  
#==============================================================================
data_global
#==============================================================================

_publ_contact_author               'Darren J Dixon'
_publ_contact_author_email          darren.dixon@chem.ox.ac.uk

loop_
_publ_author_name
_publ_author_address
 'Jakubec, Pavol '
;    
Chemistry Research Laboratory,
University of Oxford,
Mansfield Road, 
Oxford OX1 3TA, UK.
;
'Cockfield, Dane M.'
;     
School of Chemistry, 
The University of Manchester,
Manchester 
M13 9PL, UK.
;
'Helliwell, Madeleine'
;     
School of Chemistry, 
The University of Manchester,
Manchester 
M13 9PL, UK.
;
'Raftery, James'
;    
School of Chemistry, 
The University of Manchester,
Manchester 
M13 9PL, UK.
;
'Dixon, Darren J.'
;    
Chemistry Research Laboratory,
University of Oxford,
Mansfield Road, 
Oxford OX1 3TA. UK.
;
_journal_name_full                 
 'Beilstein Journal of Organic Chemistry'
_journal_volume                    '?'
_journal_page_first                '?'
_journal_page_last                 '?'
_journal_year                      '2011'
_ccdc_journal_depnumber            '?'

_publ_section_title
;
Stereoselective, nitro-Mannich/lactamization cascades for the direct 
synthesis of heavily decorated 5-nitro piperidin-2-ones and related 
heterocycles.
;

_publ_section_abstract
;  
A versatile nitro-Mannich / lactamization cascade for the direct 
stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and 
related heterocycles has been developed. A highly enantioenriched substituted 
5-nitropiperidin-2-one was synthesized in four component one-pot reaction 
combining an enantioselective Michael addition with the diastereoselective
nitro-Mannich / lactamization cascade. Protodenitration and chemoselective
reductive manipulation of the heterocycles can be used to install contiguous
and fully substituted stereocentres in the synthesis of substituted piperidines. 
;
  
#------------------ TEXT ----------------------------------------------------# 
  
_publ_section_synopsis 
; 
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? 
; 
_publ_section_abstract 
; 
# Insert blank lines between paragraphs 
 ? 
; 
  
_publ_section_comment 
; 
# Insert blank lines between paragraphs 
 ? 
; 
  
_publ_section_exptl_prep 
; 
 ? 
; 
  
_publ_section_exptl_refinement 
; 
The structure was solved by direct methods. 
The non-hydrogen atoms were refined anisotropically. 
H atoms were included in calculated positions with 
C-H lengths of 0.95(CH), 0.99(CH₂) & 0.98(CH₃)Å; 
Uiso(H) values were fixed at 1.2Ueq(C) except for 
CH₃ where it was 1.5Ueq(C). 
; 
  
# Insert blank lines between references 
  
_publ_section_references 
; 
# 
# Put all your general crystallographic references here 
# Delete as required from the document CIF 
# 
  
 M. C. Burla, R. Caliandro, M. Camalli, B. Carrozzini, 
 G. L. Cascarano, L. De Caro,C. Giacovazzo, G. Polidori 
 and R. Spagna 
 SIR2004: an improved tool for crystal structure determination 
 and refinement 
 J. Appl. Cryst. (2005). 38, 381-388 
  
 Sheldrick, G.M. (1993) SHELXL93. Program for crystal structure 
   refinement. University of Göttingen, Germany. 
  
 Sheldrick, G.M. (1997) SHELXL97. Program for crystal structure 
   refinement. University of Göttingen, Germany. 
  
 Sheldrick, G.M. (1985). SHELXS86. In Crystallographic Computing 3, 
 edited by G. M. Sheldrick, C. Kruger & R. Goddard, pp. 175-189. 
 Oxford University Press. 
  
 Sheldrick, G.M. (1997) SHELXS97. Program for Crystal Structure solution. 
   University of Göttingen, Germany. 
  
