# Electronic Supplementary Material (ESI) for Chemical Science.
# 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_data
_database_code_depnum_ccdc_archive 'CCDC 1888177'
loop_
_audit_author_name
_audit_author_address
'Krittanun Deekamwong'
;Tokyo Institute of Technology
Japan
;
_audit_update_record             
;
2019-01-01 deposited with the CCDC.	2019-10-14 downloaded from the CCDC.
;
_audit_creation_date             2018-12-17
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/1
_chemical_name_common            ?
_chemical_name_systematic        TPHAP
_chemical_formula_moiety         'C22 H13 N9'
_chemical_formula_sum            'C22 H13 N9'
_chemical_formula_weight         403.41
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C22 H12 N19'
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'

_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.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   21.083(3)
_cell_length_b                   7.0430(9)
_cell_length_c                   23.465(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3484.3(8)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    3834
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.0890
_cell_measurement_theta_min      1.9340
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74195
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    1.538
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.094
_exptl_crystal_size_mid          0.013
_exptl_crystal_size_min          0.010
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.2583
_diffrn_reflns_av_unetI/netI     0.1075
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            28788
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        23.254
_diffrn_reflns_theta_max         23.254
_diffrn_reflns_theta_min         1.736
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -110.00  70.00   0.50   60.00    --  -20.00  45.00   0.00  360
  2  ω   -110.00  70.00   0.50   60.00    --  -20.00  45.00  90.00  360
  3  ω   -110.00  70.00   0.50   60.00    --  -20.00  45.00 180.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0230610000
_diffrn_orient_matrix_UB_12      -0.0700002000
_diffrn_orient_matrix_UB_13      -0.0065580000
_diffrn_orient_matrix_UB_21      -0.0063265000
_diffrn_orient_matrix_UB_22      0.0119551000
_diffrn_orient_matrix_UB_23      -0.0294762000
_diffrn_orient_matrix_UB_31      0.0236597000
_diffrn_orient_matrix_UB_32      0.0713883000
_diffrn_orient_matrix_UB_33      -0.0014652000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1305
_reflns_number_total             2496
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     23.21
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.476
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.078
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         2496
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1495
_refine_ls_R_factor_gt           0.0666
_refine_ls_restrained_S_all      1.006
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0847P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1379
_refine_ls_wR_factor_ref         0.1886
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C21(H21), C22(H22), C24(H24), C25(H25),
 C27(H27), C28(H28), C30(H30), C31(H31), N8(H8)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
C2 C 0.2354(2) 0.4971(8) 0.6861(2) 0.0264(14) Uani 1 1 d . . . . .
H2 H 0.235260 0.451242 0.723267 0.032 Uiso 1 1 calc R . . . .
C3 C 0.2933(3) 0.5241(7) 0.6600(2) 0.0228(13) Uani 1 1 d . . . . .
H3 H 0.330693 0.495244 0.679183 0.027 Uiso 1 1 calc R . . . .
C4 C 0.2952(2) 0.5946(7) 0.6051(2) 0.0221(13) Uani 1 1 d . . . . .
C5 C 0.2377(2) 0.6296(8) 0.5784(2) 0.0238(13) Uani 1 1 d . . . . .
H5 H 0.236483 0.674541 0.541166 0.029 Uiso 1 1 calc R . . . .
C6 C 0.1823(2) 0.5964(7) 0.6082(2) 0.0261(14) Uani 1 1 d . . . . .
H6 H 0.144166 0.620489 0.589596 0.031 Uiso 1 1 calc R . . . .
C7 C 0.3554(2) 0.6328(7) 0.5734(2) 0.0215(13) Uani 1 1 d . . . . .
C9 C 0.4649(2) 0.6977(7) 0.5773(2) 0.0185(13) Uani 1 1 d . . . . .
C11 C 0.5700(2) 0.7722(7) 0.5730(2) 0.0195(13) Uani 1 1 d . . . . .
C13 C 0.5168(2) 0.7744(7) 0.4880(2) 0.0206(13) Uani 1 1 d . . . . .
C15 C 0.4577(2) 0.7666(7) 0.4065(2) 0.0187(13) Uani 1 1 d . . . . .
C17 C 0.4053(2) 0.6937(7) 0.4889(2) 0.0181(13) Uani 1 1 d . . . . .
C19 C 0.4624(2) 0.7200(7) 0.5182(2) 0.0180(13) Uani 1 1 d . . . . .
C20 C 0.6292(2) 0.8002(8) 0.6061(2) 0.0223(13) Uani 1 1 d . . . . .
