# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_cu_dm14004_0m
_database_code_depnum_ccdc_archive 'CCDC 998401'
_audit_update_record             
;
2014-04-19 deposited with the CCDC.
2016-01-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C26 H26 N4 O4'
_chemical_formula_weight         458.51

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           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                   14.9175(2)
_cell_length_b                   7.04670(10)
_cell_length_c                   22.1982(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 105.2390(10)
_cell_angle_gamma                90.00
_cell_volume                     2251.41(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    140(2)
_cell_measurement_reflns_used    9869
_cell_measurement_theta_min      3.07
_cell_measurement_theta_max      69.21

_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             968
_exptl_absorpt_coefficient_mu    0.757
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8274
_exptl_absorpt_correction_T_max  0.9281
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      140(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            15844
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_sigmaI/netI    0.0247
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         3.07
_diffrn_reflns_theta_max         69.56
_reflns_number_total             4141
_reflns_number_gt                3879
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_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)+(0.0670P)²+0.7383P] 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         4141
_refine_ls_number_parameters     312
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0407
_refine_ls_wR_factor_ref         0.1098
_refine_ls_wR_factor_gt          0.1080
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_restrained_S_all      1.036
_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
N2 N 0.37212(7) 0.83231(14) 0.55683(5) 0.0187(2) Uani 1 1 d . . .
N9 N 0.55754(7) 0.70177(15) 0.48264(5) 0.0202(2) Uani 1 1 d . . .
H9 H 0.5363 0.7032 0.4417 0.024 Uiso 1 1 calc R . .
N1' N 0.15539(7) 0.90222(15) 0.58994(5) 0.0226(2) Uani 1 1 d . . .
N3' N 0.29462(7) 1.07326(15) 0.64075(5) 0.0215(2) Uani 1 1 d . . .
O1 O 0.88739(6) 0.54937(15) 0.52096(4) 0.0301(2) Uani 1 1 d . . .
O2 O 0.30325(6) 1.25292(15) 0.72655(4) 0.0314(2) Uani 1 1 d . . .
O3 O 0.53797(7) 0.75976(15) 0.85609(4) 0.0300(2) Uani 1 1 d . . .
H3 H 0.5870 0.7081 0.8524 0.045 Uiso 1 1 calc R . .
O4 O 0.73336(8) 0.04906(15) 0.70591(5) 0.0364(3) Uani 1 1 d . . .
H4 H 0.7195 -0.0470 0.7240 0.055 Uiso 1 1 calc R . .
C1 C 0.41250(9) 0.80424(16) 0.50869(6) 0.0191(3) Uani 1 1 d . . .
C3 C 0.42070(9) 0.75294(18) 0.61997(5) 0.0217(3) Uani 1 1 d . . .
H3A H 0.4086 0.6148 0.6200 0.026 Uiso 1 1 calc R . .
H3B H 0.3940 0.8119 0.6518 0.026 Uiso 1 1 calc R . .
C4 C 0.52501(9) 0.78579(18) 0.63814(6) 0.0217(3) Uani 1 1 d . . .
H4A H 0.5385 0.9216 0.6479 0.026 Uiso 1 1 calc R . .
H4B H 0.5546 0.7104 0.6757 0.026 Uiso 1 1 calc R . .
C5 C 0.73818(9) 0.63097(18) 0.62320(6) 0.0236(3) Uani 1 1 d . . .
H5 H 0.7439 0.6344 0.6668 0.028 Uiso 1 1 calc R . .
C6 C 0.81317(9) 0.58700(19) 0.60108(6) 0.0254(3) Uani 1 1 d . . .
H6 H 0.8711 0.5588 0.6298 0.030 Uiso 1 1 calc R . .
C7 C 0.80595(9) 0.58272(18) 0.53596(6) 0.0232(3) Uani 1 1 d . . .
C8 C 0.72247(9) 0.61446(17) 0.49234(6) 0.0214(3) Uani 1 1 d . . .
H8 H 0.7170 0.6072 0.4488 0.026 Uiso 1 1 calc R . .
C10 C 0.50719(8) 0.74331(17) 0.52496(6) 0.0196(3) Uani 1 1 d . . .
C11 C 0.56294(8) 0.72736(17) 0.58495(6) 0.0201(3) Uani 1 1 d . . .
C12 C 0.65223(8) 0.67104(17) 0.58016(6) 0.0200(3) Uani 1 1 d . . .
C13 C 0.64619(8) 0.65797(17) 0.51546(6) 0.0199(3) Uani 1 1 d . . .
C14 C 0.36055(9) 0.83560(17) 0.44727(6) 0.0209(3) Uani 1 1 d . . .
H14 H 0.3888 0.8214 0.4139 0.025 Uiso 1 1 calc R . .
C15 C 0.26882(9) 0.88679(18) 0.43515(6) 0.0234(3) Uani 1 1 d . . .
H15 H 0.2323 0.9004 0.3933 0.028 Uiso 1 1 calc R . .
C16 C 0.22986(9) 0.91848(18) 0.48467(6) 0.0225(3) Uani 1 1 d . . .
H16 H 0.1666 0.9555 0.4767 0.027 Uiso 1 1 calc R . .
C17 C 0.28271(8) 0.89635(17) 0.54543(6) 0.0199(3) Uani 1 1 d . . .
C18 C 0.88628(10) 0.5695(2) 0.45648(7) 0.0319(3) Uani 1 1 d . . .
H18A H 0.8473 0.4699 0.4320 0.048 Uiso 1 1 calc R . .
H18B H 0.9497 0.5582 0.4521 0.048 Uiso 1 1 calc R . .
H18C H 0.8610 0.6942 0.4413 0.048 Uiso 1 1 calc R . .
C25 C 0.47927(10) 0.7998(2) 0.79612(6) 0.0322(3) Uani 1 1 d . . .
H25A H 0.4259 0.8747 0.8004 0.048 Uiso 1 1 calc R . .
H25B H 0.4573 0.6806 0.7745 0.048 Uiso 1 1 calc R . .
H25C H 0.5140 0.8719 0.7719 0.048 Uiso 1 1 calc R . .
C26 C 0.77535(12) 0.1860(2) 0.75074(8) 0.0414(4) Uani 1 1 d . . .
H26A H 0.7306 0.2287 0.7732 0.062 Uiso 1 1 calc R . .
H26B H 0.7953 0.2944 0.7298 0.062 Uiso 1 1 calc R . .
H26C H 0.8294 0.1300 0.7804 0.062 Uiso 1 1 calc R . .
C2' C 0.24153(8) 0.95736(17) 0.59706(6) 0.0200(3) Uani 1 1 d . . .
C4' C 0.25523(9) 1.15058(18) 0.68406(6) 0.0223(3) Uani 1 1 d . . .
C5' C 0.10819(9) 1.1880(2) 0.71827(6) 0.0273(3) Uani 1 1 d . . .
H5' H 0.1380 1.2775 0.7491 0.033 Uiso 1 1 calc R . .
C6' C 0.01727(9) 1.1378(2) 0.71284(6) 0.0309(3) Uani 1 1 d . . .
H6' H -0.0156 1.1930 0.7397 0.037 Uiso 1 1 calc R . .
C7' C -0.02691(9) 1.0053(2) 0.66770(7) 0.0295(3) Uani 1 1 d . . .
H7' H -0.0892 0.9691 0.6648 0.035 Uiso 1 1 calc R . .
C8' C 0.01898(9) 0.9272(2) 0.62759(6) 0.0270(3) Uani 1 1 d . . .
H8' H -0.0118 0.8387 0.5968 0.032 Uiso 1 1 calc R . .
C9' C 0.11197(9) 0.97853(18) 0.63210(6) 0.0222(3) Uani 1 1 d . . .
C10' C 0.15723(9) 1.10752(18) 0.67847(6) 0.0222(3) 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
N2 C17 1.3671(16) . ?
N2 C1 1.3719(15) . ?
N2 C3 1.5061(15) . ?
N9 C13 1.3669(16) . ?
N9 C10 1.3796(16) . ?
N9 H9 0.8800 . ?
N1' C2' 1.3117(16) . ?
N1' C9' 1.3795(16) . ?
N3' C2' 1.3532(16) . ?
N3' C4' 1.3649(16) . ?
O1 C7 1.3619(15) . ?
O1 C18 1.4342(17) . ?
O2 C4' 1.2521(16) . ?
O3 C25 1.4163(16) . ?
O3 H3 0.8400 . ?
O4 C26 1.4092(18) . ?
O4 H4 0.8400 . ?
C1 C14 1.3975(17) . ?
C1 C10 1.4289(17) . ?
C3 C4 1.5190(17) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 C11 1.4949(17) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 C6 1.3701(19) . ?
C5 C12 1.4115(17) . ?
C5 H5 0.9500 . ?
C6 C7 1.4214(18) . ?
C6 H6 0.9500 . ?
C7 C8 1.3800(18) . ?
C8 C13 1.3997(17) . ?
C8 H8 0.9500 . ?
C10 C11 1.3769(17) . ?
C11 C12 1.4204(17) . ?
C12 C13 1.4183(17) . ?
C14 C15 1.3715(18) . ?
C14 H14 0.9500 . ?
C15 C16 1.3900(18) . ?
C15 H15 0.9500 . ?
C16 C17 1.3806(18) . ?
C16 H16 0.9500 . ?
C17 C2' 1.4987(16) . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 0.9800 . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?
C26 H26C 0.9800 . ?
C4' C10' 1.4660(17) . ?
C5' C6' 1.376(2) . ?
C5' C10' 1.4061(18) . ?
C5' H5' 0.9500 . ?
C6' C7' 1.401(2) . ?
C6' H6' 0.9500 . ?
C7' C8' 1.373(2) . ?
C7' H7' 0.9500 . ?
C8' C9' 1.4114(18) . ?
C8' H8' 0.9500 . ?
C9' C10' 1.4058(18) . ?

