# Electronic Supplementary Material (ESI) for Nanoscale.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# 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_shelxl
_database_code_depnum_ccdc_archive 'CCDC 2130942'
loop_
_audit_author_name
_audit_author_address
'Kun Liu'
;Tianjin University
China
;
_audit_update_record             
;
2021-12-26 deposited with the CCDC.	2022-03-31 downloaded from the CCDC.
;
_audit_creation_date             2021-05-05
_audit_creation_method           
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C10 H2 N4, C12 H7 Br S'
_chemical_formula_sum            'C22 H9 Br N4 S'
_chemical_formula_weight         441.30
_chemical_melting_point          ?
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'
Br Br -0.2901 2.4595 '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'
S S 0.1246 0.1234 '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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.5508(15)
_cell_length_b                   8.0138(16)
_cell_length_c                   8.1390(16)
_cell_angle_alpha                85.38(3)
_cell_angle_beta                 77.75(3)
_cell_angle_gamma                75.07(3)
_cell_volume                     464.86(18)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    1316
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      27.8028
_cell_measurement_theta_min      2.5618
_shelx_estimated_absorpt_T_max   0.767
_shelx_estimated_absorpt_T_min   0.652
_exptl_absorpt_coefficient_mu    2.338
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.7491
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   crystalclear
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.576
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             220
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0725
_diffrn_reflns_av_unetI/netI     0.0925
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            4344
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.019
_diffrn_reflns_theta_max         25.019
_diffrn_reflns_theta_min         2.562
_diffrn_ambient_temperature      113.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1154
_reflns_number_total             1611
_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       crystalclear
_computing_data_collection       crystalclear
_computing_data_reduction        crystalclear
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_refine_diff_density_max         1.308
_refine_diff_density_min         -0.631
_refine_diff_density_rms         0.119
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     167
_refine_ls_number_reflns         1611
_refine_ls_number_restraints     64
_refine_ls_R_factor_all          0.1201
_refine_ls_R_factor_gt           0.0966
_refine_ls_restrained_S_all      1.081
_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)+(0.1336P)²+1.4248P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2469
_refine_ls_wR_factor_ref         0.2613
_refine_special_details          
;
 Refined as a 2-component twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.9879(15)
 0.0121(15)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 S1-C6 = S1-C17
 1.68 with sigma of 0.01
 C11-C12
 1.54 with sigma of 0.01
 C15-Br1
 1.88 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C9) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
5. Rigid body (RIGU) restrains
 C7, C6, C11, C10, C9, C8
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: C6(0.5) C7(0.5) H7(0.5) C8(0.5) H8(0.5) C9(0.5) H9(0.5) C10(0.5)
 H10(0.5) C11(0.5) Br1(0.5) S1(0.5) C12(0.5) C13(0.5) H13(0.5) C14(0.5)
 H14(0.5) C15(0.5) C16(0.5) H16(0.5) C17(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14), C16(H16)
7.b Fitted hexagon refined as free rotating group:
 C6(C7,C8,C9,C10,C11), C12(C13,C14,C15,C16,C17)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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
N1 N 0.3309(9) 0.5018(8) 0.3875(9) 0.0429(17) Uani 1 1 d . . . . .
N2 N 0.9717(8) -0.1719(8) 0.6780(8) 0.0366(15) Uani 1 1 d . . . . .
C1 C 0.3770(9) 0.3583(9) 0.4215(9) 0.0308(16) Uani 1 1 d . . . . .
C2 C 0.4418(9) 0.1750(8) 0.4609(8) 0.0243(14) Uani 1 1 d . . . . .
C3 C 0.6044(8) 0.1171(8) 0.5254(8) 0.0229(14) Uani 1 1 d . . . . .
H3 H 0.673321 0.195637 0.543014 0.027 Uiso 1 1 calc R U . . .
C4 C 0.6643(8) -0.0606(8) 0.5639(8) 0.0238(14) Uani 1 1 d . . . . .
C5 C 0.8348(9) -0.1234(8) 0.6274(8) 0.0247(14) Uani 1 1 d . . . . .