  
 Wilson, A.J.C. (1992) Ed. International Tables for Crystallography, 
   Volume C, Kluwer Academic Publishers, Dordrecht, The Netherlands. 
; 
_publ_section_figure_captions 
; 
 Figure 1. View of (I) (50% probability displacement ellipsoids) 
; 
_publ_section_acknowledgements 
; 
 ? 
; 
_publ_section_table_legends 
; 
Table 1. Fractional atomic coordinates and equivalent 
         isotropic displacement parameters (Å²) 
  
Table 2. Selected geometric parameters (Å ,° ) 
; 
#------------------  SECTION 2. COMPOUND(S) DETAILS -------------------------# 
  
_audit_creation_method            SHELXL-97 
_chemical_name_systematic 
; 
 ? 
; 
_chemical_name_common             ? 
_chemical_melting_point           ? 
_chemical_formula_moiety          ? 
_chemical_formula_sum 
 'C23 H24 N2 O7' 
_chemical_formula_weight          440.44 
  
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            Monoclinic 
_symmetry_space_group_name_H-M    P2(1)/c 
  
loop_ 
 _symmetry_equiv_pos_as_xyz 
 'x, y, z' 
 '-x, y+1/2, -z+1/2' 
 '-x, -y, -z' 
 'x, -y-1/2, z-1/2' 
  
_cell_length_a                    12.1135(9) 
_cell_length_b                    8.1805(6) 
_cell_length_c                    22.5942(17) 
_cell_angle_alpha                 90.00 
_cell_angle_beta                  100.0410(10) 
_cell_angle_gamma                 90.00 
_cell_volume                      2204.7(3) 
_cell_formula_units_Z             4 
_cell_measurement_temperature     100(2) 
_cell_measurement_reflns_used     4331 
_cell_measurement_theta_min 2.654 
_cell_measurement_theta_max 28.173 
  
_exptl_crystal_description        block 
_exptl_crystal_colour             white 
_exptl_crystal_size_max           0.40 
_exptl_crystal_size_mid           0.35 
_exptl_crystal_size_min           0.30 
_exptl_crystal_density_diffrn     1.327 
_exptl_crystal_density_method     'not measured' 
_exptl_crystal_F_000              928 
_exptl_absorpt_coefficient_mu     0.099 
_exptl_absorpt_correction_type    none 
_exptl_absorpt_process_details    ? 
  
_exptl_special_details 
; 
 ? 
; 
  
_diffrn_ambient_temperature       100(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_%         ? 
_diffrn_reflns_number             18245 
_diffrn_reflns_av_R_equivalents   0.0570 
_diffrn_reflns_av_sigmaI/netI     0.0592 
_diffrn_reflns_limit_h_min        -16 
_diffrn_reflns_limit_h_max        15 
_diffrn_reflns_limit_k_min        -10 
_diffrn_reflns_limit_k_max        10 
_diffrn_reflns_limit_l_min        -29 
_diffrn_reflns_limit_l_max        29 
_diffrn_reflns_theta_min          1.71 
_diffrn_reflns_theta_max          28.26 
_reflns_number_total              5188 
_reflns_number_gt                 3618 
_reflns_threshold_expression      >2sigma(I) 
  
_computing_data_collection        'Bruker SMART' 
_computing_cell_refinement        'Bruker SMART' 
_computing_data_reduction         'Bruker SAINT' 
_computing_structure_solution     'SHELXS-97 (Sheldrick, 1990)' 
_computing_structure_refinement   'SHELXL-97 (Sheldrick, 1997)' 
_computing_molecular_graphics     'Bruker SHELXTL' 
_computing_publication_material   'Bruker SHELXTL' 
  
