# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_imine_a
_database_code_depnum_ccdc_archive 'CCDC 1961068'
loop_
_audit_author_name
_audit_author_address
'Yuichiro Mutoh'
;Tokyo University of Science
Japan
;
_audit_update_record             
;
2019-10-24 deposited with the CCDC.	2019-11-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          '356 (dec)'
_chemical_formula_moiety         ?
_chemical_formula_sum            'C13 H8 Br N O2'
_chemical_formula_weight         290.11

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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -z'

_cell_length_a                   7.7641(15)
_cell_length_b                   8.5691(16)
_cell_length_c                   9.3591(18)
_cell_angle_alpha                109.386(2)
_cell_angle_beta                 107.959(2)
_cell_angle_gamma                94.303(2)
_cell_volume                     547.73(18)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)

_cell_measurement_reflns_used    4295

_cell_measurement_theta_min      2.47

_cell_measurement_theta_max      28.36


_exptl_crystal_description       prism

_exptl_crystal_colour            orange

_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.759
_exptl_crystal_F_000             288
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.12

_exptl_crystal_size_mid          0.11

_exptl_crystal_size_min          0.094

_exptl_absorpt_coefficient_mu    3.739
_shelx_estimated_absorpt_T_min   0.663
_shelx_estimated_absorpt_T_max   0.730
_exptl_absorpt_correction_type   multi-scan

_exptl_absorpt_correction_T_min  0.678

_exptl_absorpt_correction_T_max  0.730

_exptl_absorpt_process_details   'SADABS 2016/2'

_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)

_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\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            6106
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_av_R_equivalents  0.0156
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.467
_diffrn_reflns_theta_max         27.481
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measured_fraction_theta_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_point_group_measured_fraction_full 0.995
_reflns_number_total             2440
_reflns_number_gt                2323
_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    'SHELXT-2018/2 (Sheldrick, 2018)'

_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'

_computing_publication_material  
;Yadokari-XG 2009 (Wakita,Nemoto et al., 2009)
;

_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)+(0.0269P)²+0.2171P] 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         2440
_refine_ls_number_parameters     157
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0205
_refine_ls_R_factor_gt           0.0190
_refine_ls_wR_factor_ref         0.0500
_refine_ls_wR_factor_gt          0.0495
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_restrained_S_all      1.080
_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_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
O1 O 0.33060(17) 0.10134(15) 0.00388(14) 0.0183(2) Uani 1 1 d . . . . .
O2 O 0.25563(16) 0.30782(14) 0.17357(13) 0.0155(2) Uani 1 1 d . . . . .
N1 N 0.4960(2) -0.01067(18) 0.26105(18) 0.0168(3) Uani 1 1 d . . . . .
H1 H 0.529(3) -0.031(3) 0.169(3) 0.020 Uiso 1 1 d . U . . .
Br1 Br 0.07224(2) -0.01837(2) 0.31356(2) 0.01766(6) Uani 1 1 d . . . . .
C1 C 0.3230(2) 0.1640(2) 0.13641(19) 0.0133(3) Uani 1 1 d . . . . .
C2 C 0.3879(2) 0.09270(19) 0.26761(19) 0.0125(3) Uani 1 1 d . . . . .
C3 C 0.3134(2) 0.14520(19) 0.40232(19) 0.0125(3) Uani 1 1 d . . . . .
H3 H 0.398500 0.132129 0.500600 0.015 Uiso 1 1 calc R U . . .
C4 C 0.2797(2) 0.32110(19) 0.44340(19) 0.0112(3) Uani 1 1 d . . . . .
C5 C 0.2683(2) 0.41713(19) 0.59701(19) 0.0115(3) Uani 1 1 d . . . . .
C6 C 0.2877(2) 0.3518(2) 0.72092(19) 0.0142(3) Uani 1 1 d . . . . .
H6 H 0.310939 0.240966 0.703545 0.017 Uiso 1 1 calc R U . . .
C7 C 0.2734(2) 0.4471(2) 0.8656(2) 0.0177(3) Uani 1 1 d . . . . .
H7 H 0.286399 0.401384 0.947049 0.021 Uiso 1 1 calc R U . . .
C8 C 0.2395(2) 0.6122(2) 0.8945(2) 0.0179(3) Uani 1 1 d . . . . .
H8 H 0.230576 0.677294 0.995355 0.021 Uiso 1 1 calc R U . . .
C9 C 0.2193(2) 0.6788(2) 0.7770(2) 0.0153(3) Uani 1 1 d . . . . .
H9 H 0.196293 0.789965 0.797046 0.018 Uiso 1 1 calc R U . . .
C10 C 0.2325(2) 0.5833(2) 0.62597(19) 0.0119(3) Uani 1 1 d . . . . .
C11 C 0.2079(2) 0.6497(2) 0.50170(19) 0.0137(3) Uani 1 1 d . . . . .
H11 H 0.182393 0.759988 0.520302 0.016 Uiso 1 1 calc R U . . .
C12 C 0.2204(2) 0.5577(2) 0.3568(2) 0.0143(3) Uani 1 1 d . . . . .
H12 H 0.205849 0.603571 0.275189 0.017 Uiso 1 1 calc R U . . .
C13 C 0.2554(2) 0.3936(2) 0.32996(18) 0.0123(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
O1 C1 1.199(2) . ?
O2 C1 1.3556(19) . ?
O2 C13 1.4037(19) . ?
N1 C2 1.265(2) . ?
N1 H1 0.94(2) . ?
Br1 C3 2.0085(16) . ?
C1 C2 1.516(2) . ?
C2 C3 1.496(2) . ?
C3 C4 1.491(2) . ?
C3 H3 1.0000 . ?
C4 C13 1.371(2) . ?
C4 C5 1.434(2) . ?
C5 C6 1.420(2) . ?
C5 C10 1.424(2) . ?
C6 C7 1.373(2) . ?
C6 H6 0.9500 . ?
C7 C8 1.410(2) . ?
C7 H7 0.9500 . ?
C8 C9 1.372(2) . ?
C8 H8 0.9500 . ?
C9 C10 1.419(2) . ?
C9 H9 0.9500 . ?
C10 C11 1.425(2) . ?
C11 C12 1.361(2) . ?
C11 H11 0.9500 . ?
C12 C13 1.407(2) . ?
C12 H12 0.9500 . ?