C6 C 0.6512(12) 0.7303(14) 0.0914(15) 0.030(4) Uani 0.5 1 d DG . P A -1
C7 C 0.7777(14) 0.5952(10) 0.1542(14) 0.039(3) Uani 0.5 1 d G . P A -1
H7 H 0.760693 0.481266 0.160965 0.046 Uiso 0.5 1 calc R U P A -1
C8 C 0.9291(11) 0.6268(11) 0.2072(13) 0.026(3) Uani 0.5 1 d G U P A -1
H8 H 1.015543 0.534410 0.250112 0.031 Uiso 0.5 1 calc R U P A -1
C9 C 0.9539(11) 0.7935(12) 0.1973(13) 0.035(3) Uani 0.5 1 d G U P A -1
H9 H 1.057408 0.815055 0.233486 0.042 Uiso 0.5 1 calc R U P A -1
C10 C 0.8274(13) 0.9286(9) 0.1345(12) 0.029(3) Uani 0.5 1 d G . P A -1
H10 H 0.844421 1.042557 0.127714 0.035 Uiso 0.5 1 calc R U P A -1
C11 C 0.6760(12) 0.8971(12) 0.0815(13) 0.038(3) Uani 0.5 1 d DG . P A -1
Br1 Br 0.0103(3) 1.3332(2) -0.2093(2) 0.0454(6) Uani 0.5 1 d D . P A -1
S1 S 0.4584(6) 0.7214(5) 0.0177(5) 0.0371(10) Uani 0.5 1 d D . P A -1
C12 C 0.5261(10) 1.0254(9) 0.0092(14) 0.024(4) Uani 0.5 1 d DG U P A -1
C13 C 0.4942(13) 1.2033(9) -0.0170(15) 0.040(4) Uani 0.5 1 d G . P A -1
H13 H 0.578551 1.262613 0.008660 0.048 Uiso 0.5 1 calc R U P A -1
C14 C 0.3391(15) 1.2945(7) -0.0807(16) 0.046(7) Uani 0.5 1 d G . P A -1
H14 H 0.317289 1.416115 -0.098645 0.056 Uiso 0.5 1 calc R U P A -1
C15 C 0.2157(11) 1.2078(10) -0.1182(14) 0.035(3) Uani 0.5 1 d DG . P A -1
C16 C 0.2475(10) 1.0299(10) -0.0920(12) 0.034(3) Uani 0.5 1 d G . P A -1
H16 H 0.163239 0.970636 -0.117652 0.041 Uiso 0.5 1 calc R U P A -1
C17 C 0.4027(11) 0.9387(7) -0.0283(13) 0.030(3) Uani 0.5 1 d DG U P A -1


_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 1.142(9) . ?
N2 C5 1.156(9) . ?
C1 C2 1.456(9) . ?
C2 C3 1.392(9) . ?
C2 C4 1.414(9) 2_656 ?
C3 H3 0.9500 . ?
C3 C4 1.410(9) . ?
C4 C5 1.444(9) . ?
C6 C7 1.3900 . ?
C6 C11 1.3900 . ?
C6 S1 1.708(6) . ?
C7 H7 0.9500 . ?
C7 C8 1.3900 . ?
C8 H8 0.9500 . ?
C8 C9 1.3900 . ?
C9 H9 0.9500 . ?
C9 C10 1.3900 . ?
C10 H10 0.9500 . ?
C10 C11 1.3900 . ?
C11 C12 1.507(7) . ?
Br1 C15 1.879(5) . ?
S1 C17 1.713(6) . ?
C12 C13 1.3900 . ?
C12 C17 1.3900 . ?
C13 H13 0.9500 . ?
C13 C14 1.3900 . ?
C14 H14 0.9500 . ?
C14 C15 1.3900 . ?
C15 C16 1.3900 . ?
C16 H16 0.9500 . ?
C16 C17 1.3900 . ?

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
N1 C1 C2 178.0(8) . . ?
C3 C2 C1 119.2(6) . . ?
C3 C2 C4 121.6(6) . 2_656 ?
C4 C2 C1 119.1(6) 2_656 . ?
C2 C3 H3 120.8 . . ?
C2 C3 C4 118.5(6) . . ?
C4 C3 H3 120.8 . . ?
C2 C4 C5 120.9(6) 2_656 . ?
C3 C4 C2 119.9(6) . 2_656 ?
C3 C4 C5 119.2(6) . . ?
N2 C5 C4 179.2(7) . . ?
C7 C6 C11 120.0 . . ?
C7 C6 S1 128.0(6) . . ?