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
C17 N2 C1 120.67(10) . . ?
C17 N2 C3 120.15(10) . . ?
C1 N2 C3 117.96(10) . . ?
C13 N9 C10 107.97(10) . . ?
C13 N9 H9 126.0 . . ?
C10 N9 H9 126.0 . . ?
C2' N1' C9' 114.99(11) . . ?
C2' N3' C4' 117.81(11) . . ?
C7 O1 C18 116.74(10) . . ?
C25 O3 H3 109.5 . . ?
C26 O4 H4 109.5 . . ?
N2 C1 C14 119.52(11) . . ?
N2 C1 C10 116.99(11) . . ?
C14 C1 C10 123.49(11) . . ?
N2 C3 C4 113.53(10) . . ?
N2 C3 H3A 108.9 . . ?
C4 C3 H3A 108.9 . . ?
N2 C3 H3B 108.9 . . ?
C4 C3 H3B 108.9 . . ?
H3A C3 H3B 107.7 . . ?
C11 C4 C3 108.80(10) . . ?
C11 C4 H4A 109.9 . . ?
C3 C4 H4A 109.9 . . ?
C11 C4 H4B 109.9 . . ?
C3 C4 H4B 109.9 . . ?
H4A C4 H4B 108.3 . . ?
C6 C5 C12 118.99(12) . . ?
C6 C5 H5 120.5 . . ?
C12 C5 H5 120.5 . . ?
C5 C6 C7 121.23(12) . . ?
C5 C6 H6 119.4 . . ?
C7 C6 H6 119.4 . . ?
O1 C7 C8 123.70(12) . . ?
O1 C7 C6 114.73(11) . . ?
C8 C7 C6 121.55(12) . . ?
C7 C8 C13 116.68(11) . . ?
C7 C8 H8 121.7 . . ?
C13 C8 H8 121.7 . . ?
C11 C10 N9 110.04(11) . . ?
C11 C10 C1 125.07(11) . . ?
N9 C10 C1 124.80(11) . . ?
C10 C11 C12 106.88(11) . . ?
C10 C11 C4 118.92(11) . . ?
C12 C11 C4 133.88(11) . . ?
C5 C12 C13 118.49(11) . . ?
C5 C12 C11 135.08(12) . . ?
C13 C12 C11 106.42(11) . . ?
N9 C13 C8 128.31(11) . . ?
N9 C13 C12 108.68(10) . . ?
C8 C13 C12 122.96(11) . . ?
C15 C14 C1 120.12(11) . . ?
C15 C14 H14 119.9 . . ?
C1 C14 H14 119.9 . . ?
C14 C15 C16 119.34(11) . . ?
C14 C15 H15 120.3 . . ?
C16 C15 H15 120.3 . . ?
C17 C16 C15 120.29(12) . . ?
C17 C16 H16 119.9 . . ?
C15 C16 H16 119.9 . . ?
N2 C17 C16 119.80(11) . . ?
N2 C17 C2' 121.95(11) . . ?
C16 C17 C2' 118.11(11) . . ?
O1 C18 H18A 109.5 . . ?
O1 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
O1 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
O3 C25 H25A 109.5 . . ?
O3 C25 H25B 109.5 . . ?
H25A C25 H25B 109.5 . . ?
O3 C25 H25C 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 109.5 . . ?
O4 C26 H26A 109.5 . . ?
O4 C26 H26B 109.5 . . ?
H26A C26 H26B 109.5 . . ?
O4 C26 H26C 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
N1' C2' N3' 129.45(11) . . ?
N1' C2' C17 114.10(11) . . ?
N3' C2' C17 116.17(11) . . ?
O2 C4' N3' 119.57(11) . . ?
O2 C4' C10' 122.90(11) . . ?
N3' C4' C10' 117.52(11) . . ?
C6' C5' C10' 120.32(13) . . ?
C6' C5' H5' 119.8 . . ?
C10' C5' H5' 119.8 . . ?
C5' C6' C7' 120.11(12) . . ?
C5' C6' H6' 119.9 . . ?
C7' C6' H6' 119.9 . . ?
C8' C7' C6' 120.66(12) . . ?
C8' C7' H7' 119.7 . . ?
C6' C7' H7' 119.7 . . ?
C7' C8' C9' 119.98(13) . . ?
C7' C8' H8' 120.0 . . ?
C9' C8' H8' 120.0 . . ?
N1' C9' C10' 121.88(11) . . ?
N1' C9' C8' 118.68(12) . . ?
C10' C9' C8' 119.44(12) . . ?
C9' C10' C5' 119.46(12) . . ?
C9' C10' C4' 118.17(11) . . ?
C5' C10' C4' 122.36(12) . . ?

