# 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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#  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_rem
_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
(S,S)-(-)-4,5-Dihydroxy-3-[(phenylhydrazyl)methyl]cyclopent-2-enone acetonide 
;
_chemical_name_common            ?
_chemical_formula_moiety         'C15 H16 N2 O3'
_chemical_formula_sum            'C15 H16 N2 O3'
_chemical_formula_weight         272.30

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 '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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'

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                   5.61530(10)
_cell_length_b                   14.7482(3)
_cell_length_c                   16.9257(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1401.71(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       'rectangular cuboid'
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             576
_exptl_crystal_F_000'            577.82
_exptl_absorpt_coefficient_mu    0.747
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_correction_T_min  0.814
_exptl_absorpt_correction_T_max  0.874
_chemical_absolute_configuration ad
_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54180
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  mirrors
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            5297
_diffrn_reflns_av_R_equivalents  0.0610
_diffrn_reflns_av_sigmaI/netI    0.0385
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.98
_diffrn_reflns_theta_max         77.75
_reflns_number_total             2989
_reflns_number_gt                2432
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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 w=1/[\s^2^(Fo^2^)+(0.1239P)^2^+0.0838P] 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     SHELXL
_refine_ls_extinction_coef       0.0055(14)
_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   -0.3(3)
_refine_ls_number_reflns         2722
_refine_ls_number_parameters     184
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0615
_refine_ls_R_factor_gt           0.0566
_refine_ls_wR_factor_ref         0.1745
_refine_ls_wR_factor_gt          0.1588
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_restrained_S_all      1.130
_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_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.2432(4) 0.77016(13) 0.15548(12) 0.0340(4) Uani 1 d . . .
O2 O 0.5333(3) 0.83400(13) 0.28935(12) 0.0334(5) Uani 1 d . . .
O3 O 0.7289(3) 0.72007(12) 0.34945(11) 0.0296(4) Uani 1 d . . .
N1 N 0.9015(4) 0.53138(15) 0.31820(13) 0.0283(5) Uani 1 d . . .
N2 N 0.9628(4) 0.45492(14) 0.35416(15) 0.0309(5) Uani 1 d . . .
H2N H 0.8861 0.4056 0.3447 0.037 Uiso 1 calc R . .
C1 C 0.4096(5) 0.73061(17) 0.18735(14) 0.0276(5) Uani 1 d . . .
C2 C 0.4425(5) 0.63375(18) 0.19725(18) 0.0323(6) Uani 1 d . . .
H21 H 0.3441 0.5896 0.1755 0.039 Uiso 1 calc R . .
C3 C 0.6373(5) 0.61624(17) 0.24272(16) 0.0295(5) Uani 1 d . . .
C4 C 0.7614(4) 0.70303(17) 0.26696(15) 0.0270(5) Uani 1 d . . .
H41 H 0.9297 0.7037 0.2516 0.032 Uiso 1 calc R . .
C5 C 0.6188(4) 0.77834(17) 0.22684(15) 0.0283(5) Uani 1 d . . .
H51 H 0.7152 0.8126 0.1889 0.034 Uiso 1 calc R . .
C6 C 0.7170(5) 0.53045(18) 0.27171(16) 0.0304(5) Uani 1 d . . .
H61 H 0.6408 0.4767 0.2581 0.036 Uiso 1 calc R . .
C7 C 0.6801(4) 0.81423(17) 0.35564(16) 0.0292(5) Uani 1 d . . .
C8 C 0.5366(6) 0.8297(2) 0.42980(19) 0.0430(7) Uani 1 d . . .
H81 H 0.3986 0.7912 0.4292 0.052 Uiso 1 calc R . .
H82 H 0.4875 0.8919 0.4322 0.052 Uiso 1 calc R . .
H83 H 0.6324 0.8156 0.4752 0.052 Uiso 1 calc R . .
C9 C 0.9089(6) 0.8693(2) 0.3529(2) 0.0410(7) Uani 1 d . . .
H91 H 0.8712 0.9327 0.3545 0.049 Uiso 1 calc R . .
H92 H 0.9934 0.8559 0.3050 0.049 Uiso 1 calc R . .
H93 H 1.0066 0.8540 0.3975 0.049 Uiso 1 calc R . .
C10 C 1.1526(4) 0.45504(17) 0.40743(16) 0.0277(5) Uani 1 d . . .
C11 C 1.1841(5) 0.38086(19) 0.45758(18) 0.0340(6) Uani 1 d . . .
H111 H 1.0749 0.3335 0.4570 0.041 Uiso 1 calc R . .
C12 C 1.3780(6) 0.3776(2) 0.50830(18) 0.0382(6) Uani 1 d . . .
H121 H 1.3987 0.3280 0.5415 0.046 Uiso 1 calc R . .
C13 C 1.5413(5) 0.4483(2) 0.50960(18) 0.0375(6) Uani 1 d . . .
H131 H 1.6722 0.4460 0.5432 0.045 Uiso 1 calc R . .
C14 C 1.5079(5) 0.5222(2) 0.46052(18) 0.0359(6) Uani 1 d . . .
H141 H 1.6163 0.5698 0.4618 0.043 Uiso 1 calc R . .
C15 C 1.3165(5) 0.52631(18) 0.40969(15) 0.0297(5) Uani 1 d . . .
H151 H 1.2965 0.5764 0.3770 0.036 Uiso 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 0.0379(9) 0.0271(9) 0.0370(9) 0.0003(8) -0.0065(8) 0.0010(8)
O2 0.0372(10) 0.0264(9) 0.0365(10) -0.0078(8) -0.0084(8) 0.0085(8)
O3 0.0358(9) 0.0204(8) 0.0325(8) 0.0008(7) -0.0028(7) 0.0037(7)
N1 0.0330(10) 0.0196(9) 0.0322(10) 0.0005(8) 0.0050(9) 0.0027(8)
N2 0.0344(10) 0.0160(9) 0.0422(12) 0.0018(9) -0.0020(9) 0.0004(8)
C1 0.0309(12) 0.0225(11) 0.0295(11) 0.0019(10) 0.0007(9) 0.0003(10)
C2 0.0343(12) 0.0231(12) 0.0395(13) -0.0013(11) -0.0038(11) -0.0033(10)
C3 0.0330(13) 0.0225(11) 0.0330(12) 0.0019(10) 0.0050(10) -0.0004(10)
C4 0.0259(11) 0.0211(12) 0.0340(12) 0.0033(9) 0.0021(9) -0.0014(9)
C5 0.0308(12) 0.0230(11) 0.0310(11) 0.0013(10) -0.0024(9) -0.0039(10)
C6 0.0346(12) 0.0188(11) 0.0377(12) -0.0037(10) 0.0004(10) 0.0003(10)
C7 0.0324(12) 0.0216(11) 0.0337(12) -0.0023(10) -0.0049(10) 0.0046(10)
C8 0.0396(14) 0.0480(18) 0.0413(15) -0.0093(14) -0.0061(11) 0.0078(14)
C9 0.0407(14) 0.0267(12) 0.0554(17) -0.0032(13) -0.0095(14) -0.0037(12)
C10 0.0320(12) 0.0197(11) 0.0315(11) -0.0007(10) 0.0062(10) 0.0056(9)
C11 0.0420(14) 0.0228(11) 0.0373(13) 0.0007(11) 0.0055(12) 0.0050(11)
C12 0.0505(17) 0.0305(13) 0.0336(12) 0.0040(11) 0.0047(12) 0.0135(13)
C13 0.0385(14) 0.0385(15) 0.0356(13) -0.0054(12) 0.0027(11) 0.0064(12)
C14 0.0389(13) 0.0347(14) 0.0340(12) -0.0022(11) 0.0026(11) -0.0009(11)
C15 0.0367(12) 0.0235(12) 0.0290(11) -0.0004(10) 0.0026(10) 0.0027(10)