C11 C6 S1 112.0(6) . . ?
C6 C7 H7 120.0 . . ?
C6 C7 C8 120.0 . . ?
C8 C7 H7 120.0 . . ?
C7 C8 H8 120.0 . . ?
C9 C8 C7 120.0 . . ?
C9 C8 H8 120.0 . . ?
C8 C9 H9 120.0 . . ?
C8 C9 C10 120.0 . . ?
C10 C9 H9 120.0 . . ?
C9 C10 H10 120.0 . . ?
C9 C10 C11 120.0 . . ?
C11 C10 H10 120.0 . . ?
C6 C11 C12 112.3(7) . . ?
C10 C11 C6 120.0 . . ?
C10 C11 C12 127.7(7) . . ?
C6 S1 C17 93.0(5) . . ?
C13 C12 C11 131.2(6) . . ?
C13 C12 C17 120.0 . . ?
C17 C12 C11 108.7(6) . . ?
C12 C13 H13 120.0 . . ?
C12 C13 C14 120.0 . . ?
C14 C13 H13 120.0 . . ?
C13 C14 H14 120.0 . . ?
C15 C14 C13 120.0 . . ?
C15 C14 H14 120.0 . . ?
C14 C15 Br1 119.2(5) . . ?
C14 C15 C16 120.0 . . ?
C16 C15 Br1 120.8(5) . . ?
C15 C16 H16 120.0 . . ?
C17 C16 C15 120.0 . . ?
C17 C16 H16 120.0 . . ?
C12 C17 S1 114.0(5) . . ?
C16 C17 S1 126.0(5) . . ?
C16 C17 C12 120.0 . . ?

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
C1 C2 C3 C4 179.6(6) . . . . ?
C2 C3 C4 C2 -0.9(10) . . . 2_656 ?
C2 C3 C4 C5 178.7(6) . . . . ?
C4 C2 C3 C4 1.0(10) 2_656 . . . ?
C6 C7 C8 C9 0.0 . . . . ?
C6 C11 C12 C13 177.5(8) . . . . ?
C6 C11 C12 C17 -0.1(9) . . . . ?
C6 S1 C17 C12 0.2(7) . . . . ?
C6 S1 C17 C16 -177.7(8) . . . . ?
C7 C6 C11 C10 0.0 . . . . ?
C7 C6 C11 C12 179.6(9) . . . . ?
C7 C6 S1 C17 -179.5(7) . . . . ?
C7 C8 C9 C10 0.0 . . . . ?
C8 C9 C10 C11 0.0 . . . . ?
C9 C10 C11 C6 0.0 . . . . ?
C9 C10 C11 C12 -179.5(11) . . . . ?
C10 C11 C12 C13 -2.9(15) . . . . ?
C10 C11 C12 C17 179.4(7) . . . . ?
C11 C6 C7 C8 0.0 . . . . ?
C11 C6 S1 C17 -0.2(6) . . . . ?
C11 C12 C13 C14 -177.4(12) . . . . ?
C11 C12 C17 S1 -0.1(8) . . . . ?
C11 C12 C17 C16 178.0(10) . . . . ?
Br1 C15 C16 C17 178.5(8) . . . . ?
S1 C6 C7 C8 179.2(10) . . . . ?
S1 C6 C11 C10 -179.3(9) . . . . ?
S1 C6 C11 C12 0.3(8) . . . . ?
C12 C13 C14 C15 0.0 . . . . ?
C13 C12 C17 S1 -178.0(8) . . . . ?
C13 C12 C17 C16 0.0 . . . . ?
C13 C14 C15 Br1 -178.5(8) . . . . ?
C13 C14 C15 C16 0.0 . . . . ?
C14 C15 C16 C17 0.0 . . . . ?
C15 C16 C17 S1 177.8(9) . . . . ?
C15 C16 C17 C12 0.0 . . . . ?