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
C17 N2 C1 C14 -2.11(17) . . . . ?
C3 N2 C1 C14 165.29(11) . . . . ?
C17 N2 C1 C10 177.91(10) . . . . ?
C3 N2 C1 C10 -14.68(16) . . . . ?
C17 N2 C3 C4 -149.02(11) . . . . ?
C1 N2 C3 C4 43.51(14) . . . . ?
N2 C3 C4 C11 -48.78(13) . . . . ?
C12 C5 C6 C7 0.5(2) . . . . ?
C18 O1 C7 C8 6.93(18) . . . . ?
C18 O1 C7 C6 -171.69(12) . . . . ?
C5 C6 C7 O1 175.81(12) . . . . ?
C5 C6 C7 C8 -2.8(2) . . . . ?
O1 C7 C8 C13 -176.23(11) . . . . ?
C6 C7 C8 C13 2.30(18) . . . . ?
C13 N9 C10 C11 0.25(14) . . . . ?
C13 N9 C10 C1 177.02(11) . . . . ?
N2 C1 C10 C11 -6.17(18) . . . . ?
C14 C1 C10 C11 173.86(12) . . . . ?
N2 C1 C10 N9 177.55(11) . . . . ?
C14 C1 C10 N9 -2.43(19) . . . . ?
N9 C10 C11 C12 -0.69(14) . . . . ?
C1 C10 C11 C12 -177.45(11) . . . . ?
N9 C10 C11 C4 173.70(11) . . . . ?
C1 C10 C11 C4 -3.05(18) . . . . ?
C3 C4 C11 C10 30.16(15) . . . . ?
C3 C4 C11 C12 -157.29(13) . . . . ?
C6 C5 C12 C13 2.06(18) . . . . ?
C6 C5 C12 C11 -177.18(13) . . . . ?
C10 C11 C12 C5 -179.85(14) . . . . ?
C4 C11 C12 C5 7.0(2) . . . . ?
C10 C11 C12 C13 0.84(13) . . . . ?
C4 C11 C12 C13 -172.34(13) . . . . ?
C10 N9 C13 C8 -177.09(12) . . . . ?
C10 N9 C13 C12 0.29(13) . . . . ?
C7 C8 C13 N9 177.44(12) . . . . ?
C7 C8 C13 C12 0.40(18) . . . . ?
C5 C12 C13 N9 179.85(11) . . . . ?
C11 C12 C13 N9 -0.71(13) . . . . ?
C5 C12 C13 C8 -2.60(18) . . . . ?
C11 C12 C13 C8 176.84(11) . . . . ?
N2 C1 C14 C15 -2.56(18) . . . . ?
C10 C1 C14 C15 177.41(11) . . . . ?
C1 C14 C15 C16 3.96(19) . . . . ?
C14 C15 C16 C17 -0.80(19) . . . . ?
C1 N2 C17 C16 5.28(18) . . . . ?
C3 N2 C17 C16 -161.84(11) . . . . ?
C1 N2 C17 C2' -170.24(11) . . . . ?
C3 N2 C17 C2' 22.64(17) . . . . ?
C15 C16 C17 N2 -3.83(19) . . . . ?
C15 C16 C17 C2' 171.86(11) . . . . ?
C9' N1' C2' N3' 2.23(19) . . . . ?
C9' N1' C2' C17 -171.39(10) . . . . ?
C4' N3' C2' N1' -1.5(2) . . . . ?
C4' N3' C2' C17 172.06(10) . . . . ?
N2 C17 C2' N1' -139.12(12) . . . . ?
C16 C17 C2' N1' 45.29(16) . . . . ?
N2 C17 C2' N3' 46.37(16) . . . . ?
C16 C17 C2' N3' -129.22(12) . . . . ?
C2' N3' C4' O2 177.40(11) . . . . ?
C2' N3' C4' C10' -2.19(17) . . . . ?
C10' C5' C6' C7' 0.3(2) . . . . ?
C5' C6' C7' C8' -1.4(2) . . . . ?
C6' C7' C8' C9' 0.8(2) . . . . ?
C2' N1' C9' C10' 0.78(17) . . . . ?
C2' N1' C9' C8' 179.75(11) . . . . ?
C7' C8' C9' N1' -178.04(12) . . . . ?
C7' C8' C9' C10' 0.96(19) . . . . ?
N1' C9' C10' C5' 176.89(12) . . . . ?
C8' C9' C10' C5' -2.07(18) . . . . ?
N1' C9' C10' C4' -4.11(18) . . . . ?
C8' C9' C10' C4' 176.92(11) . . . . ?
C6' C5' C10' C9' 1.5(2) . . . . ?
C6' C5' C10' C4' -177.48(12) . . . . ?
O2 C4' C10' C9' -174.83(12) . . . . ?
N3' C4' C10' C9' 4.74(17) . . . . ?
O2 C4' C10' C5' 4.1(2) . . . . ?
N3' C4' C10' C5' -176.29(12) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N9 H9 O3 0.88 1.93 2.7602(13) 157.9 4_575
O3 H3 N3' 0.84 1.98 2.8067(14) 169.9 2_646
O4 H4 O2 0.84 1.87 2.7076(14) 173.0 2_636
C3 H3A O3 0.99 2.64 3.5451(16) 152.6 2_646
C3 H3B N3' 0.99 2.34 3.0499(16) 128.3 .
C4 H4A O3 0.99 2.63 3.4810(17) 143.7 2_656
C4 H4B O2 0.99 2.62 3.4050(15) 136.1 2_646
C18 H18A N1' 0.98 2.66 3.4872(19) 141.7 3_666
C18 H18B O1 0.98 2.46 3.3857(16) 156.5 3_766