_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)+(0.1019P)²+0.2235P] where P=(Fo²+2Fc²)/3' 
_atom_sites_solution_primary      direct 
_atom_sites_solution_secondary    difmap 
_atom_sites_solution_hydrogens    geom 
_refine_ls_hydrogen_treatment constr 
_refine_ls_extinction_method      none 
_refine_ls_extinction_coef        ? 
_refine_ls_number_reflns          5188 
_refine_ls_number_parameters      292 
_refine_ls_number_restraints      0 
_refine_ls_R_factor_all           0.0894 
_refine_ls_R_factor_gt            0.0624 
_refine_ls_wR_factor_ref          0.1817 
_refine_ls_wR_factor_gt           0.1678 
_refine_ls_goodness_of_fit_ref    1.064 
_refine_ls_restrained_S_all       1.064 
_refine_ls_shift/su_max           0.001 
_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 
C1 C 0.62109(18) 0.6998(3) 0.00784(10) 0.0168(5) Uani 1 1 d . . . 
C2 C 0.74143(18) 0.7130(3) 0.04129(10) 0.0187(5) Uani 1 1 d . . . 
H2 H 0.7586 0.8324 0.0458 0.022 Uiso 1 1 calc R . . 
C3 C 0.75809(17) 0.6422(3) 0.10492(10) 0.0159(4) Uani 1 1 d . . . 
H3 H 0.7420 0.5225 0.1006 0.019 Uiso 1 1 calc R . . 
C4 C 0.67002(18) 0.7149(3) 0.13916(10) 0.0157(4) Uani 1 1 d . . . 
H4 H 0.6784 0.6598 0.1792 0.019 Uiso 1 1 calc R . . 
C5 C 0.55046(18) 0.6856(3) 0.10612(9) 0.0157(4) Uani 1 1 d . . . 
H5 H 0.5324 0.5687 0.1132 0.019 Uiso 1 1 calc R . . 
C6 C 0.46543(17) 0.7888(3) 0.13203(10) 0.0149(4) Uani 1 1 d . . . 
C7 C 0.46783(18) 0.7844(3) 0.19435(10) 0.0159(4) Uani 1 1 d . . . 
H7 H 0.5185 0.7131 0.2187 0.019 Uiso 1 1 calc R . . 
C8 C 0.39725(18) 0.8826(3) 0.22058(9) 0.0157(4) Uani 1 1 d . . . 
C9 C 0.32410(18) 0.9915(3) 0.18444(10) 0.0157(4) Uani 1 1 d . . . 
C10 C 0.31853(18) 0.9901(3) 0.12300(10) 0.0171(5) Uani 1 1 d . . . 
H10 H 0.2669 1.0599 0.0985 0.021 Uiso 1 1 calc R . . 
C11 C 0.38797(18) 0.8870(3) 0.09615(9) 0.0154(4) Uani 1 1 d . . . 
C12 C 0.37464(19) 0.8795(3) 0.02855(10) 0.0184(5) Uani 1 1 d . . . 
H12A H 0.4146 0.9726 0.0138 0.022 Uiso 1 1 calc R . . 
H12B H 0.2943 0.8879 0.0106 0.022 Uiso 1 1 calc R . . 
C13 C 0.42186(18) 0.7201(3) 0.00968(10) 0.0186(5) Uani 1 1 d . . . 