_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 C1 1.227(3) . ?
O2 C7 1.422(3) . ?
O2 C5 1.423(3) . ?
O3 C7 1.419(3) . ?
O3 C4 1.430(3) . ?
N1 C6 1.301(4) . ?
N1 N2 1.327(3) . ?
N2 C10 1.396(3) . ?
C1 C2 1.450(4) . ?
C1 C5 1.524(4) . ?
C2 C3 1.362(4) . ?
C3 C6 1.429(4) . ?
C3 C4 1.514(4) . ?
C4 C5 1.528(3) . ?
C7 C8 1.509(4) . ?
C7 C9 1.520(4) . ?
C10 C11 1.396(4) . ?
C10 C15 1.398(4) . ?
C11 C12 1.387(4) . ?
C12 C13 1.389(5) . ?
C13 C14 1.382(4) . ?
C14 C15 1.378(4) . ?

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
C7 O2 C5 105.83(18) . . ?
C7 O3 C4 105.6(2) . . ?
C6 N1 N2 118.4(2) . . ?
N1 N2 C10 119.6(2) . . ?
O1 C1 C2 128.1(3) . . ?
O1 C1 C5 124.1(2) . . ?
C2 C1 C5 107.8(2) . . ?
C3 C2 C1 110.8(2) . . ?
C2 C3 C6 127.8(3) . . ?
C2 C3 C4 111.3(2) . . ?
C6 C3 C4 120.7(2) . . ?
O3 C4 C3 110.7(2) . . ?
O3 C4 C5 103.8(2) . . ?
C3 C4 C5 104.6(2) . . ?
O2 C5 C1 109.4(2) . . ?
O2 C5 C4 105.4(2) . . ?
C1 C5 C4 105.3(2) . . ?
N1 C6 C3 116.6(2) . . ?
O3 C7 O2 104.7(2) . . ?
O3 C7 C8 108.2(2) . . ?
O2 C7 C8 108.4(2) . . ?
O3 C7 C9 110.9(2) . . ?
O2 C7 C9 110.9(2) . . ?
C8 C7 C9 113.3(2) . . ?
N2 C10 C11 119.3(2) . . ?
N2 C10 C15 121.4(2) . . ?
C11 C10 C15 119.3(3) . . ?
C12 C11 C10 120.2(3) . . ?
C11 C12 C13 120.2(3) . . ?
C14 C13 C12 119.5(3) . . ?
C15 C14 C13 121.1(3) . . ?
C14 C15 C10 119.8(3) . . ?

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        77.75
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.063
_chemical_melting_point          460-462
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: ethanol'
_database_code_depnum_ccdc_archive 'CCDC 1011113'