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
C1 O2 C13 121.61(12) . . ?
C2 N1 H1 110.8(13) . . ?
O1 C1 O2 118.98(15) . . ?
O1 C1 C2 123.56(15) . . ?
O2 C1 C2 117.46(13) . . ?
N1 C2 C3 121.38(15) . . ?
N1 C2 C1 121.45(15) . . ?
C3 C2 C1 117.13(13) . . ?
C4 C3 C2 112.95(13) . . ?
C4 C3 Br1 109.69(10) . . ?
C2 C3 Br1 103.42(10) . . ?
C4 C3 H3 110.2 . . ?
C2 C3 H3 110.2 . . ?
Br1 C3 H3 110.2 . . ?
C13 C4 C5 118.38(14) . . ?
C13 C4 C3 119.26(14) . . ?
C5 C4 C3 122.35(14) . . ?
C6 C5 C10 118.46(14) . . ?
C6 C5 C4 122.55(14) . . ?
C10 C5 C4 118.99(14) . . ?
C7 C6 C5 120.72(15) . . ?
C7 C6 H6 119.6 . . ?
C5 C6 H6 119.6 . . ?
C6 C7 C8 120.75(15) . . ?
C6 C7 H7 119.6 . . ?
C8 C7 H7 119.6 . . ?
C9 C8 C7 119.95(15) . . ?
C9 C8 H8 120.0 . . ?
C7 C8 H8 120.0 . . ?
C8 C9 C10 120.71(15) . . ?
C8 C9 H9 119.6 . . ?
C10 C9 H9 119.6 . . ?
C9 C10 C5 119.41(14) . . ?
C9 C10 C11 121.23(15) . . ?
C5 C10 C11 119.36(14) . . ?
C12 C11 C10 121.09(14) . . ?
C12 C11 H11 119.5 . . ?
C10 C11 H11 119.5 . . ?
C11 C12 C13 118.83(14) . . ?
C11 C12 H12 120.6 . . ?
C13 C12 H12 120.6 . . ?
C4 C13 O2 122.88(14) . . ?
C4 C13 C12 123.35(14) . . ?
O2 C13 C12 113.72(13) . . ?

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
C13 O2 C1 O1 -175.43(14) . . . . ?
C13 O2 C1 C2 3.7(2) . . . . ?
O1 C1 C2 N1 18.4(2) . . . . ?
O2 C1 C2 N1 -160.61(15) . . . . ?
O1 C1 C2 C3 -159.52(15) . . . . ?
O2 C1 C2 C3 21.4(2) . . . . ?
N1 C2 C3 C4 148.75(15) . . . . ?
C1 C2 C3 C4 -33.30(19) . . . . ?
N1 C2 C3 Br1 -92.76(16) . . . . ?
C1 C2 C3 Br1 85.20(14) . . . . ?
C2 C3 C4 C13 22.3(2) . . . . ?
Br1 C3 C4 C13 -92.47(15) . . . . ?
C2 C3 C4 C5 -158.90(14) . . . . ?
Br1 C3 C4 C5 86.32(15) . . . . ?
C13 C4 C5 C6 178.67(15) . . . . ?
C3 C4 C5 C6 -0.1(2) . . . . ?
C13 C4 C5 C10 -0.1(2) . . . . ?
C3 C4 C5 C10 -178.89(14) . . . . ?
C10 C5 C6 C7 -0.4(2) . . . . ?
C4 C5 C6 C7 -179.11(15) . . . . ?
C5 C6 C7 C8 -0.2(2) . . . . ?
C6 C7 C8 C9 0.4(3) . . . . ?
C7 C8 C9 C10 -0.1(2) . . . . ?
C8 C9 C10 C5 -0.4(2) . . . . ?
C8 C9 C10 C11 178.64(15) . . . . ?
C6 C5 C10 C9 0.6(2) . . . . ?
C4 C5 C10 C9 179.44(14) . . . . ?
C6 C5 C10 C11 -178.44(14) . . . . ?
C4 C5 C10 C11 0.4(2) . . . . ?
C9 C10 C11 C12 -179.91(15) . . . . ?
C5 C10 C11 C12 -0.9(2) . . . . ?
C10 C11 C12 C13 1.0(2) . . . . ?
C5 C4 C13 O2 -177.07(13) . . . . ?
C3 C4 C13 O2 1.8(2) . . . . ?
C5 C4 C13 C12 0.3(2) . . . . ?
C3 C4 C13 C12 179.11(14) . . . . ?
C1 O2 C13 C4 -16.1(2) . . . . ?
C1 O2 C13 C12 166.33(14) . . . . ?
C11 C12 C13 C4 -0.7(2) . . . . ?
C11 C12 C13 O2 176.82(14) . . . . ?

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
_geom_hbond_publ_flag
N1 H1 O1 0.94(2) 2.17(2) 3.0824(19) 163.9(18) 2_655 yes
C3 H3 N1 1.00 2.70 3.638(2) 157.0 2_656 yes

_refine_diff_density_max         0.413
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.064


_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1
_diffrn_radiation_source         ?
_diffrn_radiation_monochromator  ?
_chemical_absolute_configuration .
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# 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_TW2k
_database_code_depnum_ccdc_archive 'CCDC 1961069'
loop_
_audit_author_name
_audit_author_address
'Yuichiro Mutoh'
;Tokyo University of Science
Japan
;
_audit_update_record             
;
2019-10-24 deposited with the CCDC.	2019-11-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          539--540
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H19 N O6'
_chemical_formula_weight         381.37

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'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -z'

_cell_length_a                   8.7306(9)
_cell_length_b                   10.3043(10)
_cell_length_c                   11.4339(12)
_cell_angle_alpha                64.7120(10)
_cell_angle_beta                 83.5510(10)
_cell_angle_gamma                73.3560(10)
_cell_volume                     891.03(16)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)

_cell_measurement_reflns_used    4608

_cell_measurement_theta_min      2.27

_cell_measurement_theta_max      28.22


_exptl_crystal_description       prism

_exptl_crystal_colour            colourless

_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_F_000             400
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.22

_exptl_crystal_size_mid          0.203

_exptl_crystal_size_min          0.078

_exptl_absorpt_coefficient_mu    0.105
_shelx_estimated_absorpt_T_min   0.977
_shelx_estimated_absorpt_T_max   0.992
_exptl_absorpt_correction_type   multi-scan

_exptl_absorpt_correction_T_min  0.920

_exptl_absorpt_correction_T_max  0.992

_exptl_absorpt_process_details   'SADABS 2016/2'

_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)

_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\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            10013
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_av_R_equivalents  0.0180
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         1.970
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measured_fraction_theta_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_point_group_measured_fraction_full 0.995
_reflns_number_total             3975
_reflns_number_gt                3465
_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    'SHELXT-2018/2 (Sheldrick, 2018)'

_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'

_computing_publication_material  
;Yadokari-XG 2009 (Wakita,Nemoto et al., 2009)
;

_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)+(0.0450P)²+0.2854P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    ?