H13A H 0.3774 0.6269 0.0207 0.022 Uiso 1 1 calc R . . 
H13B H 0.4188 0.7187 -0.0344 0.022 Uiso 1 1 calc R . . 
C14 C 0.8165(2) 0.6454(3) 0.00007(11) 0.0263(6) Uani 1 1 d . . . 
C15 C 0.8683(3) 0.4051(4) -0.04566(14) 0.0430(8) Uani 1 1 d . . . 
H15A H 0.8117 0.3846 -0.0815 0.064 Uiso 1 1 calc R . . 
H15B H 0.9024 0.3012 -0.0304 0.064 Uiso 1 1 calc R . . 
H15C H 0.9264 0.4777 -0.0560 0.064 Uiso 1 1 calc R . . 
C16 C 0.87636(18) 0.6583(3) 0.14032(10) 0.0177(5) Uani 1 1 d . . . 
C17 C 0.94933(19) 0.7796(3) 0.12846(10) 0.0211(5) Uani 1 1 d . . . 
H17 H 0.9260 0.8558 0.0970 0.025 Uiso 1 1 calc R . . 
C18 C 1.0569(2) 0.7904(3) 0.16246(11) 0.0249(5) Uani 1 1 d . . . 
H18 H 1.1067 0.8731 0.1538 0.030 Uiso 1 1 calc R . . 
C19 C 1.0912(2) 0.6813(3) 0.20866(11) 0.0250(5) Uani 1 1 d . . . 
H19 H 1.1644 0.6889 0.2318 0.030 Uiso 1 1 calc R . . 
C20 C 1.0184(2) 0.5611(3) 0.22113(11) 0.0263(6) Uani 1 1 d . . . 
H20 H 1.0414 0.4864 0.2531 0.032 Uiso 1 1 calc R . . 
C21 C 0.9118(2) 0.5494(3) 0.18699(11) 0.0230(5) Uani 1 1 d . . . 
H21 H 0.8625 0.4659 0.1956 0.028 Uiso 1 1 calc R . . 
C22 C 0.4632(2) 0.7717(3) 0.31772(10) 0.0228(5) Uani 1 1 d . . . 
H22A H 0.4471 0.6607 0.3023 0.034 Uiso 1 1 calc R . . 
H22B H 0.4492 0.7781 0.3591 0.034 Uiso 1 1 calc R . . 
H22C H 0.5418 0.7982 0.3170 0.034 Uiso 1 1 calc R . . 
C23 C 0.1943(2) 1.2113(3) 0.17948(11) 0.0249(5) Uani 1 1 d . . . 
H23A H 0.2418 1.2829 0.1599 0.037 Uiso 1 1 calc R . . 
H23B H 0.1549 1.2766 0.2056 0.037 Uiso 1 1 calc R . . 
H23C H 0.1394 1.1566 0.1489 0.037 Uiso 1 1 calc R . . 
N1 N 0.53830(15) 0.7068(2) 0.04064(8) 0.0163(4) Uani 1 1 d . . . 
N2 N 0.69248(15) 0.8953(2) 0.14974(8) 0.0172(4) Uani 1 1 d . . . 
O1 O 0.60378(13) 0.6938(2) -0.04714(7) 0.0225(4) Uani 1 1 d . . . 
O2 O 0.81496(15) 0.4825(2) 0.00082(8) 0.0327(5) Uani 1 1 d . . . 
O3 O 0.86910(16) 0.7267(3) -0.02918(8) 0.0355(5) Uani 1 1 d . . . 
O4 O 0.66839(15) 0.9893(2) 0.10726(7) 0.0240(4) Uani 1 1 d . . . 
O5 O 0.73357(15) 0.9378(2) 0.20033(7) 0.0287(4) Uani 1 1 d . . . 
O6 O 0.39188(13) 0.8860(2) 0.28068(7) 0.0196(4) Uani 1 1 d . . . 
O7 O 0.26245(13) 1.0913(2) 0.21465(7) 0.0207(4) Uani 1 1 d . . . 
  
