6A O5A 108.94(14) . . ?
O4A C6A C7A 106.02(19) . . ?
O5A C6A C7A 112.03(18) . . ?
O4A C6A C8A 110.64(17) . . ?
O5A C6A C8A 105.98(17) . . ?
C7A C6A C8A 113.2(2) . . ?

_diffrn_measured_fraction_theta_max 0.976
_diffrn_reflns_theta_full        27.48
_diffrn_measured_fraction_theta_full 0.976
_refine_diff_density_max         0.287
_refine_diff_density_min         -0.175
_refine_diff_density_rms         0.036