# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
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# 
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#  data retrieval see:
#                         www.ccdc.cam.ac.uk
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#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
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data_11

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
(2S,3S,3aR,4S)-ethyl 4-(benzyloxy)-2-((E)-carbamoyldiazenyl)-2-methylhexahydropyrrolo[1,2-b]isoxazole-3-carboxylate
;
_chemical_melting_point          359
_chemical_formula_sum            'C18 H24 N4 O5'
_chemical_formula_weight         376.17

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 21 21 21'

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'

_cell_length_a                   9.0217(7)
_cell_length_b                   13.8727(15)
_cell_length_c                   15.2216(13)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1905.1(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    728
_cell_measurement_theta_min      3.7060
_cell_measurement_theta_max      20.0160

_exptl_crystal_description       block
_exptl_crystal_colour            transparent
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.13
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             768
_exptl_absorpt_coefficient_mu    0.095
_exptl_absorpt_correction_T_min  0.63484
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(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 16.3990
_diffrn_standards_decay_%        'no decay'
_diffrn_reflns_number            6794
_diffrn_reflns_av_R_equivalents  0.0704
_diffrn_reflns_av_sigmaI/netI    0.1512
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.94
_diffrn_reflns_theta_max         26.26
_reflns_number_total             3148
_reflns_number_gt                1917
_reflns_threshold_expression     >2σ(I)

_computing_data_collection       'Bruker SMART V5.625'
_computing_cell_refinement       'Bruker SMART V5.625'
_computing_data_reduction        'Bruker SAINT V6.28A'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'SHELXTL  Rel. 6.12/V (Siemens, 1996)'
_computing_publication_material  'SHELX-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 > 2σ(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)+(0.0276P)²+0.0000P] 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     SHELXL
_refine_ls_extinction_coef       0.0053(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   1(2)
_refine_ls_number_reflns         3148
_refine_ls_number_parameters     245
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1360
_refine_ls_R_factor_gt           0.0730
_refine_ls_wR_factor_ref         0.1185
_refine_ls_wR_factor_gt          0.0936
_refine_ls_goodness_of_fit_ref   0.966
_refine_ls_restrained_S_all      0.966
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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 0.0988(3) 0.0891(2) 0.5867(2) 0.0273(9) Uani 1 1 d . . .
O2 O 0.2526(3) 0.3632(3) 0.4486(2) 0.0337(9) Uani 1 1 d . . .
O3 O 0.0226(3) 0.3741(3) 0.3928(2) 0.0286(9) Uani 1 1 d . . .
O4 O 0.1349(3) 0.4165(2) 0.6534(2) 0.0265(9) Uani 1 1 d . . .
O5 O -0.3612(3) 0.3119(3) 0.7384(2) 0.0382(10) Uani 1 1 d . . .
N1 N 0.2005(4) 0.3215(3) 0.6673(3) 0.0255(11) Uani 1 1 d . . .
N2 N -0.1251(4) 0.3879(3) 0.6553(2) 0.0278(11) Uani 1 1 d . . .
N3 N -0.2305(4) 0.3599(3) 0.6113(3) 0.0276(11) Uani 1 1 d . . .
N4 N -0.4820(3) 0.3607(3) 0.6150(2) 0.0277(11) Uani 1 1 d . . .
H4A H -0.5699 0.3506 0.6348 0.033 Uiso 1 1 calc R . .
H4B H -0.4698 0.3826 0.5627 0.033 Uiso 1 1 calc R . .
C1 C 0.1464(5) 0.2796(4) 0.7509(3) 0.0372(14) Uani 1 1 d . . .
H1A H 0.0478 0.3026 0.7650 0.045 Uiso 1 1 calc R . .
H1B H 0.2129 0.2943 0.7991 0.045 Uiso 1 1 calc R . .
C2 C 0.1457(5) 0.1720(4) 0.7304(3) 0.0340(14) Uani 1 1 d . . .
H2A H 0.2454 0.1459 0.7286 0.041 Uiso 1 1 calc R . .
H2B H 0.0874 0.1362 0.7729 0.041 Uiso 1 1 calc R . .
C3 C 0.0742(5) 0.1712(4) 0.6408(3) 0.0238(13) Uani 1 1 d . . .
H3 H -0.0327 0.1817 0.6471 0.029 Uiso 1 1 calc R . .
C4 C 0.1437(4) 0.2583(4) 0.5952(3) 0.0238(12) Uani 1 1 d . . .
H4 H 0.2277 0.2363 0.5596 0.029 Uiso 1 1 calc R . .
C5 C 0.0433(4) 0.3216(4) 0.5384(3) 0.0191(12) Uani 1 1 d . . .
H5 H -0.0480 0.2869 0.5236 0.023 Uiso 1 1 calc R . .
C7 C -0.0174(5) 0.5057(3) 0.5550(3) 0.0340(14) Uani 1 1 d . . .
H7A H -0.1037 0.5023 0.5183 0.051 Uiso 1 1 calc R . .
H7B H 0.0673 0.5221 0.5200 0.051 Uiso 1 1 calc R . .
H7C H -0.0318 0.5540 0.5994 0.051 Uiso 1 1 calc R . .
C6 C 0.0083(4) 0.4075(4) 0.5990(3) 0.0229(12) Uani 1 1 d . . .
C8 C 0.1197(5) 0.3543(4) 0.4563(3) 0.0243(12) Uani 1 1 d . . .
C10 C 0.0436(5) 0.0011(4) 0.6250(4) 0.0364(15) Uani 1 1 d . . .
H10A H -0.0545 0.0117 0.6492 0.044 Uiso 1 1 calc R . .
H10B H 0.1085 -0.0196 0.6722 0.044 Uiso 1 1 calc R . .
C11 C 0.0372(5) -0.0748(4) 0.5554(3) 0.0268(13) Uani 1 1 d . . .
C12 C 0.1385(6) -0.1487(4) 0.5506(4) 0.0415(15) Uani 1 1 d . . .
H12 H 0.2125 -0.1536 0.5929 0.050 Uiso 1 1 calc R . .
C13 C 0.1317(7) -0.2158(4) 0.4836(4) 0.0524(18) Uani 1 1 d . . .
H13 H 0.2005 -0.2657 0.4815 0.063 Uiso 1 1 calc R . .
C14 C 0.0236(6) -0.2094(4) 0.4199(4) 0.0450(16) Uani 1 1 d . . .
H14 H 0.0193 -0.2547 0.3749 0.054 Uiso 1 1 calc R . .
C15 C -0.0770(5) -0.1361(4) 0.4233(4) 0.0375(15) Uani 1 1 d . . .
H15 H -0.1501 -0.1313 0.3805 0.045 Uiso 1 1 calc R . .
C16 C -0.0706(5) -0.0690(4) 0.4900(4) 0.0346(15) Uani 1 1 d . . .
H16 H -0.1393 -0.0191 0.4915 0.042 Uiso 1 1 calc R . .
C17 C -0.3656(5) 0.3423(4) 0.6650(3) 0.0261(13) Uani 1 1 d . . .
C18 C 0.0994(6) 0.5204(4) 0.3174(4) 0.0525(18) Uani 1 1 d . . .
H18A H 0.1392 0.5448 0.2633 0.079 Uiso 1 1 calc R . .
H18B H 0.1654 0.5360 0.3648 0.079 Uiso 1 1 calc R . .
H18C H 0.0043 0.5492 0.3281 0.079 Uiso 1 1 calc R . .
C09 C 0.0825(5) 0.4131(4) 0.3111(3) 0.0402(16) Uani 1 1 d . . .
H09A H 0.0167 0.3974 0.2628 0.048 Uiso 1 1 calc R . .
H09B H 0.1783 0.3841 0.2993 0.048 Uiso 1 1 calc R . .