C17 C12 C13 C14 0.0 . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.9879(15)
2 0.0121(15)

####################################################################### 
# 
# 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_shelxl_CCDC1
_database_code_depnum_ccdc_archive 'CCDC 2130945'
loop_
_audit_author_name
_audit_author_address
'Kun Liu'
;Tianjin University
China
;
_audit_update_record             
;
2021-12-26 deposited with the CCDC.	2022-03-31 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          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H9 Br N4 S'
_chemical_formula_weight         441.30

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 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'
S S 0.1246 0.1234 '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      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                   7.4921(15)
_cell_length_b                   8.1212(16)
_cell_length_c                   30.277(6)
_cell_angle_alpha                90
_cell_angle_beta                 92.33(3)
_cell_angle_gamma                90
_cell_volume                     1840.6(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    113(2)
_cell_measurement_reflns_used    3239
_cell_measurement_theta_min      1.3463
_cell_measurement_theta_max      27.8545

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_F_000             880
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    2.362
_shelx_estimated_absorpt_T_min   0.649
_shelx_estimated_absorpt_T_max   0.765
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.5777
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   crystalclear
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      113(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'rigaku saturn'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            14182
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_av_R_equivalents  0.0691
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_theta_min         2.597
_diffrn_reflns_theta_max         25.019
_diffrn_reflns_theta_full        25.019
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3235
_reflns_number_gt                2289
_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       crystalclear
_computing_cell_refinement       crystalclear
_computing_data_reduction        crystalclear
_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          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0800P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.0103(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3235
_refine_ls_number_parameters     333
_refine_ls_number_restraints     268
_refine_ls_R_factor_all          0.0817
_refine_ls_R_factor_gt           0.0551
_refine_ls_wR_factor_ref         0.1506
_refine_ls_wR_factor_gt          0.1379
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_restrained_S_all      1.099
_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 0.1470(4) 0.3249(4) 0.00255(10) 0.0456(8) Uani 1 1 d . . . . .
N2 N -0.1522(5) 0.8195(4) 0.16801(11) 0.0526(9) Uani 1 1 d . . . . .
N3 N -0.1535(5) 0.4433(5) 0.24932(11) 0.0700(11) Uani 1 1 d . . . . .
N4 N 0.1202(5) -0.0641(4) 0.08102(11) 0.0504(8) Uani 1 1 d . . . . .
C1 C 0.1019(5) 0.3387(4) 0.03812(12) 0.0359(8) Uani 1 1 d . . . . .
C2 C 0.0452(4) 0.3593(4) 0.08287(10) 0.0299(8) Uani 1 1 d . . . . .
C3 C -0.0041(4) 0.5136(4) 0.09769(10) 0.0315(8) Uani 1 1 d . . . . .
H3A H -0.001375 0.606143 0.078555 0.038 Uiso 1 1 calc R U . . .
C4 C -0.0575(4) 0.5313(4) 0.14062(10) 0.0317(8) Uani 1 1 d . . . . .
C5 C -0.0621(4) 0.3941(4) 0.16907(11) 0.0340(8) Uani 1 1 d . . . . .
C6 C -0.0148(5) 0.2409(4) 0.15422(11) 0.0351(8) Uani 1 1 d . . . . .
H6A H -0.017829 0.148301 0.173346 0.042 Uiso 1 1 calc R U . . .
C7 C 0.0376(4) 0.2226(4) 0.11091(11) 0.0311(8) Uani 1 1 d . . . . .
C8 C 0.0842(5) 0.0606(5) 0.09428(11) 0.0370(8) Uani 1 1 d . . . . .
C9 C -0.1108(5) 0.6916(5) 0.15618(12) 0.0399(9) Uani 1 1 d . . . . .
C10 C -0.1146(5) 0.4186(5) 0.21396(12) 0.0462(10) Uani 1 1 d . . . . .