C21 C 0.6321(3) 0.7603(7) 0.6634(2) 0.0264(14) Uani 1 1 d . . . . .
H21 H 0.596598 0.713493 0.682182 0.032 Uiso 1 1 calc R . . . .
C22 C 0.6880(3) 0.7897(8) 0.6930(2) 0.0299(15) Uani 1 1 d . . . . .
H22 H 0.688958 0.756774 0.731395 0.036 Uiso 1 1 calc R . . . .
C24 C 0.7371(3) 0.9079(9) 0.6145(2) 0.0392(16) Uani 1 1 d . . . . .
H24 H 0.772764 0.960194 0.597327 0.047 Uiso 1 1 calc R . . . .
C25 C 0.6833(3) 0.8813(9) 0.5817(3) 0.0371(16) Uani 1 1 d . . . . .
H25 H 0.683122 0.917252 0.543575 0.045 Uiso 1 1 calc R . . . .
C26 C 0.4516(2) 0.7924(7) 0.3439(2) 0.0206(13) Uani 1 1 d . . . . .
C27 C 0.3964(2) 0.7386(7) 0.3171(2) 0.0221(13) Uani 1 1 d . . . . .
H27 H 0.363813 0.681953 0.337761 0.027 Uiso 1 1 calc R . . . .
C28 C 0.3897(3) 0.7694(8) 0.2593(2) 0.0329(15) Uani 1 1 d . . . . .
H28 H 0.352379 0.728315 0.242103 0.039 Uiso 1 1 calc R . . . .
C30 C 0.4866(3) 0.9036(8) 0.2530(2) 0.0297(15) Uani 1 1 d . . . . .
H30 H 0.518016 0.961238 0.231241 0.036 Uiso 1 1 calc R . . . .
C31 C 0.4987(2) 0.8749(7) 0.3111(2) 0.0240(14) Uani 1 1 d . . . . .
H31 H 0.537242 0.910220 0.327109 0.029 Uiso 1 1 calc R . . . .
N1 N 0.1793(2) 0.5326(6) 0.66137(19) 0.0266(12) Uani 1 1 d . . . . .
N8 N 0.41038(19) 0.6508(6) 0.60394(17) 0.0219(11) Uani 1 1 d . . . . .
H8 H 0.410170 0.632248 0.640161 0.026 Uiso 1 1 calc R . . . .
N10 N 0.51975(19) 0.7183(6) 0.60547(17) 0.0213(11) Uani 1 1 d . . . . .
N12 N 0.57244(19) 0.8007(6) 0.51673(18) 0.0227(11) Uani 1 1 d . . . . .
N14 N 0.51481(19) 0.7985(6) 0.43036(17) 0.0212(11) Uani 1 1 d . . . . .
N16 N 0.40262(19) 0.7134(6) 0.43214(17) 0.0211(11) Uani 1 1 d . . . . .
N18 N 0.35054(19) 0.6505(6) 0.51797(17) 0.0208(11) Uani 1 1 d . . . . .
N23 N 0.7404(2) 0.8618(7) 0.6703(2) 0.0376(13) Uani 1 1 d . . . . .
N29 N 0.4325(2) 0.8531(6) 0.22663(17) 0.0256(12) 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
C2 H2 0.9300 . ?
C2 C3 1.379(7) . ?
C2 N1 1.341(6) . ?
C3 H3 0.9300 . ?
C3 C4 1.382(7) . ?
C4 C5 1.386(7) . ?
C4 C7 1.494(7) . ?
C5 H5 0.9300 . ?
C5 C6 1.382(7) . ?
C6 H6 0.9300 . ?
C6 N1 1.327(6) . ?
C7 N8 1.370(6) . ?
C7 N18 1.310(6) . ?
C9 C19 1.399(7) . ?
C9 N8 1.349(6) . ?
C9 N10 1.339(6) . ?
C11 C20 1.484(7) . ?
C11 N10 1.359(6) . ?
C11 N12 1.337(6) . ?
C13 C19 1.401(7) . ?
C13 N12 1.366(6) . ?
C13 N14 1.364(6) . ?
C15 C26 1.487(7) . ?
C15 N14 1.347(6) . ?
C15 N16 1.360(6) . ?
C17 C19 1.397(7) . ?
C17 N16 1.341(6) . ?
C17 N18 1.374(6) . ?
C20 C21 1.374(7) . ?
C20 C25 1.398(7) . ?
C21 H21 0.9300 . ?
C21 C22 1.384(7) . ?