_geom_special_details            
;
 All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell s.u.'s are taken
 into account individually in the estimation of s.u.'s in distances, angles
 and torsion angles; correlations between s.u.'s in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell s.u.'s is used for estimating s.u.'s 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 C3 1.422(5) . ?
O1 C10 1.442(5) . ?
O2 C8 1.210(5) . ?
O3 C8 1.334(5) . ?
O3 C09 1.460(5) . ?
O4 C6 1.417(5) . ?
O4 N1 1.460(5) . ?
O5 C17 1.195(5) . ?
N1 C1 1.481(6) . ?
N1 C4 1.496(5) . ?
N2 N3 1.226(4) . ?
N2 C6 1.502(5) . ?
N3 C17 1.488(6) . ?
N4 C17 1.321(5) . ?
C1 C2 1.525(6) . ?
C2 C3 1.510(6) . ?
C3 C4 1.528(6) . ?
C4 C5 1.531(6) . ?
C5 C8 1.497(6) . ?
C5 C6 1.540(6) . ?
C7 C6 1.536(6) . ?
C10 C11 1.495(7) . ?
C11 C12 1.376(6) . ?
C11 C16 1.393(6) . ?
C12 C13 1.381(7) . ?
C13 C14 1.378(7) . ?
C14 C15 1.364(7) . ?
C15 C16 1.379(7) . ?
C18 C09 1.499(6) . ?

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
C3 O1 C10 113.0(3) . . ?
C8 O3 C09 116.7(3) . . ?
C6 O4 N1 109.4(3) . . ?
O4 N1 C1 110.2(4) . . ?
O4 N1 C4 106.5(3) . . ?
C1 N1 C4 106.7(3) . . ?
N3 N2 C6 111.5(3) . . ?
N2 N3 C17 112.7(4) . . ?
N1 C1 C2 102.2(4) . . ?
C3 C2 C1 101.2(4) . . ?
O1 C3 C2 117.5(4) . . ?
O1 C3 C4 107.8(3) . . ?
C2 C3 C4 103.2(4) . . ?
N1 C4 C3 105.7(4) . . ?
N1 C4 C5 106.3(4) . . ?
C3 C4 C5 117.9(3) . . ?
C8 C5 C4 111.9(3) . . ?
C8 C5 C6 111.1(4) . . ?
C4 C5 C6 103.1(3) . . ?
O4 C6 N2 109.2(4) . . ?
O4 C6 C7 107.3(4) . . ?
N2 C6 C7 106.8(4) . . ?
O4 C6 C5 104.7(4) . . ?
N2 C6 C5 111.5(4) . . ?
C7 C6 C5 117.1(4) . . ?
O2 C8 O3 124.0(4) . . ?
O2 C8 C5 124.6(4) . . ?
O3 C8 C5 111.4(4) . . ?
O1 C10 C11 108.9(4) . . ?
C12 C11 C16 118.0(5) . . ?
C12 C11 C10 122.4(5) . . ?
C16 C11 C10 119.5(5) . . ?
C11 C12 C13 120.8(5) . . ?
C14 C13 C12 120.5(5) . . ?
C15 C14 C13 119.5(6) . . ?
C14 C15 C16 120.2(5) . . ?
C15 C16 C11 121.1(5) . . ?
O5 C17 N4 129.2(5) . . ?
O5 C17 N3 123.0(4) . . ?
N4 C17 N3 107.7(4) . . ?
O3 C09 C18 110.6(5) . . ?

_diffrn_measured_fraction_theta_max 0.980
_diffrn_reflns_theta_full        26.26
_diffrn_measured_fraction_theta_full 0.980
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.215
_refine_diff_density_rms         0.055
_database_code_depnum_ccdc_archive 'CCDC 1002299'