  
_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 
C1 O1 1.224(3) . ? 
C1 N1 1.348(3) . ? 
C1 C2 1.524(3) . ? 
C2 C14 1.515(3) . ? 
C2 C3 1.531(3) . ? 
C2 H2 1.0000 . ? 
C3 C16 1.520(3) . ? 
C3 C4 1.542(3) . ? 
C3 H3 1.0000 . ? 
C4 N2 1.512(3) . ? 
C4 C5 1.528(3) . ? 
C4 H4 1.0000 . ? 
C5 N1 1.471(3) . ? 
C5 C6 1.526(3) . ? 
C5 H5 1.0000 . ? 
C6 C11 1.385(3) . ? 
C6 C7 1.404(3) . ? 
C7 C8 1.380(3) . ? 
C7 H7 0.9500 . ? 
C8 O6 1.371(3) . ? 
C8 C9 1.412(3) . ? 
C9 O7 1.367(3) . ? 
C9 C10 1.378(3) . ? 
C10 C11 1.402(3) . ? 
C10 H10 0.9500 . ? 
C11 C12 1.509(3) . ? 
C12 C13 1.515(3) . ? 
C12 H12A 0.9900 . ? 
C12 H12B 0.9900 . ? 
C13 N1 1.465(3) . ? 
C13 H13A 0.9900 . ? 
C13 H13B 0.9900 . ? 
C14 O3 1.197(3) . ? 
C14 O2 1.333(3) . ? 
C15 O2 1.469(3) . ? 
C15 H15A 0.9800 . ? 
C15 H15B 0.9800 . ? 
C15 H15C 0.9800 . ? 
C16 C17 1.386(3) . ? 
C16 C21 1.390(3) . ? 
C17 C18 1.395(3) . ? 
C17 H17 0.9500 . ? 
C18 C19 1.381(4) . ? 
C18 H18 0.9500 . ? 
C19 C20 1.382(4) . ? 
C19 H19 0.9500 . ? 
C20 C21 1.387(3) . ? 
C20 H20 0.9500 . ? 
C21 H21 0.9500 . ? 
C22 O6 1.439(3) . ? 
C22 H22A 0.9800 . ? 
C22 H22B 0.9800 . ? 
C22 H22C 0.9800 . ? 
C23 O7 1.431(3) . ? 
C23 H23A 0.9800 . ? 
C23 H23B 0.9800 . ? 
C23 H23C 0.9800 . ? 
N2 O5 1.215(2) . ? 
N2 O4 1.225(2) . ? 
  