_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3975
_refine_ls_number_parameters     260
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0403
_refine_ls_R_factor_gt           0.0350
_refine_ls_wR_factor_ref         0.0943
_refine_ls_wR_factor_gt          0.0901
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_restrained_S_all      1.068
_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_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
O1 O 0.18167(10) 0.34057(9) 1.11759(8) 0.01777(19) Uani 1 1 d . . . . .
N1 N 0.14421(12) 0.57139(11) 0.84506(9) 0.0147(2) Uani 1 1 d . . . . .
H1 H 0.0420(18) 0.5847(16) 0.8745(14) 0.018 Uiso 1 1 d . U . . .
C1 C 0.18630(13) 0.65573(13) 0.72437(11) 0.0153(2) Uani 1 1 d . . . . .
H1A H 0.113214 0.731647 0.658717 0.018 Uiso 1 1 calc R U . . .
C2 C 0.35050(13) 0.61595(12) 0.71000(11) 0.0136(2) Uani 1 1 d . . . . .
C3 C 0.41171(13) 0.49820(12) 0.83068(11) 0.0125(2) Uani 1 1 d . . . . .
C4 C 0.56851(13) 0.40360(12) 0.88098(10) 0.0123(2) Uani 1 1 d . . . . .
C5 C 0.71280(13) 0.40998(12) 0.81178(11) 0.0135(2) Uani 1 1 d . . . . .
H5 H 0.710264 0.479019 0.723842 0.016 Uiso 1 1 calc R U . . .
C6 C 0.85665(13) 0.31780(13) 0.86986(11) 0.0143(2) Uani 1 1 d . . . . .
C7 C 0.86208(13) 0.21189(12) 1.00044(11) 0.0140(2) Uani 1 1 d . . . . .
C8 C 0.72170(13) 0.20154(12) 1.06906(11) 0.0139(2) Uani 1 1 d . . . . .
H8 H 0.723774 0.130331 1.156150 0.017 Uiso 1 1 calc R U . . .
C9 C 0.57728(13) 0.29716(12) 1.00844(11) 0.0127(2) Uani 1 1 d . . . . .
O2 O 0.44223(9) 0.27910(9) 1.08493(7) 0.01458(18) Uani 1 1 d . . . . .
C10 C 0.29073(13) 0.36562(12) 1.04161(11) 0.0133(2) Uani 1 1 d . . . . .
C11 C 0.28097(13) 0.47468(12) 0.91127(11) 0.0132(2) Uani 1 1 d . . . . .
O3 O 1.00212(9) 0.31953(9) 0.81097(8) 0.01822(19) Uani 1 1 d . . . . .
O4 O 1.01082(10) 0.12695(9) 1.04857(8) 0.01846(19) Uani 1 1 d . . . . .
C12 C 1.00019(15) 0.41437(14) 0.67681(12) 0.0221(3) Uani 1 1 d . . . . .
H12 H 0.942825 0.383040 0.628907 0.033 Uiso 1 1 calc R U . . .
H12A H 1.110186 0.408164 0.645700 0.033 Uiso 1 1 calc R U . . .
H12B H 0.946227 0.517238 0.663416 0.033 Uiso 1 1 calc R U . . .
C13 C 1.02120(15) 0.01890(14) 1.17988(12) 0.0208(3) Uani 1 1 d . . . . .
H13 H 0.974847 0.068977 1.236731 0.031 Uiso 1 1 calc R U . . .
H13A H 1.133589 -0.033570 1.203917 0.031 Uiso 1 1 calc R U . . .
H13B H 0.962266 -0.052731 1.188950 0.031 Uiso 1 1 calc R U . . .
C14 C 0.43561(13) 0.68499(12) 0.58909(11) 0.0131(2) Uani 1 1 d . . . . .
C15 C 0.39959(13) 0.68076(13) 0.47591(11) 0.0151(2) Uani 1 1 d . . . . .
H15 H 0.320076 0.633946 0.476534 0.018 Uiso 1 1 calc R U . . .
C16 C 0.47866(14) 0.74445(13) 0.36084(11) 0.0153(2) Uani 1 1 d . . . . .
H16 H 0.452602 0.740779 0.284040 0.018 Uiso 1 1 calc R U . . .
C17 C 0.59493(13) 0.81287(12) 0.35880(11) 0.0133(2) Uani 1 1 d . . . . .
C18 C 0.63165(13) 0.81966(12) 0.47284(11) 0.0132(2) Uani 1 1 d . . . . .
C19 C 0.55217(13) 0.75669(12) 0.58634(11) 0.0137(2) Uani 1 1 d . . . . .
H19 H 0.576487 0.761937 0.662879 0.016 Uiso 1 1 calc R U . . .
O5 O 0.68081(10) 0.87676(9) 0.25258(8) 0.01603(18) Uani 1 1 d . . . . .
O6 O 0.74640(10) 0.89186(9) 0.45972(8) 0.01785(19) Uani 1 1 d . . . . .
C20 C 0.64280(15) 0.87458(14) 0.13519(11) 0.0196(3) Uani 1 1 d . . . . .
H20 H 0.659056 0.771340 0.147706 0.029 Uiso 1 1 calc R U . . .
H20A H 0.712379 0.921423 0.066104 0.029 Uiso 1 1 calc R U . . .
H20B H 0.530913 0.929486 0.111269 0.029 Uiso 1 1 calc R U . . .
C21 C 0.77365(14) 0.91655(13) 0.56830(11) 0.0172(2) Uani 1 1 d . . . . .
H21 H 0.673950 0.974563 0.590402 0.026 Uiso 1 1 calc R U . . .
H21A H 0.855227 0.971442 0.546883 0.026 Uiso 1 1 calc R U . . .
H21B H 0.810498 0.820616 0.642245 0.026 Uiso 1 1 calc R U . . .