_diffrn_measured_fraction_theta_max 0.978
_diffrn_reflns_theta_full        69.56
_diffrn_measured_fraction_theta_full 0.978
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.338
_refine_diff_density_rms         0.063
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_cu_dm14027_0m
_database_code_depnum_ccdc_archive 'CCDC 998402'
_audit_update_record             
;
2014-04-19 deposited with the CCDC.
2016-01-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C18 H22 N2 O5'
_chemical_formula_weight         346.38

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           Trigonal
_symmetry_space_group_name_H-M   P3(2)

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z+2/3'
'-x+y, -x, z+1/3'

_cell_length_a                   13.7436(2)
_cell_length_b                   13.7436(2)
_cell_length_c                   7.59540(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     1242.46(3)
_cell_formula_units_Z            3
_cell_measurement_temperature    140(2)
_cell_measurement_reflns_used    5797
_cell_measurement_theta_min      6.44
_cell_measurement_theta_max      69.60

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             552
_exptl_absorpt_coefficient_mu    0.845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8837
_exptl_absorpt_correction_T_max  0.9590
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      140(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            9294
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_sigmaI/netI    0.0458
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         6.44
_diffrn_reflns_theta_max         70.12
_reflns_number_total             2890
_reflns_number_gt                2824
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_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)+(0.0773P)²+0.0352P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.06(16)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         2890
_refine_ls_number_parameters     230
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0380
_refine_ls_wR_factor_ref         0.1055
_refine_ls_wR_factor_gt          0.1048
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_restrained_S_all      1.051
_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
O1 O 0.27637(12) 0.92990(14) -0.17237(19) 0.0334(3) Uani 1 1 d . . .
O2 O 0.77769(11) 1.25465(12) 0.7594(2) 0.0281(3) Uani 1 1 d . . .
O3 O 0.05700(10) 1.01716(12) 0.31542(18) 0.0255(3) Uani 1 1 d . . .
H3 H 0.0254 1.0008 0.4143 0.038 Uiso 1 1 calc R . .
O4 O 0.20354(13) 1.25994(13) 0.3802(2) 0.0342(3) Uani 1 1 d . . .
H4 H 0.1383 1.2476 0.3595 0.051 Uiso 1 1 calc R . .
C1 C 0.26223(15) 0.86005(15) 0.2925(3) 0.0209(4) Uani 1 1 d . . .
N2 N 0.27376(13) 0.85782(14) 0.0969(2) 0.0235(3) Uani 1 1 d . . .
C3 C 0.35408(17) 0.82263(18) 0.0392(3) 0.0291(4) Uani 1 1 d . . .
H3A H 0.3485 0.8114 -0.0900 0.035 Uiso 1 1 calc R . .
H3B H 0.3347 0.7502 0.0954 0.035 Uiso 1 1 calc R . .
C4 C 0.47475(17) 0.91113(18) 0.0883(3) 0.0293(4) Uani 1 1 d . . .
H4A H 0.5238 0.8775 0.0827 0.035 Uiso 1 1 calc R . .
H4B H 0.5037 0.9742 0.0035 0.035 Uiso 1 1 calc R . .
C5 C 0.68626(17) 1.08714(17) 0.3617(3) 0.0258(4) Uani 1 1 d . . .
H5 H 0.7203 1.0763 0.2604 0.031 Uiso 1 1 calc R . .
C6 C 0.75147(16) 1.16072(17) 0.4914(3) 0.0263(4) Uani 1 1 d . . .
H6 H 0.8308 1.2013 0.4783 0.032 Uiso 1 1 calc R . .
C7 C 0.70254(15) 1.17683(15) 0.6430(3) 0.0236(4) Uani 1 1 d . . .
C8 C 0.58713(16) 1.11842(15) 0.6691(2) 0.0216(4) Uani 1 1 d . . .
H8 H 0.5540 1.1281 0.7725 0.026 Uiso 1 1 calc R . .
N9 N 0.40702(12) 0.98207(13) 0.5212(2) 0.0201(3) Uani 1 1 d . . .
H9A H 0.3584 0.9773 0.6010 0.024 Uiso 1 1 calc R . .
C10 C 0.38110(15) 0.92844(14) 0.3610(3) 0.0200(3) Uani 1 1 d . . .
C11 C 0.47674(16) 0.95368(16) 0.2704(3) 0.0229(4) Uani 1 1 d . . .
C12 C 0.56864(16) 1.02800(15) 0.3803(3) 0.0217(4) Uani 1 1 d . . .
C13 C 0.52228(15) 1.04455(15) 0.5352(3) 0.0198(3) Uani 1 1 d . . .
O14 O 0.19679(10) 0.90880(10) 0.34177(16) 0.0204(3) Uani 1 1 d . . .
C15 C 0.22704(14) 1.01031(15) 0.2468(2) 0.0204(4) Uani 1 1 d . . .
H15 H 0.3107 1.0587 0.2475 0.025 Uiso 1 1 calc R . .
C21 C 0.19817(17) 0.74085(16) 0.3667(3) 0.0285(4) Uani 1 1 d . . .
H21A H 0.1885 0.7441 0.4940 0.043 Uiso 1 1 calc R . .
H21B H 0.2406 0.7023 0.3436 0.043 Uiso 1 1 calc R . .
H21C H 0.1243 0.6996 0.3102 0.043 Uiso 1 1 calc R . .
C16 C 0.18817(16) 0.97486(17) 0.0588(3) 0.0258(4) Uani 1 1 d . . .
H16A H 0.1061 0.9221 0.0566 0.031 Uiso 1 1 calc R . .
H16B H 0.2043 1.0414 -0.0129 0.031 Uiso 1 1 calc R . .
C17 C 0.24941(15) 0.91867(16) -0.0161(3) 0.0248(4) Uani 1 1 d . . .
C18 C 0.73205(18) 1.27550(19) 0.9145(3) 0.0323(5) Uani 1 1 d . . .
H18A H 0.6850 1.3075 0.8815 0.049 Uiso 1 1 calc R . .
H18B H 0.7934 1.3285 0.9905 0.049 Uiso 1 1 calc R . .
H18C H 0.6865 1.2048 0.9780 0.049 Uiso 1 1 calc R . .
C19 C 0.17626(15) 1.07285(16) 0.3386(2) 0.0214(4) Uani 1 1 d . . .
H19 H 0.1928 1.0763 0.4674 0.026 Uiso 1 1 calc R . .
C20 C 0.22768(16) 1.19239(16) 0.2687(3) 0.0253(4) Uani 1 1 d . . .
H20A H 0.3101 1.2257 0.2590 0.030 Uiso 1 1 calc R . .
H20B H 0.1978 1.1908 0.1495 0.030 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 C17 1.230(2) . ?
O2 C7 1.374(2) . ?
O2 C18 1.430(3) . ?
O3 C19 1.431(2) . ?
O3 H3 0.8400 . ?
O4 C20 1.413(2) . ?
O4 H4 0.8400 . ?
C1 O14 1.414(2) . ?
C1 N2 1.496(2) . ?
C1 C10 1.512(2) . ?
C1 C21 1.528(2) . ?
N2 C17 1.352(3) . ?
N2 C3 1.476(2) . ?
C3 C4 1.534(3) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 C11 1.497(3) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 C6 1.375(3) . ?
C5 C12 1.407(3) . ?
C5 H5 0.9500 . ?
C6 C7 1.406(3) . ?
C6 H6 0.9500 . ?
C7 C8 1.388(3) . ?
C8 C13 1.398(3) . ?
C8 H8 0.9500 . ?
N9 C10 1.374(3) . ?
N9 C13 1.378(2) . ?
N9 H9A 0.8800 . ?
C10 C11 1.366(3) . ?
C11 C12 1.430(3) . ?
C12 C13 1.409(3) . ?
O14 C15 1.435(2) . ?
C15 C16 1.517(3) . ?
C15 C19 1.520(2) . ?
C15 H15 1.0000 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C16 C17 1.510(3) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?
C19 C20 1.523(3) . ?
C19 H19 1.0000 . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?