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 
O1 C1 N1 123.2(2) . . ? 
O1 C1 C2 119.1(2) . . ? 
N1 C1 C2 117.60(19) . . ? 
C14 C2 C1 107.10(18) . . ? 
C14 C2 C3 116.35(19) . . ? 
C1 C2 C3 113.39(19) . . ? 
C14 C2 H2 106.5 . . ? 
C1 C2 H2 106.5 . . ? 
C3 C2 H2 106.5 . . ? 
C16 C3 C2 114.78(18) . . ? 
C16 C3 C4 111.94(18) . . ? 
C2 C3 C4 109.60(17) . . ? 
C16 C3 H3 106.7 . . ? 
C2 C3 H3 106.7 . . ? 
C4 C3 H3 106.7 . . ? 
N2 C4 C5 111.07(17) . . ? 
N2 C4 C3 109.56(17) . . ? 
C5 C4 C3 111.96(17) . . ? 
N2 C4 H4 108.0 . . ? 
C5 C4 H4 108.0 . . ? 
C3 C4 H4 108.0 . . ? 
N1 C5 C6 111.38(17) . . ? 
N1 C5 C4 113.14(18) . . ? 
C6 C5 C4 111.80(17) . . ? 
N1 C5 H5 106.7 . . ? 
C6 C5 H5 106.7 . . ? 
C4 C5 H5 106.7 . . ? 
C11 C6 C7 119.7(2) . . ? 
C11 C6 C5 122.02(19) . . ? 
C7 C6 C5 118.25(19) . . ? 
C8 C7 C6 120.6(2) . . ? 
C8 C7 H7 119.7 . . ? 
C6 C7 H7 119.7 . . ? 
O6 C8 C7 125.27(19) . . ? 
O6 C8 C9 115.23(19) . . ? 
C7 C8 C9 119.5(2) . . ? 
O7 C9 C10 125.0(2) . . ? 
O7 C9 C8 115.51(18) . . ? 
C10 C9 C8 119.5(2) . . ? 
C9 C10 C11 120.9(2) . . ? 
C9 C10 H10 119.6 . . ? 
C11 C10 H10 119.6 . . ? 
C6 C11 C10 119.5(2) . . ? 
C6 C11 C12 120.7(2) . . ? 
C10 C11 C12 119.75(19) . . ? 
C11 C12 C13 109.93(18) . . ? 
C11 C12 H12A 109.7 . . ? 
C13 C12 H12A 109.7 . . ? 
C11 C12 H12B 109.7 . . ? 
C13 C12 H12B 109.7 . . ? 
H12A C12 H12B 108.2 . . ? 
N1 C13 C12 108.00(18) . . ? 
N1 C13 H13A 110.1 . . ? 
C12 C13 H13A 110.1 . . ? 
N1 C13 H13B 110.1 . . ? 
C12 C13 H13B 110.1 . . ? 
H13A C13 H13B 108.4 . . ? 
O3 C14 O2 125.0(3) . . ? 
O3 C14 C2 124.8(3) . . ? 
O2 C14 C2 110.3(2) . . ? 
O2 C15 H15A 109.5 . . ? 
O2 C15 H15B 109.5 . . ? 
H15A C15 H15B 109.5 . . ? 
O2 C15 H15C 109.5 . . ? 
H15A C15 H15C 109.5 . . ? 
H15B C15 H15C 109.5 . . ? 
C17 C16 C21 118.8(2) . . ? 
C17 C16 C3 122.3(2) . . ? 
C21 C16 C3 118.8(2) . . ? 
C16 C17 C18 120.3(2) . . ? 
C16 C17 H17 119.8 . . ? 
C18 C17 H17 119.8 . . ? 
C19 C18 C17 120.3(2) . . ? 
C19 C18 H18 119.9 . . ? 
C17 C18 H18 119.9 . . ? 
C18 C19 C20 119.7(2) . . ? 
C18 C19 H19 120.2 . . ? 
C20 C19 H19 120.2 . . ? 
C19 C20 C21 120.0(2) . . ? 
C19 C20 H20 120.0 . . ? 
C21 C20 H20 120.0 . . ? 
C20 C21 C16 120.8(2) . . ? 
C20 C21 H21 119.6 . . ? 
C16 C21 H21 119.6 . . ? 
O6 C22 H22A 109.5 . . ? 
O6 C22 H22B 109.5 . . ? 
H22A C22 H22B 109.5 . . ? 
O6 C22 H22C 109.5 . . ? 
H22A C22 H22C 109.5 . . ? 
H22B C22 H22C 109.5 . . ? 
O7 C23 H23A 109.5 . . ? 
O7 C23 H23B 109.5 . . ? 
H23A C23 H23B 109.5 . . ? 
O7 C23 H23C 109.5 . . ? 
H23A C23 H23C 109.5 . . ? 
H23B C23 H23C 109.5 . . ? 
C1 N1 C13 119.16(18) . . ? 
C1 N1 C5 126.44(18) . . ? 
C13 N1 C5 114.09(17) . . ? 
O5 N2 O4 124.1(2) . . ? 
O5 N2 C4 117.45(18) . . ? 
O4 N2 C4 118.50(17) . . ? 
C14 O2 C15 114.4(2) . . ? 
C8 O6 C22 115.80(17) . . ? 
C9 O7 C23 116.43(17) . . ? 
  