_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 C10 1.2212(13) . ?
N1 C1 1.3561(15) . ?
N1 C11 1.3670(14) . ?
N1 H1 0.911(15) . ?
C1 C2 1.3850(16) . ?
C1 H1A 0.9500 . ?
C2 C3 1.4233(15) . ?
C2 C14 1.4837(15) . ?
C3 C11 1.3935(15) . ?
C3 C4 1.4451(15) . ?
C4 C9 1.3943(16) . ?
C4 C5 1.4129(15) . ?
C5 C6 1.3732(16) . ?
C5 H5 0.9500 . ?
C6 O3 1.3702(13) . ?
C6 C7 1.4201(16) . ?
C7 O4 1.3612(13) . ?
C7 C8 1.3844(15) . ?
C8 C9 1.3937(15) . ?
C8 H8 0.9500 . ?
C9 O2 1.3946(13) . ?
O2 C10 1.3726(13) . ?
C10 C11 1.4262(16) . ?
O3 C12 1.4226(15) . ?
O4 C13 1.4307(14) . ?
C12 H12 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C13 H13 0.9800 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C14 C15 1.3867(16) . ?
C14 C19 1.4094(16) . ?
C15 C16 1.3985(16) . ?
C15 H15 0.9500 . ?
C16 C17 1.3852(16) . ?
C16 H16 0.9500 . ?
C17 O5 1.3659(13) . ?
C17 C18 1.4116(16) . ?
C18 O6 1.3702(14) . ?
C18 C19 1.3868(15) . ?
C19 H19 0.9500 . ?
O5 C20 1.4291(14) . ?
O6 C21 1.4260(14) . ?
C20 H20 0.9800 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C21 H21 0.9800 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?

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
C1 N1 C11 107.74(9) . . ?
C1 N1 H1 123.6(9) . . ?
C11 N1 H1 128.5(9) . . ?
N1 C1 C2 110.66(10) . . ?
N1 C1 H1A 124.7 . . ?
C2 C1 H1A 124.7 . . ?
C1 C2 C3 105.65(10) . . ?
C1 C2 C14 124.42(10) . . ?
C3 C2 C14 129.92(10) . . ?
C11 C3 C2 106.79(10) . . ?
C11 C3 C4 118.09(10) . . ?
C2 C3 C4 135.10(10) . . ?
C9 C4 C5 117.58(10) . . ?
C9 C4 C3 116.95(10) . . ?
C5 C4 C3 125.47(10) . . ?
C6 C5 C4 120.93(10) . . ?
C6 C5 H5 119.5 . . ?
C4 C5 H5 119.5 . . ?
O3 C6 C5 124.65(10) . . ?
O3 C6 C7 115.14(10) . . ?
C5 C6 C7 120.20(10) . . ?
O4 C7 C8 124.92(10) . . ?
O4 C7 C6 115.31(10) . . ?
C8 C7 C6 119.77(10) . . ?
C7 C8 C9 119.00(10) . . ?
C7 C8 H8 120.5 . . ?
C9 C8 H8 120.5 . . ?
C8 C9 C4 122.49(10) . . ?
C8 C9 O2 115.04(10) . . ?
C4 C9 O2 122.47(10) . . ?
C10 O2 C9 122.84(9) . . ?
O1 C10 O2 117.08(10) . . ?
O1 C10 C11 127.96(11) . . ?
O2 C10 C11 114.96(9) . . ?
N1 C11 C3 109.16(10) . . ?
N1 C11 C10 126.16(10) . . ?
C3 C11 C10 124.68(10) . . ?
C6 O3 C12 116.64(9) . . ?
C7 O4 C13 116.96(9) . . ?
O3 C12 H12 109.5 . . ?
O3 C12 H12A 109.5 . . ?
H12 C12 H12A 109.5 . . ?
O3 C12 H12B 109.5 . . ?
H12 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
O4 C13 H13 109.5 . . ?
O4 C13 H13A 109.5 . . ?
H13 C13 H13A 109.5 . . ?
O4 C13 H13B 109.5 . . ?
H13 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C15 C14 C19 118.93(10) . . ?
C15 C14 C2 119.87(10) . . ?
C19 C14 C2 121.20(10) . . ?
C14 C15 C16 120.94(11) . . ?
C14 C15 H15 119.5 . . ?
C16 C15 H15 119.5 . . ?
C17 C16 C15 120.04(10) . . ?
C17 C16 H16 120.0 . . ?
C15 C16 H16 120.0 . . ?
O5 C17 C16 124.95(10) . . ?
O5 C17 C18 115.34(10) . . ?
C16 C17 C18 119.71(10) . . ?
O6 C18 C19 125.18(10) . . ?
O6 C18 C17 115.00(10) . . ?
C19 C18 C17 119.82(10) . . ?
C18 C19 C14 120.54(10) . . ?
C18 C19 H19 119.7 . . ?
C14 C19 H19 119.7 . . ?
C17 O5 C20 116.32(9) . . ?
C18 O6 C21 116.74(9) . . ?
O5 C20 H20 109.5 . . ?
O5 C20 H20A 109.5 . . ?
H20 C20 H20A 109.5 . . ?
O5 C20 H20B 109.5 . . ?
H20 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
O6 C21 H21 109.5 . . ?
O6 C21 H21A 109.5 . . ?
H21 C21 H21A 109.5 . . ?
O6 C21 H21B 109.5 . . ?
H21 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?