C22 H22 0.9300 . ?
C22 N23 1.327(7) . ?
C24 H24 0.9300 . ?
C24 C25 1.384(7) . ?
C24 N23 1.349(7) . ?
C25 H25 0.9300 . ?
C26 C27 1.376(7) . ?
C26 C31 1.384(7) . ?
C27 H27 0.9300 . ?
C27 C28 1.380(7) . ?
C28 H28 0.9300 . ?
C28 N29 1.323(7) . ?
C30 H30 0.9300 . ?
C30 C31 1.401(7) . ?
C30 N29 1.345(6) . ?
C31 H31 0.9300 . ?
N8 H8 0.8600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 C2 H2 117.9 . . ?
N1 C2 H2 117.9 . . ?
N1 C2 C3 124.2(5) . . ?
C2 C3 H3 120.3 . . ?
C2 C3 C4 119.3(5) . . ?
C4 C3 H3 120.3 . . ?
C3 C4 C5 117.4(5) . . ?
C3 C4 C7 123.6(5) . . ?
C5 C4 C7 119.0(5) . . ?
C4 C5 H5 120.6 . . ?
C6 C5 C4 118.8(5) . . ?
C6 C5 H5 120.6 . . ?
C5 C6 H6 117.6 . . ?
N1 C6 C5 124.9(5) . . ?
N1 C6 H6 117.6 . . ?
N8 C7 C4 118.4(5) . . ?
N18 C7 C4 116.4(5) . . ?
N18 C7 N8 125.2(5) . . ?
N8 C9 C19 117.0(5) . . ?
N10 C9 C19 120.7(5) . . ?
N10 C9 N8 122.3(4) . . ?
N10 C11 C20 113.5(4) . . ?
N12 C11 C20 117.7(5) . . ?
N12 C11 N10 128.7(5) . . ?
N12 C13 C19 119.4(5) . . ?
N14 C13 C19 120.6(5) . . ?
N14 C13 N12 119.9(5) . . ?
N14 C15 C26 117.9(4) . . ?
N14 C15 N16 128.7(5) . . ?
N16 C15 C26 113.4(5) . . ?
N16 C17 C19 120.7(5) . . ?
N16 C17 N18 118.7(5) . . ?
N18 C17 C19 120.6(5) . . ?
C9 C19 C13 120.0(5) . . ?
C17 C19 C9 120.4(5) . . ?
C17 C19 C13 119.6(5) . . ?
C21 C20 C11 121.5(5) . . ?
C21 C20 C25 116.6(5) . . ?
C25 C20 C11 121.7(5) . . ?
C20 C21 H21 120.0 . . ?
C20 C21 C22 119.9(5) . . ?
C22 C21 H21 120.0 . . ?
C21 C22 H22 117.9 . . ?
N23 C22 C21 124.3(5) . . ?
N23 C22 H22 117.9 . . ?
C25 C24 H24 118.3 . . ?
N23 C24 H24 118.3 . . ?
N23 C24 C25 123.3(5) . . ?
C20 C25 H25 120.1 . . ?
C24 C25 C20 119.7(6) . . ?
C24 C25 H25 120.1 . . ?
C27 C26 C15 119.4(5) . . ?
C27 C26 C31 118.0(5) . . ?
C31 C26 C15 122.6(5) . . ?
C26 C27 H27 120.3 . . ?
C26 C27 C28 119.4(5) . . ?
C28 C27 H27 120.3 . . ?
C27 C28 H28 117.6 . . ?
N29 C28 C27 124.7(5) . . ?
N29 C28 H28 117.6 . . ?
C31 C30 H30 117.8 . . ?
N29 C30 H30 117.8 . . ?
N29 C30 C31 124.3(5) . . ?
C26 C31 C30 118.1(5) . . ?
C26 C31 H31 121.0 . . ?
C30 C31 H31 121.0 . . ?
C6 N1 C2 115.4(4) . . ?
C7 N8 H8 119.9 . . ?
C9 N8 C7 120.2(4) . . ?
C9 N8 H8 119.9 . . ?
C9 N10 C11 115.3(4) . . ?
C11 N12 C13 115.7(4) . . ?
C15 N14 C13 114.7(4) . . ?
C17 N16 C15 115.6(4) . . ?
C7 N18 C17 116.6(4) . . ?
C22 N23 C24 116.0(5) . . ?
C28 N29 C30 115.4(5) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.491
_oxdiff_exptl_absorpt_empirical_full_min 0.568
_exptl_crystal_recrystallization_method 'Vapour deposition'