C11 C 0.562(3) 0.3480(11) 0.0784(4) 0.051(4) Uani 0.4066(12) 1 d DG U P A 1
C12 C 0.618(3) 0.3650(10) 0.0355(3) 0.048(3) Uani 0.4066(12) 1 d G U P A 1
H12A H 0.613209 0.469564 0.021435 0.058 Uiso 0.4066(12) 1 calc R U P A 1
C13 C 0.6820(18) 0.2290(12) 0.0132(3) 0.036(3) Uani 0.4066(12) 1 d G . P A 1
H13A H 0.720557 0.240638 -0.016189 0.043 Uiso 0.4066(12) 1 calc R U P A 1
C14 C 0.6894(17) 0.0760(10) 0.0337(3) 0.036(3) Uani 0.4066(12) 1 d G U P A 1
H14A H 0.732936 -0.016893 0.018462 0.043 Uiso 0.4066(12) 1 calc R U P A 1
C15 C 0.633(2) 0.0591(10) 0.0767(3) 0.040(3) Uani 0.4066(12) 1 d G U P A 1
H15A H 0.637966 -0.045500 0.090738 0.049 Uiso 0.4066(12) 1 calc R U P A 1
C16 C 0.569(3) 0.1950(12) 0.0990(3) 0.038(3) Uani 0.4066(12) 1 d DG U P A 1
Br1 Br 0.33904(16) 0.74492(14) 0.17598(4) 0.0615(5) Uani 0.4066(12) 1 d . . P A
1
S1 S 0.4974(3) 0.5326(3) 0.09149(8) 0.0354(6) Uani 0.4066(12) 1 d . . P A 1
C17 C 0.4934(8) 0.2744(8) 0.14333(16) 0.0337(18) Uani 0.4066(12) 1 d DG U P A 1
C18 C 0.4572(11) 0.4422(8) 0.1419(2) 0.027(2) Uani 0.4066(12) 1 d G U P A 1
C19 C 0.3930(12) 0.5209(6) 0.1789(3) 0.036(2) Uani 0.4066(12) 1 d G U P A 1
C20 C 0.3650(10) 0.4318(9) 0.2171(2) 0.055(2) Uani 0.4066(12) 1 d G U P A 1
H20A H 0.321086 0.485567 0.242366 0.066 Uiso 0.4066(12) 1 calc R U P A 1
C21 C 0.4012(9) 0.2640(8) 0.21853(16) 0.051(2) Uani 0.4066(12) 1 d G U P A 1
H21A H 0.381996 0.203029 0.244699 0.061 Uiso 0.4066(12) 1 calc R U P A 1
C22 C 0.4654(9) 0.1853(6) 0.1816(2) 0.046(2) Uani 0.4066(12) 1 d G U P A 1
H22A H 0.490097 0.070563 0.182571 0.055 Uiso 0.4066(12) 1 calc R U P A 1
Br1' Br 0.33863(11) 0.38319(12) 0.24105(2) 0.0672(4) Uani 0.5934(12) 1 d . . P
A 2
S1' S 0.5020(2) 0.1704(2) 0.15658(6) 0.0405(5) Uani 0.5934(12) 1 d . . P A 2
C11' C 0.561(2) 0.1860(9) 0.1044(2) 0.053(3) Uani 0.5934(12) 1 d DG U P A 2
C12' C 0.6137(17) 0.0348(7) 0.0879(3) 0.062(3) Uani 0.5934(12) 1 d G U P A 2
H12B H 0.610351 -0.060726 0.105920 0.074 Uiso 0.5934(12) 1 calc R U P A 2
C13' C 0.6717(13) 0.0233(7) 0.0449(3) 0.052(3) Uani 0.5934(12) 1 d G . P A 2
H13B H 0.707969 -0.080056 0.033666 0.062 Uiso 0.5934(12) 1 calc R U P A 2
C14' C 0.6767(13) 0.1631(9) 0.0185(2) 0.056(3) Uani 0.5934(12) 1 d G U P A 2
H14B H 0.716306 0.155218 -0.010819 0.067 Uiso 0.5934(12) 1 calc R U P A 2
C15' C 0.6236(17) 0.3143(7) 0.0350(2) 0.050(2) Uani 0.5934(12) 1 d G U P A 2
H15B H 0.627024 0.409824 0.016950 0.060 Uiso 0.5934(12) 1 calc R U P A 2
C16' C 0.566(2) 0.3258(7) 0.0779(3) 0.039(2) Uani 0.5934(12) 1 d DG U P A 2
C17' C 0.4951(5) 0.4492(5) 0.11263(13) 0.0299(12) Uani 0.5934(12) 1 d DG U P A
2
C18' C 0.4652(6) 0.6161(5) 0.10525(12) 0.0426(16) Uani 0.5934(12) 1 d G U P A 2
H18A H 0.490461 0.663391 0.077498 0.051 Uiso 0.5934(12) 1 calc R U P A 2
C19' C 0.3983(6) 0.7136(4) 0.13847(15) 0.0490(16) Uani 0.5934(12) 1 d G U P A 2
H19A H 0.377855 0.827658 0.133430 0.059 Uiso 0.5934(12) 1 calc R U P A 2
C20' C 0.3614(6) 0.6444(6) 0.17908(13) 0.0533(18) Uani 0.5934(12) 1 d G U P A 2
H20B H 0.315650 0.711054 0.201784 0.064 Uiso 0.5934(12) 1 calc R U P A 2
C21' C 0.3913(8) 0.4775(6) 0.18646(12) 0.0377(18) Uani 0.5934(12) 1 d G U P A 2
C22' C 0.4582(7) 0.3799(4) 0.15323(16) 0.0300(15) Uani 0.5934(12) 1 d G U P A 2


_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 1.147(4) . ?