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
C11 N1 C1 C2 -0.18(13) . . . . ?
N1 C1 C2 C3 0.45(13) . . . . ?
N1 C1 C2 C14 179.08(10) . . . . ?
C1 C2 C3 C11 -0.53(12) . . . . ?
C14 C2 C3 C11 -179.06(11) . . . . ?
C1 C2 C3 C4 177.63(12) . . . . ?
C14 C2 C3 C4 -0.9(2) . . . . ?
C11 C3 C4 C9 -1.34(15) . . . . ?
C2 C3 C4 C9 -179.35(12) . . . . ?
C11 C3 C4 C5 178.52(10) . . . . ?
C2 C3 C4 C5 0.5(2) . . . . ?
C9 C4 C5 C6 -2.14(16) . . . . ?
C3 C4 C5 C6 177.99(10) . . . . ?
C4 C5 C6 O3 -178.14(10) . . . . ?
C4 C5 C6 C7 1.31(17) . . . . ?
O3 C6 C7 O4 -0.11(14) . . . . ?
C5 C6 C7 O4 -179.61(10) . . . . ?
O3 C6 C7 C8 179.66(10) . . . . ?
C5 C6 C7 C8 0.16(17) . . . . ?
O4 C7 C8 C9 179.02(10) . . . . ?
C6 C7 C8 C9 -0.72(16) . . . . ?
C7 C8 C9 C4 -0.18(17) . . . . ?
C7 C8 C9 O2 -179.83(9) . . . . ?
C5 C4 C9 C8 1.59(16) . . . . ?
C3 C4 C9 C8 -178.53(10) . . . . ?
C5 C4 C9 O2 -178.79(9) . . . . ?
C3 C4 C9 O2 1.09(16) . . . . ?
C8 C9 O2 C10 178.75(10) . . . . ?
C4 C9 O2 C10 -0.90(16) . . . . ?
C9 O2 C10 O1 -179.35(9) . . . . ?
C9 O2 C10 C11 0.86(15) . . . . ?
C1 N1 C11 C3 -0.17(13) . . . . ?
C1 N1 C11 C10 -179.74(11) . . . . ?
C2 C3 C11 N1 0.44(13) . . . . ?
C4 C3 C11 N1 -178.09(9) . . . . ?
C2 C3 C11 C10 -179.98(10) . . . . ?
C4 C3 C11 C10 1.48(17) . . . . ?
O1 C10 C11 N1 -1.5(2) . . . . ?
O2 C10 C11 N1 178.30(10) . . . . ?
O1 C10 C11 C3 179.03(11) . . . . ?
O2 C10 C11 C3 -1.21(16) . . . . ?
C5 C6 O3 C12 -6.19(16) . . . . ?
C7 C6 O3 C12 174.34(10) . . . . ?
C8 C7 O4 C13 0.25(16) . . . . ?
C6 C7 O4 C13 180.00(10) . . . . ?
C1 C2 C14 C15 -58.65(16) . . . . ?
C3 C2 C14 C15 119.63(13) . . . . ?
C1 C2 C14 C19 120.71(13) . . . . ?
C3 C2 C14 C19 -61.01(16) . . . . ?
C19 C14 C15 C16 0.91(16) . . . . ?
C2 C14 C15 C16 -179.71(10) . . . . ?
C14 C15 C16 C17 0.07(17) . . . . ?
C15 C16 C17 O5 179.12(10) . . . . ?
C15 C16 C17 C18 -0.82(16) . . . . ?
O5 C17 C18 O6 1.10(14) . . . . ?
C16 C17 C18 O6 -178.95(9) . . . . ?
O5 C17 C18 C19 -179.38(9) . . . . ?
C16 C17 C18 C19 0.57(16) . . . . ?
O6 C18 C19 C14 179.89(10) . . . . ?
C17 C18 C19 C14 0.43(16) . . . . ?
C15 C14 C19 C18 -1.16(16) . . . . ?
C2 C14 C19 C18 179.47(10) . . . . ?
C16 C17 O5 C20 1.60(16) . . . . ?
C18 C17 O5 C20 -178.46(9) . . . . ?
C19 C18 O6 C21 -6.63(16) . . . . ?
C17 C18 O6 C21 172.86(9) . . . . ?

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
_geom_hbond_publ_flag
N1 H1 O1 0.911(15) 1.890(15) 2.7712(13) 162.0(13) 2_567 yes
C8 H8 O5 0.95 2.49 3.2011(14) 131.8 1_546 yes
C21 H21B O1 0.98 2.53 3.4152(15) 150.7 2_667 yes

_refine_diff_density_max         0.311
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.043


_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1
_diffrn_radiation_source         ?
_diffrn_radiation_monochromator  ?
_chemical_absolute_configuration ?
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: chloroform/MTBE'
####################################################################### 
# 
# 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_TW15902
_database_code_depnum_ccdc_archive 'CCDC 1961070'
loop_
_audit_author_name
_audit_author_address
'Yuichiro Mutoh'
;Tokyo University of Science
Japan
;
_audit_update_record             
;
2019-10-24 deposited with the CCDC.	2019-11-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          495
_chemical_formula_moiety         ?
_chemical_formula_sum            'C13 H11 N O3'
_chemical_formula_weight         229.23

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'

_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                   12.444(2)
_cell_length_b                   6.8139(11)
_cell_length_c                   25.885(4)
_cell_angle_alpha                90
_cell_angle_beta                 102.691(2)
_cell_angle_gamma                90
_cell_volume                     2141.3(6)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)

_cell_measurement_reflns_used    3029

_cell_measurement_theta_min      2.57

_cell_measurement_theta_max      27.26


_exptl_crystal_description       prism

_exptl_crystal_colour            colourless

_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_F_000             960
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.175

_exptl_crystal_size_mid          0.153

_exptl_crystal_size_min          0.061

_exptl_absorpt_coefficient_mu    0.102
_shelx_estimated_absorpt_T_min   0.983
_shelx_estimated_absorpt_T_max   0.994
_exptl_absorpt_correction_type   multi-scan

_exptl_absorpt_correction_T_min  0.896

_exptl_absorpt_correction_T_max  0.994

_exptl_absorpt_process_details   'SADABS 2016/2'

_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)

_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\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            11176
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         1.613
_diffrn_reflns_theta_max         27.270
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measured_fraction_theta_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             4693
_reflns_number_gt                3681
_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    'SHELXT-2018//2 (Sheldrick, 2018)'

_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'

_computing_publication_material  
;Yadokari-XG 2009 (Wakita,Nemoto et al., 2009)
;