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 C18 116.87(16) . . ?
C19 O3 H3 109.5 . . ?
C20 O4 H4 109.5 . . ?
O14 C1 N2 111.81(15) . . ?
O14 C1 C10 111.08(14) . . ?
N2 C1 C10 105.17(15) . . ?
O14 C1 C21 104.38(14) . . ?
N2 C1 C21 110.76(15) . . ?
C10 C1 C21 113.81(16) . . ?
C17 N2 C3 118.12(16) . . ?
C17 N2 C1 123.79(16) . . ?
C3 N2 C1 113.94(16) . . ?
N2 C3 C4 110.94(16) . . ?
N2 C3 H3A 109.5 . . ?
C4 C3 H3A 109.5 . . ?
N2 C3 H3B 109.5 . . ?
C4 C3 H3B 109.5 . . ?
H3A C3 H3B 108.0 . . ?
C11 C4 C3 109.62(16) . . ?
C11 C4 H4A 109.7 . . ?
C3 C4 H4A 109.7 . . ?
C11 C4 H4B 109.7 . . ?
C3 C4 H4B 109.7 . . ?
H4A C4 H4B 108.2 . . ?
C6 C5 C12 119.42(19) . . ?
C6 C5 H5 120.3 . . ?
C12 C5 H5 120.3 . . ?
C5 C6 C7 121.03(18) . . ?
C5 C6 H6 119.5 . . ?
C7 C6 H6 119.5 . . ?
O2 C7 C8 123.73(18) . . ?
O2 C7 C6 114.65(17) . . ?
C8 C7 C6 121.62(18) . . ?
C7 C8 C13 116.43(17) . . ?
C7 C8 H8 121.8 . . ?
C13 C8 H8 121.8 . . ?
C10 N9 C13 108.15(15) . . ?
C10 N9 H9A 125.9 . . ?
C13 N9 H9A 125.9 . . ?
C11 C10 N9 110.56(16) . . ?
C11 C10 C1 126.03(18) . . ?
N9 C10 C1 123.20(16) . . ?
C10 C11 C12 106.37(17) . . ?
C10 C11 C4 122.60(18) . . ?
C12 C11 C4 130.95(18) . . ?
C5 C12 C13 118.16(18) . . ?
C5 C12 C11 134.70(19) . . ?
C13 C12 C11 107.05(16) . . ?
N9 C13 C8 128.72(18) . . ?
N9 C13 C12 107.86(16) . . ?
C8 C13 C12 123.30(17) . . ?
C1 O14 C15 112.58(13) . . ?
O14 C15 C16 106.04(15) . . ?
O14 C15 C19 109.13(14) . . ?
C16 C15 C19 115.18(15) . . ?
O14 C15 H15 108.8 . . ?
C16 C15 H15 108.8 . . ?
C19 C15 H15 108.8 . . ?
C1 C21 H21A 109.5 . . ?
C1 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C1 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C17 C16 C15 108.81(15) . . ?
C17 C16 H16A 109.9 . . ?
C15 C16 H16A 109.9 . . ?
C17 C16 H16B 109.9 . . ?
C15 C16 H16B 109.9 . . ?
H16A C16 H16B 108.3 . . ?
O1 C17 N2 122.55(19) . . ?
O1 C17 C16 120.65(19) . . ?
N2 C17 C16 116.79(16) . . ?
O2 C18 H18A 109.5 . . ?
O2 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
O2 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
O3 C19 C15 111.60(15) . . ?
O3 C19 C20 108.88(14) . . ?
C15 C19 C20 110.71(15) . . ?
O3 C19 H19 108.5 . . ?
C15 C19 H19 108.5 . . ?
C20 C19 H19 108.5 . . ?
O4 C20 C19 111.42(16) . . ?
O4 C20 H20A 109.3 . . ?
C19 C20 H20A 109.3 . . ?
O4 C20 H20B 109.3 . . ?
C19 C20 H20B 109.3 . . ?
H20A C20 H20B 108.0 . . ?