N2 C9 1.146(4) . ?
N3 C10 1.139(4) . ?
N4 C8 1.126(4) . ?
C1 C2 1.446(5) . ?
C2 C3 1.386(4) . ?
C2 C7 1.400(4) . ?
C3 C4 1.383(4) . ?
C3 H3A 0.9500 . ?
C4 C5 1.410(5) . ?
C4 C9 1.446(5) . ?
C5 C6 1.374(5) . ?
C5 C10 1.444(5) . ?
C6 C7 1.392(4) . ?
C6 H6A 0.9500 . ?
C7 C8 1.456(5) . ?
C11 C12 1.3900 . ?
C11 C16 1.3900 . ?
C11 S1 1.628(8) . ?
C12 C13 1.3900 . ?
C12 H12A 0.9500 . ?
C13 C14 1.3900 . ?
C13 H13A 0.9500 . ?
C14 C15 1.3900 . ?
C14 H14A 0.9500 . ?
C15 C16 1.3900 . ?
C15 H15A 0.9500 . ?
C16 C17 1.612(7) . ?
Br1 C19 1.865(5) . ?
S1 C18 1.732(5) . ?
C17 C18 1.3900 . ?
C17 C22 1.3900 . ?
C18 C19 1.3900 . ?
C19 C20 1.3900 . ?
C20 C21 1.3900 . ?
C20 H20A 0.9500 . ?
C21 C22 1.3900 . ?
C21 H21A 0.9500 . ?
C22 H22A 0.9500 . ?
Br1' C21' 1.878(3) . ?
S1' C11' 1.663(6) . ?
S1' C22' 1.736(4) . ?
C11' C12' 1.3900 . ?
C11' C16' 1.3900 . ?
C12' C13' 1.3900 . ?
C12' H12B 0.9500 . ?
C13' C14' 1.3900 . ?
C13' H13B 0.9500 . ?
C14' C15' 1.3900 . ?
C14' H14B 0.9500 . ?
C15' C16' 1.3900 . ?
C15' H15B 0.9500 . ?
C16' C17' 1.560(5) . ?
C17' C18' 1.3900 . ?
C17' C22' 1.3900 . ?
C18' C19' 1.3900 . ?
C18' H18A 0.9500 . ?
C19' C20' 1.3900 . ?
C19' H19A 0.9500 . ?
C20' C21' 1.3900 . ?
C20' H20B 0.9500 . ?
C21' C22' 1.3900 . ?

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
N1 C1 C2 179.0(4) . . ?
C3 C2 C7 120.1(3) . . ?
C3 C2 C1 120.0(3) . . ?
C7 C2 C1 119.8(3) . . ?
C4 C3 C2 119.3(3) . . ?
C4 C3 H3A 120.3 . . ?
C2 C3 H3A 120.3 . . ?
C3 C4 C5 120.5(3) . . ?
C3 C4 C9 119.6(3) . . ?
C5 C4 C9 119.9(3) . . ?
C6 C5 C4 120.2(3) . . ?
C6 C5 C10 121.1(3) . . ?
C4 C5 C10 118.7(3) . . ?
C5 C6 C7 119.4(3) . . ?
C5 C6 H6A 120.3 . . ?
C7 C6 H6A 120.3 . . ?
C6 C7 C2 120.5(3) . . ?
C6 C7 C8 120.2(3) . . ?
C2 C7 C8 119.4(3) . . ?
N4 C8 C7 179.3(4) . . ?
N2 C9 C4 179.1(4) . . ?
N3 C10 C5 177.6(4) . . ?
C12 C11 C16 120.0 . . ?
C12 C11 S1 103.9(5) . . ?
C16 C11 S1 136.1(5) . . ?
C13 C12 C11 120.0 . . ?