_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)+(0.0523P)²+1.0215P] 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         4693
_refine_ls_number_parameters     315
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0479
_refine_ls_wR_factor_ref         0.1249
_refine_ls_wR_factor_gt          0.1168
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_restrained_S_all      1.054
_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_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 0.67690(12) 0.1961(2) 0.59673(6) 0.0178(3) Uani 1 1 d . . . . .
H1 H 0.6090(16) 0.205(3) 0.5730(7) 0.021 Uiso 1 1 d . U . . .
C1 C 0.69372(14) 0.1954(2) 0.65052(7) 0.0166(3) Uani 1 1 d . . . . .
H1A H 0.636813 0.193489 0.669700 0.020 Uiso 1 1 calc R U . . .
C2 C 0.80642(13) 0.1978(2) 0.67361(6) 0.0153(3) Uani 1 1 d . . . . .
C3 C 0.96747(13) 0.2010(3) 0.61463(6) 0.0174(4) Uani 1 1 d . . . . .
H3 H 1.010749 0.319491 0.628045 0.021 Uiso 1 1 calc R U . . .
H3A H 1.010717 0.082848 0.628344 0.021 Uiso 1 1 calc R U . . .
O1 O 0.93741(9) 0.20002(18) 0.55660(5) 0.0211(3) Uani 1 1 d . . . . .
C4 C 0.82513(14) 0.1980(3) 0.53847(7) 0.0194(4) Uani 1 1 d . . . . .
C5 C 0.85850(13) 0.2016(2) 0.63004(6) 0.0156(3) Uani 1 1 d . . . . .
C6 C 0.77822(13) 0.2003(2) 0.58466(6) 0.0163(3) Uani 1 1 d . . . . .
O2 O 0.78468(10) 0.1937(2) 0.49133(5) 0.0292(3) Uani 1 1 d . . . . .
C7 C 0.85985(13) 0.1977(2) 0.73035(6) 0.0146(3) Uani 1 1 d . . . . .
C8 C 0.80591(13) 0.1361(2) 0.76936(7) 0.0173(4) Uani 1 1 d . . . . .
H8 H 0.731994 0.091216 0.759295 0.021 Uiso 1 1 calc R U . . .
C9 C 0.85818(13) 0.1391(2) 0.82285(7) 0.0178(4) Uani 1 1 d . . . . .
H9 H 0.819616 0.098075 0.848829 0.021 Uiso 1 1 calc R U . . .
C10 C 0.96677(14) 0.2023(2) 0.83812(6) 0.0160(3) Uani 1 1 d . . . . .
C11 C 1.02242(14) 0.2625(2) 0.79944(6) 0.0164(3) Uani 1 1 d . . . . .
H11 H 1.096858 0.304631 0.809538 0.020 Uiso 1 1 calc R U . . .
C12 C 0.96962(13) 0.2609(2) 0.74665(6) 0.0159(3) Uani 1 1 d . . . . .
H12 H 1.008199 0.303447 0.720823 0.019 Uiso 1 1 calc R U . . .
O3 O 1.02701(10) 0.20923(18) 0.88929(4) 0.0210(3) Uani 1 1 d . . . . .
C13 C 0.96691(16) 0.2030(3) 0.93072(7) 0.0275(4) Uani 1 1 d . . . . .
H13 H 0.908287 0.301785 0.923863 0.041 Uiso 1 1 calc R U . . .
H13A H 1.017049 0.230375 0.964792 0.041 Uiso 1 1 calc R U . . .
H13B H 0.934406 0.072407 0.931759 0.041 Uiso 1 1 calc R U . . .
N2 N 0.58373(12) 0.2164(2) 0.41806(6) 0.0202(3) Uani 1 1 d . . . . .
H2 H 0.6519(16) 0.203(3) 0.4423(8) 0.024 Uiso 1 1 d . U . . .
C14 C 0.56581(14) 0.2150(2) 0.36420(7) 0.0197(4) Uani 1 1 d . . . . .
H14 H 0.621240 0.193626 0.344766 0.024 Uiso 1 1 calc R U . . .
C15 C 0.45502(14) 0.2491(2) 0.34151(7) 0.0168(4) Uani 1 1 d . . . . .
C16 C 0.29725(13) 0.2998(3) 0.40119(6) 0.0184(4) Uani 1 1 d . . . . .
H16 H 0.262566 0.426239 0.388047 0.022 Uiso 1 1 calc R U . . .
H16A H 0.245717 0.191603 0.387524 0.022 Uiso 1 1 calc R U . . .
O4 O 0.32786(10) 0.29703(19) 0.45910(5) 0.0234(3) Uani 1 1 d . . . . .
C17 C 0.43888(14) 0.2662(3) 0.47681(7) 0.0210(4) Uani 1 1 d . . . . .
C18 C 0.40460(13) 0.2732(2) 0.38518(7) 0.0169(4) Uani 1 1 d . . . . .
C19 C 0.48424(13) 0.2528(2) 0.43035(7) 0.0177(4) Uani 1 1 d . . . . .
O5 O 0.47912(10) 0.2551(2) 0.52380(5) 0.0300(3) Uani 1 1 d . . . . .
C20 C 0.40157(14) 0.2614(2) 0.28488(7) 0.0164(3) Uani 1 1 d . . . . .
C21 C 0.44909(14) 0.1857(2) 0.24508(7) 0.0191(4) Uani 1 1 d . . . . .
H21 H 0.518404 0.121466 0.254496 0.023 Uiso 1 1 calc R U . . .
C22 C 0.39696(14) 0.2022(2) 0.19172(7) 0.0198(4) Uani 1 1 d . . . . .
H22 H 0.430843 0.149870 0.165226 0.024 Uiso 1 1 calc R U . . .
C23 C 0.29504(14) 0.2958(2) 0.17734(7) 0.0182(4) Uani 1 1 d . . . . .
C24 C 0.24665(14) 0.3719(2) 0.21674(7) 0.0183(4) Uani 1 1 d . . . . .
H24 H 0.177258 0.435845 0.207339 0.022 Uiso 1 1 calc R U . . .
C25 C 0.29896(13) 0.3549(2) 0.26920(7) 0.0174(4) Uani 1 1 d . . . . .
H25 H 0.264768 0.407731 0.295527 0.021 Uiso 1 1 calc R U . . .
O6 O 0.23567(10) 0.31980(19) 0.12652(5) 0.0239(3) Uani 1 1 d . . . . .
C26 C 0.28157(18) 0.2450(3) 0.08447(7) 0.0301(5) Uani 1 1 d . . . . .
H26 H 0.353136 0.307046 0.085718 0.045 Uiso 1 1 calc R U . . .
H26A H 0.231750 0.274025 0.050414 0.045 Uiso 1 1 calc R U . . .
H26B H 0.291271 0.102666 0.088453 0.045 Uiso 1 1 calc R U . . .