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
O14 C1 N2 C17 15.3(2) . . . . ?
C10 C1 N2 C17 -105.39(18) . . . . ?
C21 C1 N2 C17 131.23(18) . . . . ?
O14 C1 N2 C3 171.84(14) . . . . ?
C10 C1 N2 C3 51.18(18) . . . . ?
C21 C1 N2 C3 -72.20(19) . . . . ?
C17 N2 C3 C4 89.9(2) . . . . ?
C1 N2 C3 C4 -68.0(2) . . . . ?
N2 C3 C4 C11 42.2(2) . . . . ?
C12 C5 C6 C7 0.7(3) . . . . ?
C18 O2 C7 C8 -0.4(3) . . . . ?
C18 O2 C7 C6 179.03(17) . . . . ?
C5 C6 C7 O2 -178.60(17) . . . . ?
C5 C6 C7 C8 0.8(3) . . . . ?
O2 C7 C8 C13 178.19(16) . . . . ?
C6 C7 C8 C13 -1.2(2) . . . . ?
C13 N9 C10 C11 0.5(2) . . . . ?
C13 N9 C10 C1 -174.53(15) . . . . ?
O14 C1 C10 C11 -137.98(18) . . . . ?
N2 C1 C10 C11 -16.8(2) . . . . ?
C21 C1 C10 C11 104.6(2) . . . . ?
O14 C1 C10 N9 36.2(2) . . . . ?
N2 C1 C10 N9 157.37(16) . . . . ?
C21 C1 C10 N9 -81.2(2) . . . . ?
N9 C10 C11 C12 -0.1(2) . . . . ?
C1 C10 C11 C12 174.72(16) . . . . ?
N9 C10 C11 C4 -177.40(17) . . . . ?
C1 C10 C11 C4 -2.6(3) . . . . ?
C3 C4 C11 C10 -9.8(3) . . . . ?
C3 C4 C11 C12 173.64(19) . . . . ?
C6 C5 C12 C13 -1.8(3) . . . . ?
C6 C5 C12 C11 174.4(2) . . . . ?
C10 C11 C12 C5 -176.77(19) . . . . ?
C4 C11 C12 C5 0.2(4) . . . . ?
C10 C11 C12 C13 -0.3(2) . . . . ?
C4 C11 C12 C13 176.7(2) . . . . ?
C10 N9 C13 C8 175.42(17) . . . . ?
C10 N9 C13 C12 -0.66(19) . . . . ?
C7 C8 C13 N9 -175.47(16) . . . . ?
C7 C8 C13 C12 0.1(3) . . . . ?
C5 C12 C13 N9 177.75(16) . . . . ?
C11 C12 C13 N9 0.59(19) . . . . ?
C5 C12 C13 C8 1.4(3) . . . . ?
C11 C12 C13 C8 -175.75(17) . . . . ?
N2 C1 O14 C15 -45.23(18) . . . . ?
C10 C1 O14 C15 71.92(19) . . . . ?
C21 C1 O14 C15 -165.01(15) . . . . ?
C1 O14 C15 C16 70.10(17) . . . . ?
C1 O14 C15 C19 -165.27(14) . . . . ?
O14 C15 C16 C17 -61.62(17) . . . . ?
C19 C15 C16 C17 177.58(15) . . . . ?
C3 N2 C17 O1 12.2(3) . . . . ?
C1 N2 C17 O1 167.86(17) . . . . ?
C3 N2 C17 C16 -166.90(16) . . . . ?
C1 N2 C17 C16 -11.2(2) . . . . ?
C15 C16 C17 O1 -145.12(18) . . . . ?
C15 C16 C17 N2 34.0(2) . . . . ?
O14 C15 C19 O3 -71.66(18) . . . . ?
C16 C15 C19 O3 47.4(2) . . . . ?
O14 C15 C19 C20 166.88(14) . . . . ?
C16 C15 C19 C20 -74.0(2) . . . . ?
O3 C19 C20 O4 71.8(2) . . . . ?
C15 C19 C20 O4 -165.19(15) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O4 H4 O1 0.84 2.25 2.777(2) 121.3 2_675
C4 H4A O4 0.99 2.65 3.459(3) 138.8 2_774
N9 H9A O1 0.88 1.98 2.805(2) 155.4 1_556
C15 H15 O2 1.00 2.55 3.413(2) 143.9 3_574
C20 H20A O2 0.99 2.64 3.505(2) 146.2 3_574
C20 H20B O14 0.99 2.65 3.408(2) 133.3 2_674

_diffrn_measured_fraction_theta_max 0.985
_diffrn_reflns_theta_full        70.12
_diffrn_measured_fraction_theta_full 0.985
_refine_diff_density_max         0.241
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.055
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_dm13610
_database_code_depnum_ccdc_archive 'CCDC 998403'
_audit_update_record             
;
2014-04-19 deposited with the CCDC.
2016-01-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15 H17 N3 O4'
_chemical_formula_weight         303.32

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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
; 
The symmetry employed for this shelxl refinement is uniquely defined 
by the following loop, which should always be used as a source of 
symmetry information in preference to the above space-group names. 
They are only intended as comments. 
;

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

_cell_length_a                   10.7205(2)
_cell_length_b                   11.74740(10)
_cell_length_c                   11.46760(10)
_cell_angle_alpha                90
_cell_angle_beta                 107.73
_cell_angle_gamma                90
_cell_volume                     1375.59(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    140(2)
_cell_measurement_reflns_used    7922
_cell_measurement_theta_min      4.33
_cell_measurement_theta_max      68.91

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.465
_exptl_crystal_F_000             640
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    0.900
_shelx_estimated_absorpt_T_min   0.806
_shelx_estimated_absorpt_T_max   0.855
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5338
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      140(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            11612
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         4.330
_diffrn_reflns_theta_max         69.639
_diffrn_reflns_theta_full        67.679
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measured_fraction_theta_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_point_group_measured_fraction_full 0.977
_reflns_number_total             2496
_reflns_number_gt                2412
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
; 
 Reflections were merged by SHELXL according to the crystal 
 class for the calculation of statistics and refinement. 
  