C13 C12 H12A 120.0 . . ?
C11 C12 H12A 120.0 . . ?
C14 C13 C12 120.0 . . ?
C14 C13 H13A 120.0 . . ?
C12 C13 H13A 120.0 . . ?
C13 C14 C15 120.0 . . ?
C13 C14 H14A 120.0 . . ?
C15 C14 H14A 120.0 . . ?
C16 C15 C14 120.0 . . ?
C16 C15 H15A 120.0 . . ?
C14 C15 H15A 120.0 . . ?
C15 C16 C11 120.0 . . ?
C15 C16 C17 149.6(5) . . ?
C11 C16 C17 90.4(5) . . ?
C11 S1 C18 83.6(4) . . ?
C18 C17 C22 120.0 . . ?
C18 C17 C16 116.2(5) . . ?
C22 C17 C16 123.8(5) . . ?
C19 C18 C17 120.0 . . ?
C19 C18 S1 126.3(4) . . ?
C17 C18 S1 113.7(4) . . ?
C18 C19 C20 120.0 . . ?
C18 C19 Br1 119.5(4) . . ?
C20 C19 Br1 120.5(4) . . ?
C21 C20 C19 120.0 . . ?
C21 C20 H20A 120.0 . . ?
C19 C20 H20A 120.0 . . ?
C20 C21 C22 120.0 . . ?
C20 C21 H21A 120.0 . . ?
C22 C21 H21A 120.0 . . ?
C21 C22 C17 120.0 . . ?
C21 C22 H22A 120.0 . . ?
C17 C22 H22A 120.0 . . ?
C11' S1' C22' 85.8(3) . . ?
C12' C11' C16' 120.0 . . ?
C12' C11' S1' 111.4(4) . . ?
C16' C11' S1' 128.6(4) . . ?
C11' C12' C13' 120.0 . . ?
C11' C12' H12B 120.0 . . ?
C13' C12' H12B 120.0 . . ?
C14' C13' C12' 120.0 . . ?
C14' C13' H13B 120.0 . . ?
C12' C13' H13B 120.0 . . ?
C13' C14' C15' 120.0 . . ?
C13' C14' H14B 120.0 . . ?
C15' C14' H14B 120.0 . . ?
C16' C15' C14' 120.0 . . ?
C16' C15' H15B 120.0 . . ?
C14' C15' H15B 120.0 . . ?
C15' C16' C11' 120.0 . . ?
C15' C16' C17' 143.1(4) . . ?
C11' C16' C17' 96.9(4) . . ?
C18' C17' C22' 120.0 . . ?
C18' C17' C16' 125.1(4) . . ?
C22' C17' C16' 114.9(4) . . ?
C17' C18' C19' 120.0 . . ?
C17' C18' H18A 120.0 . . ?
C19' C18' H18A 120.0 . . ?
C20' C19' C18' 120.0 . . ?
C20' C19' H19A 120.0 . . ?
C18' C19' H19A 120.0 . . ?
C19' C20' C21' 120.0 . . ?
C19' C20' H20B 120.0 . . ?
C21' C20' H20B 120.0 . . ?
C22' C21' C20' 120.0 . . ?
C22' C21' Br1' 119.9(3) . . ?
C20' C21' Br1' 120.0(3) . . ?
C21' C22' C17' 120.0 . . ?
C21' C22' S1' 126.1(3) . . ?
C17' C22' S1' 113.9(3) . . ?

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
C7 C2 C3 C4 1.2(5) . . . . ?
C1 C2 C3 C4 -179.8(3) . . . . ?
C2 C3 C4 C5 -0.1(5) . . . . ?
C2 C3 C4 C9 -179.4(3) . . . . ?
C3 C4 C5 C6 -0.5(5) . . . . ?
C9 C4 C5 C6 178.8(3) . . . . ?
C3 C4 C5 C10 178.6(3) . . . . ?
C9 C4 C5 C10 -2.2(5) . . . . ?
C4 C5 C6 C7 0.0(5) . . . . ?
C10 C5 C6 C7 -179.0(3) . . . . ?
C5 C6 C7 C2 1.1(5) . . . . ?
C5 C6 C7 C8 -178.6(3) . . . . ?
C3 C2 C7 C6 -1.8(5) . . . . ?
C1 C2 C7 C6 179.3(3) . . . . ?