_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 C1 1.362(2) . ?
N1 C6 1.364(2) . ?
N1 H1 0.931(19) . ?
C1 C2 1.399(2) . ?
C1 H1A 0.9500 . ?
C2 C5 1.419(2) . ?
C2 C7 1.473(2) . ?
C3 O1 1.4661(19) . ?
C3 C5 1.495(2) . ?
C3 H3 0.9900 . ?
C3 H3A 0.9900 . ?
O1 C4 1.373(2) . ?
C4 O2 1.214(2) . ?
C4 C6 1.441(2) . ?
C5 C6 1.365(2) . ?
C7 C8 1.394(2) . ?
C7 C12 1.406(2) . ?
C8 C9 1.395(2) . ?
C8 H8 0.9500 . ?
C9 C10 1.390(2) . ?
C9 H9 0.9500 . ?
C10 O3 1.3719(19) . ?
C10 C11 1.398(2) . ?
C11 C12 1.380(2) . ?
C11 H11 0.9500 . ?
C12 H12 0.9500 . ?
O3 C13 1.437(2) . ?
C13 H13 0.9800 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
N2 C14 1.363(2) . ?
N2 C19 1.367(2) . ?
N2 H2 0.94(2) . ?
C14 C15 1.394(2) . ?
C14 H14 0.9500 . ?
C15 C18 1.418(2) . ?
C15 C20 1.473(2) . ?
C16 O4 1.4634(19) . ?
C16 C18 1.494(2) . ?
C16 H16 0.9900 . ?
C16 H16A 0.9900 . ?
O4 C17 1.373(2) . ?
C17 O5 1.212(2) . ?
C17 C19 1.439(2) . ?
C18 C19 1.364(2) . ?
C20 C21 1.395(2) . ?
C20 C25 1.405(2) . ?
C21 C22 1.396(2) . ?
C21 H21 0.9500 . ?
C22 C23 1.395(2) . ?
C22 H22 0.9500 . ?
C23 O6 1.370(2) . ?
C23 C24 1.394(2) . ?
C24 C25 1.376(2) . ?
C24 H24 0.9500 . ?
C25 H25 0.9500 . ?
O6 C26 1.430(2) . ?
C26 H26 0.9800 . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?

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
C1 N1 C6 106.98(14) . . ?
C1 N1 H1 126.1(12) . . ?
C6 N1 H1 126.7(12) . . ?
N1 C1 C2 110.57(15) . . ?
N1 C1 H1A 124.7 . . ?
C2 C1 H1A 124.7 . . ?
C1 C2 C5 104.52(14) . . ?
C1 C2 C7 128.07(15) . . ?
C5 C2 C7 127.41(14) . . ?
O1 C3 C5 103.36(12) . . ?
O1 C3 H3 111.1 . . ?
C5 C3 H3 111.1 . . ?
O1 C3 H3A 111.1 . . ?
C5 C3 H3A 111.1 . . ?
H3 C3 H3A 109.1 . . ?
C4 O1 C3 111.21(12) . . ?
O2 C4 O1 120.68(15) . . ?
O2 C4 C6 132.85(16) . . ?
O1 C4 C6 106.47(14) . . ?
C6 C5 C2 107.96(15) . . ?
C6 C5 C3 107.80(14) . . ?
C2 C5 C3 144.22(15) . . ?
N1 C6 C5 109.97(15) . . ?
N1 C6 C4 138.84(15) . . ?
C5 C6 C4 111.15(15) . . ?
C8 C7 C12 117.73(15) . . ?
C8 C7 C2 122.59(15) . . ?
C12 C7 C2 119.67(14) . . ?
C7 C8 C9 121.40(15) . . ?
C7 C8 H8 119.3 . . ?
C9 C8 H8 119.3 . . ?
C10 C9 C8 119.93(15) . . ?
C10 C9 H9 120.0 . . ?
C8 C9 H9 120.0 . . ?
O3 C10 C9 125.17(15) . . ?
O3 C10 C11 115.44(14) . . ?
C9 C10 C11 119.38(15) . . ?
C12 C11 C10 120.25(15) . . ?
C12 C11 H11 119.9 . . ?
C10 C11 H11 119.9 . . ?
C11 C12 C7 121.29(15) . . ?
C11 C12 H12 119.4 . . ?
C7 C12 H12 119.4 . . ?
C10 O3 C13 117.13(14) . . ?
O3 C13 H13 109.5 . . ?
O3 C13 H13A 109.5 . . ?
H13 C13 H13A 109.5 . . ?
O3 C13 H13B 109.5 . . ?
H13 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C14 N2 C19 106.65(14) . . ?
C14 N2 H2 127.0(12) . . ?
C19 N2 H2 126.3(12) . . ?
N2 C14 C15 110.74(15) . . ?
N2 C14 H14 124.6 . . ?
C15 C14 H14 124.6 . . ?
C14 C15 C18 104.68(15) . . ?
C14 C15 C20 128.11(16) . . ?
C18 C15 C20 127.20(15) . . ?
O4 C16 C18 103.61(13) . . ?
O4 C16 H16 111.0 . . ?
C18 C16 H16 111.0 . . ?
O4 C16 H16A 111.0 . . ?
C18 C16 H16A 111.0 . . ?
H16 C16 H16A 109.0 . . ?
C17 O4 C16 111.12(13) . . ?
O5 C17 O4 120.55(16) . . ?
O5 C17 C19 133.11(16) . . ?
O4 C17 C19 106.34(14) . . ?
C19 C18 C15 107.83(15) . . ?
C19 C18 C16 107.46(15) . . ?
C15 C18 C16 144.54(15) . . ?
C18 C19 N2 110.11(15) . . ?
C18 C19 C17 111.43(15) . . ?
N2 C19 C17 138.38(16) . . ?
C21 C20 C25 117.42(15) . . ?
C21 C20 C15 122.82(15) . . ?
C25 C20 C15 119.76(15) . . ?
C20 C21 C22 121.39(16) . . ?
C20 C21 H21 119.3 . . ?
C22 C21 H21 119.3 . . ?
C23 C22 C21 119.92(16) . . ?
C23 C22 H22 120.0 . . ?
C21 C22 H22 120.0 . . ?
O6 C23 C24 115.45(15) . . ?
O6 C23 C22 125.31(15) . . ?
C24 C23 C22 119.24(16) . . ?
C25 C24 C23 120.28(15) . . ?
C25 C24 H24 119.9 . . ?
C23 C24 H24 119.9 . . ?
C24 C25 C20 121.76(15) . . ?
C24 C25 H25 119.1 . . ?
C20 C25 H25 119.1 . . ?
C23 O6 C26 117.84(14) . . ?
O6 C26 H26 109.5 . . ?
O6 C26 H26A 109.5 . . ?
H26 C26 H26A 109.5 . . ?
O6 C26 H26B 109.5 . . ?
H26 C26 H26B 109.5 . . ?
H26A C26 H26B 109.5 . . ?