 _reflns_Friedel_fraction is defined as the number of unique 
 Friedel pairs measured divided by the number that would be 
 possible theoretically, ignoring centric projections and 
 systematic absences. 
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 ? 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0810P)²+1.7004P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2496
_refine_ls_number_parameters     206
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0592
_refine_ls_wR_factor_ref         0.1674
_refine_ls_wR_factor_gt          0.1574
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_restrained_S_all      1.107
_refine_ls_shift/su_max          0.018
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.76582(17) 0.42952(15) 0.21183(16) 0.0198(4) Uani 1 1 d . . . . .
N3 N 0.62328(17) 0.32621(16) 0.04750(16) 0.0203(4) Uani 1 1 d . . . . .
N2' N 0.9796(2) 0.22318(17) 0.24931(17) 0.0267(5) Uani 1 1 d . . . . .
O1 O 0.40093(15) 0.33372(14) -0.00560(15) 0.0285(4) Uani 1 1 d . . . . .
O2 O 0.86558(15) 0.40767(14) -0.01275(14) 0.0248(4) Uani 1 1 d . . . . .
H2 H 0.8769 0.3801 -0.0764 0.037 Uiso 1 1 calc R U . . .
O3 O 0.88141(19) 0.16764(15) 0.26796(16) 0.0359(5) Uani 1 1 d . . . . .
O1S O 0.9764(2) 0.5236(2) 0.6145(3) 0.0819(10) Uani 1 1 d D . . . .
H1S H 0.978(5) 0.5627(12) 0.556(2) 0.123 Uiso 1 1 d D U . . .
H2S H 1.049(3) 0.534(5) 0.664(4) 0.123 Uiso 1 1 d D U . . .
C2 C 0.7435(2) 0.36330(17) 0.11850(18) 0.0187(5) Uani 1 1 d . . . . .
C4 C 0.5070(2) 0.36363(18) 0.06380(19) 0.0208(5) Uani 1 1 d . . . . .
C5 C 0.4199(2) 0.4772(2) 0.2039(2) 0.0266(5) Uani 1 1 d . . . . .
H5 H 0.3336 0.4580 0.1553 0.032 Uiso 1 1 calc R U . . .
C6 C 0.4386(3) 0.5445(2) 0.3061(2) 0.0308(6) Uani 1 1 d . . . . .
H6 H 0.3655 0.5714 0.3285 0.037 Uiso 1 1 calc R U . . .
C7 C 0.5660(3) 0.5733(2) 0.3767(2) 0.0291(5) Uani 1 1 d . . . . .
H7 H 0.5787 0.6194 0.4475 0.035 Uiso 1 1 calc R U . . .
C8 C 0.6728(2) 0.53575(19) 0.3452(2) 0.0249(5) Uani 1 1 d . . . . .
H8 H 0.7585 0.5566 0.3936 0.030 Uiso 1 1 calc R U . . .
C9 C 0.8460(2) 0.31828(19) 0.06295(19) 0.0220(5) Uani 1 1 d . . . . .
C10 C 0.7759(2) 0.21511(19) -0.0111(2) 0.0244(5) Uani 1 1 d . . . . .
H10A H 0.8066 0.2013 -0.0829 0.029 Uiso 1 1 calc R U . . .
H10B H 0.7908 0.1457 0.0403 0.029 Uiso 1 1 calc R U . . .
C11 C 0.6310(2) 0.2489(2) -0.05109(19) 0.0241(5) Uani 1 1 d . . . . .
H11A H 0.6060 0.2883 -0.1312 0.029 Uiso 1 1 calc R U . . .
H11B H 0.5740 0.1816 -0.0564 0.029 Uiso 1 1 calc R U . . .
C1' C 0.9732(2) 0.2908(2) 0.1596(2) 0.0267(5) Uani 1 1 d . . . . .
C3' C 1.1137(3) 0.2127(3) 0.3369(3) 0.0455(8) Uani 1 1 d . . . . .
H3'1 H 1.1442 0.1327 0.3431 0.055 Uiso 1 1 calc R U . . .
H3'2 H 1.1161 0.2398 0.4194 0.055 Uiso 1 1 calc R U . . .
C4' C 1.1962(3) 0.2870(3) 0.2831(3) 0.0442(7) Uani 1 1 d . . . . .
H4'1 H 1.2624 0.2407 0.2602 0.053 Uiso 1 1 calc R U . . .
H4'2 H 1.2422 0.3454 0.3431 0.053 Uiso 1 1 calc R U . . .
C5' C 1.1023(3) 0.3437(5) 0.1692(3) 0.0715(13) Uani 1 1 d . . . . .
H5'1 H 1.0995 0.4271 0.1801 0.086 Uiso 1 1 calc R U . . .
H5'2 H 1.1289 0.3275 0.0954 0.086 Uiso 1 1 calc R U . . .
C1A C 0.6556(2) 0.46679(18) 0.24167(19) 0.0195(5) Uani 1 1 d . . . . .
C4A C 0.5276(2) 0.43678(18) 0.17136(19) 0.0203(5) 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
N1 C2 1.285(3) . ?
N1 C1A 1.397(3) . ?
N3 C2 1.369(3) . ?
N3 C4 1.388(3) . ?
N3 C11 1.472(3) . ?
N2' C1' 1.284(3) . ?
N2' O3 1.311(3) . ?
N2' C3' 1.487(3) . ?
O1 C4 1.224(3) . ?
O2 C9 1.418(3) . ?
O2 H2 0.8400 . ?
O1S H1S 0.818(10) . ?
O1S H2S 0.819(10) . ?
C2 C9 1.523(3) . ?
C4 C4A 1.464(3) . ?
C5 C6 1.377(3) . ?
C5 C4A 1.400(3) . ?
C5 H5 0.9500 . ?
C6 C7 1.400(4) . ?
C6 H6 0.9500 . ?
C7 C8 1.375(3) . ?
C7 H7 0.9500 . ?
C8 C1A 1.402(3) . ?
C8 H8 0.9500 . ?
C9 C1' 1.507(3) . ?
C9 C10 1.538(3) . ?
C10 C11 1.532(3) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C1' C5' 1.491(4) . ?
C3' C4' 1.503(5) . ?
C3' H3'1 0.9900 . ?
C3' H3'2 0.9900 . ?
C4' C5' 1.537(4) . ?
C4' H4'1 0.9900 . ?
C4' H4'2 0.9900 . ?
C5' H5'1 0.9900 . ?
C5' H5'2 0.9900 . ?
C1A C4A 1.408(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
C2 N1 C1A 115.90(18) . . ?
C2 N3 C4 122.74(18) . . ?
C2 N3 C11 112.97(18) . . ?
C4 N3 C11 124.19(18) . . ?
C1' N2' O3 126.0(2) . . ?
C1' N2' C3' 113.4(2) . . ?
O3 N2' C3' 120.5(2) . . ?
C9 O2 H2 109.5 . . ?
H1S O1S H2S 104(2) . . ?
N1 C2 N3 126.2(2) . . ?
N1 C2 C9 125.68(19) . . ?
N3 C2 C9 108.01(18) . . ?
O1 C4 N3 121.1(2) . . ?
O1 C4 C4A 126.1(2) . . ?
N3 C4 C4A 112.83(18) . . ?
C6 C5 C4A 120.2(2) . . ?
C6 C5 H5 119.9 . . ?
C4A C5 H5 119.9 . . ?
C5 C6 C7 119.7(2) . . ?
C5 C6 H6 120.2 . . ?
C7 C6 H6 120.2 . . ?
C8 C7 C6 120.9(2) . . ?
C8 C7 H7 119.6 . . ?
C6 C7 H7 119.6 . . ?
C7 C8 C1A 120.2(2) . . ?
C7 C8 H8 119.9 . . ?
C1A C8 H8 119.9 . . ?
O2 C9 C1' 109.87(19) . . ?
O2 C9 C2 105.01(17) . . ?
C1' C9 C2 111.90(18) . . ?
O2 C9 C10 112.60(17) . . ?
C1' C9 C10 114.69(19) . . ?
C2 C9 C10 102.15(17) . . ?
C11 C10 C9 104.00(17) . . ?
C11 C10 H10A 111.0 . . ?
C9 C10 H10A 111.0 . . ?
C11 C10 H10B 111.0 . . ?
C9 C10 H10B 111.0 . . ?
H10A C10 H10B 109.0 . . ?
N3 C11 C10 102.63(16) . . ?
N3 C11 H11A 111.2 . . ?
C10 C11 H11A 111.2 . . ?
N3 C11 H11B 111.2 . . ?
C10 C11 H11B 111.2 . . ?
H11A C11 H11B 109.2 . . ?
N2' C1' C5' 112.1(2) . . ?
N2' C1' C9 122.5(2) . . ?
C5' C1' C9 125.2(2) . . ?
N2' C3' C4' 104.1(2) . . ?
N2' C3' H3'1 110.9 . . ?
C4' C3' H3'1 110.9 . . ?
N2' C3' H3'2 110.9 . . ?
C4' C3' H3'2 110.9 . . ?
H3'1 C3' H3'2 109.0 . . ?
C3' C4' C5' 106.6(2) . . ?
C3' C4' H4'1 110.4 . . ?
C5' C4' H4'1 110.4 . . ?
C3' C4' H4'2 110.4 . . ?
C5' C4' H4'2 110.4 . . ?
H4'1 C4' H4'2 108.6 . . ?
C1' C5' C4' 103.6(3) . . ?
C1' C5' H5'1 111.0 . . ?
C4' C5' H5'1 111.0 . . ?
C1' C5' H5'2 111.0 . . ?
C4' C5' H5'2 111.0 . . ?
H5'1 C5' H5'2 109.0 . . ?
N1 C1A C8 119.07(19) . . ?
N1 C1A C4A 122.05(19) . . ?
C8 C1A C4A 118.9(2) . . ?
C5 C4A C1A 120.1(2) . . ?
C5 C4A C4 119.9(2) . . ?
C1A C4A C4 120.0(2) . . ?