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 
O1 C1 C2 C14 -23.5(3) . . . . ? 
N1 C1 C2 C14 161.0(2) . . . . ? 
O1 C1 C2 C3 -153.2(2) . . . . ? 
N1 C1 C2 C3 31.3(3) . . . . ? 
C14 C2 C3 C16 57.0(3) . . . . ? 
C1 C2 C3 C16 -178.10(18) . . . . ? 
C14 C2 C3 C4 -176.00(19) . . . . ? 
C1 C2 C3 C4 -51.1(2) . . . . ? 
C16 C3 C4 N2 61.3(2) . . . . ? 
C2 C3 C4 N2 -67.3(2) . . . . ? 
C16 C3 C4 C5 -175.04(18) . . . . ? 
C2 C3 C4 C5 56.4(2) . . . . ? 
N2 C4 C5 N1 82.4(2) . . . . ? 
C3 C4 C5 N1 -40.5(2) . . . . ? 
N2 C4 C5 C6 -44.3(2) . . . . ? 
C3 C4 C5 C6 -167.18(18) . . . . ? 
N1 C5 C6 C11 0.4(3) . . . . ? 
C4 C5 C6 C11 128.1(2) . . . . ? 
N1 C5 C6 C7 -178.74(19) . . . . ? 
C4 C5 C6 C7 -51.1(3) . . . . ? 
C11 C6 C7 C8 -3.0(3) . . . . ? 
C5 C6 C7 C8 176.2(2) . . . . ? 
C6 C7 C8 O6 179.1(2) . . . . ? 
C6 C7 C8 C9 -1.7(3) . . . . ? 
O6 C8 C9 O7 3.3(3) . . . . ? 
C7 C8 C9 O7 -175.98(19) . . . . ? 
O6 C8 C9 C10 -176.15(19) . . . . ? 
C7 C8 C9 C10 4.6(3) . . . . ? 
O7 C9 C10 C11 177.8(2) . . . . ? 
C8 C9 C10 C11 -2.8(3) . . . . ? 
C7 C6 C11 C10 4.8(3) . . . . ? 
C5 C6 C11 C10 -174.4(2) . . . . ? 
C7 C6 C11 C12 -172.9(2) . . . . ? 
C5 C6 C11 C12 7.9(3) . . . . ? 
C9 C10 C11 C6 -1.9(3) . . . . ? 
C9 C10 C11 C12 175.8(2) . . . . ? 
C6 C11 C12 C13 20.0(3) . . . . ? 
C10 C11 C12 C13 -157.7(2) . . . . ? 
C11 C12 C13 N1 -55.2(2) . . . . ? 
C1 C2 C14 O3 101.2(3) . . . . ? 
C3 C2 C14 O3 -130.7(3) . . . . ? 
C1 C2 C14 O2 -78.4(2) . . . . ? 
C3 C2 C14 O2 49.6(3) . . . . ? 
C2 C3 C16 C17 25.4(3) . . . . ? 
C4 C3 C16 C17 -100.4(2) . . . . ? 
C2 C3 C16 C21 -155.9(2) . . . . ? 
C4 C3 C16 C21 78.4(3) . . . . ? 
C21 C16 C17 C18 0.8(3) . . . . ? 
C3 C16 C17 C18 179.5(2) . . . . ? 
C16 C17 C18 C19 -0.7(4) . . . . ? 
C17 C18 C19 C20 0.0(4) . . . . ? 
C18 C19 C20 C21 0.6(4) . . . . ? 
C19 C20 C21 C16 -0.5(4) . . . . ? 
C17 C16 C21 C20 -0.2(4) . . . . ? 
C3 C16 C21 C20 -179.0(2) . . . . ? 
O1 C1 N1 C13 -4.7(3) . . . . ? 
C2 C1 N1 C13 170.60(19) . . . . ? 
O1 C1 N1 C5 168.5(2) . . . . ? 
C2 C1 N1 C5 -16.1(3) . . . . ? 
C12 C13 N1 C1 -118.3(2) . . . . ? 
C12 C13 N1 C5 67.6(2) . . . . ? 
C6 C5 N1 C1 147.9(2) . . . . ? 
C4 C5 N1 C1 21.0(3) . . . . ? 
C6 C5 N1 C13 -38.5(2) . . . . ? 
C4 C5 N1 C13 -165.48(18) . . . . ? 
C5 C4 N2 O5 130.4(2) . . . . ? 
C3 C4 N2 O5 -105.4(2) . . . . ? 
C5 C4 N2 O4 -49.6(3) . . . . ? 
C3 C4 N2 O4 74.6(2) . . . . ? 
O3 C14 O2 C15 -10.2(4) . . . . ? 
C2 C14 O2 C15 169.4(2) . . . . ? 
C7 C8 O6 C22 -2.8(3) . . . . ? 
C9 C8 O6 C22 177.9(2) . . . . ? 
C10 C9 O7 C23 -5.3(3) . . . . ? 
C8 C9 O7 C23 175.3(2) . . . . ? 
  
_diffrn_measured_fraction_theta_max    0.951 
_diffrn_reflns_theta_full              25.00 
_diffrn_measured_fraction_theta_full   1.000 
_refine_diff_density_max    1.511 
_refine_diff_density_min   -0.244 
_refine_diff_density_rms    0.080 