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
C6 N1 C1 C2 -0.38(18) . . . . ?
N1 C1 C2 C5 0.42(18) . . . . ?
N1 C1 C2 C7 -179.92(15) . . . . ?
C5 C3 O1 C4 -0.61(17) . . . . ?
C3 O1 C4 O2 -178.80(16) . . . . ?
C3 O1 C4 C6 0.76(18) . . . . ?
C1 C2 C5 C6 -0.31(18) . . . . ?
C7 C2 C5 C6 -179.97(15) . . . . ?
C1 C2 C5 C3 -177.9(2) . . . . ?
C7 C2 C5 C3 2.4(3) . . . . ?
O1 C3 C5 C6 0.20(17) . . . . ?
O1 C3 C5 C2 177.8(2) . . . . ?
C1 N1 C6 C5 0.17(18) . . . . ?
C1 N1 C6 C4 177.8(2) . . . . ?
C2 C5 C6 N1 0.09(19) . . . . ?
C3 C5 C6 N1 178.61(13) . . . . ?
C2 C5 C6 C4 -178.26(14) . . . . ?
C3 C5 C6 C4 0.25(19) . . . . ?
O2 C4 C6 N1 1.2(4) . . . . ?
O1 C4 C6 N1 -178.28(19) . . . . ?
O2 C4 C6 C5 178.86(19) . . . . ?
O1 C4 C6 C5 -0.63(19) . . . . ?
C1 C2 C7 C8 20.0(3) . . . . ?
C5 C2 C7 C8 -160.40(16) . . . . ?
C1 C2 C7 C12 -160.19(16) . . . . ?
C5 C2 C7 C12 19.4(2) . . . . ?
C12 C7 C8 C9 0.8(2) . . . . ?
C2 C7 C8 C9 -179.44(15) . . . . ?
C7 C8 C9 C10 -0.8(2) . . . . ?
C8 C9 C10 O3 -179.11(15) . . . . ?
C8 C9 C10 C11 0.1(2) . . . . ?
O3 C10 C11 C12 179.87(14) . . . . ?
C9 C10 C11 C12 0.6(2) . . . . ?
C10 C11 C12 C7 -0.6(2) . . . . ?
C8 C7 C12 C11 -0.1(2) . . . . ?
C2 C7 C12 C11 -179.87(14) . . . . ?
C9 C10 O3 C13 -17.8(2) . . . . ?
C11 C10 O3 C13 162.96(15) . . . . ?
C19 N2 C14 C15 -0.34(19) . . . . ?
N2 C14 C15 C18 0.30(19) . . . . ?
N2 C14 C15 C20 179.27(15) . . . . ?
C18 C16 O4 C17 -1.81(18) . . . . ?
C16 O4 C17 O5 -178.39(16) . . . . ?
C16 O4 C17 C19 1.39(18) . . . . ?
C14 C15 C18 C19 -0.14(18) . . . . ?
C20 C15 C18 C19 -179.12(15) . . . . ?
C14 C15 C18 C16 -174.5(2) . . . . ?
C20 C15 C18 C16 6.6(4) . . . . ?
O4 C16 C18 C19 1.52(17) . . . . ?
O4 C16 C18 C15 175.8(2) . . . . ?
C15 C18 C19 N2 -0.06(19) . . . . ?
C16 C18 C19 N2 176.48(14) . . . . ?
C15 C18 C19 C17 -177.32(14) . . . . ?
C16 C18 C19 C17 -0.78(19) . . . . ?
C14 N2 C19 C18 0.24(19) . . . . ?
C14 N2 C19 C17 176.4(2) . . . . ?
O5 C17 C19 C18 179.4(2) . . . . ?
O4 C17 C19 C18 -0.36(19) . . . . ?
O5 C17 C19 N2 3.3(4) . . . . ?
O4 C17 C19 N2 -176.5(2) . . . . ?
C14 C15 C20 C21 18.9(3) . . . . ?
C18 C15 C20 C21 -162.35(16) . . . . ?
C14 C15 C20 C25 -160.27(17) . . . . ?
C18 C15 C20 C25 18.5(2) . . . . ?
C25 C20 C21 C22 0.1(2) . . . . ?
C15 C20 C21 C22 -179.08(15) . . . . ?
C20 C21 C22 C23 -0.1(2) . . . . ?
C21 C22 C23 O6 -179.52(15) . . . . ?
C21 C22 C23 C24 0.1(2) . . . . ?
O6 C23 C24 C25 179.64(14) . . . . ?
C22 C23 C24 C25 0.0(2) . . . . ?
C23 C24 C25 C20 0.0(3) . . . . ?
C21 C20 C25 C24 0.0(2) . . . . ?
C15 C20 C25 C24 179.20(15) . . . . ?
C24 C23 O6 C26 179.81(15) . . . . ?
C22 C23 O6 C26 -0.6(2) . . . . ?

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
_geom_hbond_publ_flag
N1 H1 O5 0.931(19) 1.86(2) 2.7823(19) 172.3(18) . yes
N2 H2 O2 0.94(2) 1.85(2) 2.7913(19) 176.3(19) . yes

_refine_diff_density_max         0.342
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.050


_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P2(1)/c
_diffrn_radiation_source         ?
_diffrn_radiation_monochromator  ?
_chemical_absolute_configuration ?
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: methylene chloride/hexane'