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
C1A N1 C2 N3 -0.4(3) . . . . ?
C1A N1 C2 C9 175.56(19) . . . . ?
C4 N3 C2 N1 4.8(3) . . . . ?
C11 N3 C2 N1 -178.7(2) . . . . ?
C4 N3 C2 C9 -171.80(18) . . . . ?
C11 N3 C2 C9 4.7(2) . . . . ?
C2 N3 C4 O1 175.8(2) . . . . ?
C11 N3 C4 O1 -0.3(3) . . . . ?
C2 N3 C4 C4A -5.8(3) . . . . ?
C11 N3 C4 C4A 178.05(18) . . . . ?
C4A C5 C6 C7 0.6(4) . . . . ?
C5 C6 C7 C8 0.4(4) . . . . ?
C6 C7 C8 C1A -0.6(4) . . . . ?
N1 C2 C9 O2 -81.6(2) . . . . ?
N3 C2 C9 O2 94.96(19) . . . . ?
N1 C2 C9 C1' 37.5(3) . . . . ?
N3 C2 C9 C1' -145.89(19) . . . . ?
N1 C2 C9 C10 160.7(2) . . . . ?
N3 C2 C9 C10 -22.7(2) . . . . ?
O2 C9 C10 C11 -80.8(2) . . . . ?
C1' C9 C10 C11 152.56(19) . . . . ?
C2 C9 C10 C11 31.3(2) . . . . ?
C2 N3 C11 C10 15.4(2) . . . . ?
C4 N3 C11 C10 -168.06(19) . . . . ?
C9 C10 C11 N3 -28.7(2) . . . . ?
O3 N2' C1' C5' 177.5(3) . . . . ?
C3' N2' C1' C5' -1.6(4) . . . . ?
O3 N2' C1' C9 1.9(4) . . . . ?
C3' N2' C1' C9 -177.2(2) . . . . ?
O2 C9 C1' N2' 171.0(2) . . . . ?
C2 C9 C1' N2' 54.8(3) . . . . ?
C10 C9 C1' N2' -61.0(3) . . . . ?
O2 C9 C1' C5' -4.0(4) . . . . ?
C2 C9 C1' C5' -120.2(3) . . . . ?
C10 C9 C1' C5' 124.0(3) . . . . ?
C1' N2' C3' C4' -1.3(3) . . . . ?
O3 N2' C3' C4' 179.5(2) . . . . ?
N2' C3' C4' C5' 3.5(4) . . . . ?
N2' C1' C5' C4' 3.7(4) . . . . ?
C9 C1' C5' C4' 179.2(2) . . . . ?
C3' C4' C5' C1' -4.3(4) . . . . ?
C2 N1 C1A C8 177.60(19) . . . . ?
C2 N1 C1A C4A -2.1(3) . . . . ?
C7 C8 C1A N1 -179.8(2) . . . . ?
C7 C8 C1A C4A -0.1(3) . . . . ?
C6 C5 C4A C1A -1.3(3) . . . . ?
C6 C5 C4A C4 179.0(2) . . . . ?
N1 C1A C4A C5 -179.26(19) . . . . ?
C8 C1A C4A C5 1.1(3) . . . . ?
N1 C1A C4A C4 0.5(3) . . . . ?
C8 C1A C4A C4 -179.18(19) . . . . ?
O1 C4 C4A C5 1.3(3) . . . . ?
N3 C4 C4A C5 -176.95(19) . . . . ?
O1 C4 C4A C1A -178.4(2) . . . . ?
N3 C4 C4A C1A 3.3(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O2 H2 O3 0.84 1.89 2.719(2) 171.5 4_565
O1S H2S N1 0.819(10) 2.107(12) 2.925(3) 177(5) 3_766
C10 H10A O3 0.99 2.60 3.368(3) 134.2 4_565
C10 H10B O3 0.99 2.51 3.102(3) 118.4 .

_refine_diff_density_max         0.563
_refine_diff_density_min         -0.639
_refine_diff_density_rms         0.107

_shelxl_version_number           2013-4