C3 C2 C7 C8 177.9(3) . . . . ?
C1 C2 C7 C8 -1.0(5) . . . . ?
C16 C11 C12 C13 0.0 . . . . ?
S1 C11 C12 C13 -179.5(15) . . . . ?
C11 C12 C13 C14 0.0 . . . . ?
C12 C13 C14 C15 0.0 . . . . ?
C13 C14 C15 C16 0.0 . . . . ?
C14 C15 C16 C11 0.0 . . . . ?
C14 C15 C16 C17 -177(3) . . . . ?
C12 C11 C16 C15 0.0 . . . . ?
S1 C11 C16 C15 179(2) . . . . ?
C12 C11 C16 C17 178.7(15) . . . . ?
S1 C11 C16 C17 -2.1(13) . . . . ?
C12 C11 S1 C18 -178.1(9) . . . . ?
C16 C11 S1 C18 2.6(14) . . . . ?
C15 C16 C17 C18 178(2) . . . . ?
C11 C16 C17 C18 0.1(9) . . . . ?
C15 C16 C17 C22 -2(3) . . . . ?
C11 C16 C17 C22 -179.3(8) . . . . ?
C22 C17 C18 C19 0.0 . . . . ?
C16 C17 C18 C19 -179.4(10) . . . . ?
C22 C17 C18 S1 -179.3(5) . . . . ?
C16 C17 C18 S1 1.3(11) . . . . ?
C11 S1 C18 C19 179.0(10) . . . . ?
C11 S1 C18 C17 -1.7(10) . . . . ?
C17 C18 C19 C20 0.0 . . . . ?
S1 C18 C19 C20 179.2(6) . . . . ?
C17 C18 C19 Br1 -178.3(6) . . . . ?
S1 C18 C19 Br1 0.9(5) . . . . ?
C18 C19 C20 C21 0.0 . . . . ?
Br1 C19 C20 C21 178.3(6) . . . . ?
C19 C20 C21 C22 0.0 . . . . ?
C20 C21 C22 C17 0.0 . . . . ?
C18 C17 C22 C21 0.0 . . . . ?
C16 C17 C22 C21 179.4(11) . . . . ?
C22' S1' C11' C12' -179.6(7) . . . . ?
C22' S1' C11' C16' 2.0(8) . . . . ?
C16' C11' C12' C13' 0.0 . . . . ?
S1' C11' C12' C13' -178.5(11) . . . . ?
C11' C12' C13' C14' 0.0 . . . . ?
C12' C13' C14' C15' 0.0 . . . . ?
C13' C14' C15' C16' 0.0 . . . . ?
C14' C15' C16' C11' 0.0 . . . . ?
C14' C15' C16' C17' 179.9(17) . . . . ?
C12' C11' C16' C15' 0.0 . . . . ?
S1' C11' C16' C15' 178.3(13) . . . . ?
C12' C11' C16' C17' -179.9(10) . . . . ?
S1' C11' C16' C17' -1.7(8) . . . . ?
C15' C16' C17' C18' 1.7(18) . . . . ?
C11' C16' C17' C18' -178.4(5) . . . . ?
C15' C16' C17' C22' -179.6(12) . . . . ?
C11' C16' C17' C22' 0.3(7) . . . . ?
C22' C17' C18' C19' 0.0 . . . . ?
C16' C17' C18' C19' 178.6(8) . . . . ?
C17' C18' C19' C20' 0.0 . . . . ?
C18' C19' C20' C21' 0.0 . . . . ?
C19' C20' C21' C22' 0.0 . . . . ?
C19' C20' C21' Br1' -179.2(4) . . . . ?
C20' C21' C22' C17' 0.0 . . . . ?
Br1' C21' C22' C17' 179.2(4) . . . . ?
C20' C21' C22' S1' -179.6(4) . . . . ?
Br1' C21' C22' S1' -0.4(3) . . . . ?
C18' C17' C22' C21' 0.0 . . . . ?
C16' C17' C22' C21' -178.8(7) . . . . ?
C18' C17' C22' S1' 179.6(4) . . . . ?
C16' C17' C22' S1' 0.9(7) . . . . ?
C11' S1' C22' C21' 178.2(6) . . . . ?
C11' S1' C22' C17' -1.4(6) . . . . ?

_refine_diff_density_max         0.411
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.066

