# Electronic Supplementary Material (ESI) for Materials Advances.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_srp1
_database_code_depnum_ccdc_archive 'CCDC 2265208'
loop_
_audit_author_name
_audit_author_address
'Mark Elsegood'
;Loughborough University
United Kingdom
;
_audit_update_record             
;
2023-05-24 deposited with the CCDC.	2023-11-27 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT075_srp1                
;
PROBLEM: Occupancy      2.000 Greater Than 1.0 for ......          H1F
RESPONSE: False alert. The formula is actually correct. Tjis alert has been triggered due to the close proximity of the this H to a symmetry element. The actual occupancy is correct at 0.5.
;
# Added during the CSD deposition process: Wednesday 24 May 2023 03:06 PM
# end Validation Reply Form


_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '(Bi Br6 3-), 3(C H6 N 1+), 2(C2 H6 O S)'
_chemical_formula_sum            'C7 H30 Bi Br6 N3 O2 S2'
_chemical_formula_weight         940.90

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'
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'
Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_H-M_alt        'C 2/m'
_space_group_name_Hall           '-C 2y'

_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'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z'
'-x, -y, -z'
'x, -y, z'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z'

_cell_length_a                   14.5874(4)
_cell_length_b                   9.2026(2)
_cell_length_c                   9.5884(3)
_cell_angle_alpha                90
_cell_angle_beta                 103.333(3)
_cell_angle_gamma                90
_cell_volume                     1252.47(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    8059
_cell_measurement_theta_min      2.61
_cell_measurement_theta_max      31.58

_exptl_crystal_description       block
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    2.495
_exptl_crystal_F_000             868
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.090
_exptl_absorpt_coefficient_mu    16.781
_shelx_estimated_absorpt_T_min   0.127
_shelx_estimated_absorpt_T_max   0.314
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_correction_T_min  0.072
_exptl_absorpt_correction_T_max  0.210
_exptl_absorpt_process_details   
; 
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021) 
Analytical numeric absorption correction using a multifaceted crystal 
model based on expressions derived by R.C. Clark & J.S. Reid. 
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) 
Empirical absorption correction using spherical harmonics, 
implemented in SCALE3 ABSPACK scaling algorithm. 
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, UG2 κ goniometer'
_diffrn_source                   'Rotating Anode'
_diffrn_measurement_device_type  
; 
Rigaku FRE+ equipped with Arc)Sec VHF Varimax confocal mirrors and an UG2 
goniometer and HyPix 6000HE detector 
;
_diffrn_measurement_method       'profile data from ω-scans'
_diffrn_radiation_collimation    0.2
_diffrn_detector_area_resol_mean 10
_diffrn_reflns_number            54706
_diffrn_reflns_av_unetI/netI     0.0125
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.183
_diffrn_reflns_theta_max         31.699
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2171
_reflns_number_gt                2106
_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       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_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)+(0.0119P)²+9.1935P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.00041(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2171
_refine_ls_number_parameters     79
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0213
_refine_ls_R_factor_gt           0.0200
_refine_ls_wR_factor_ref         0.0418
_refine_ls_wR_factor_gt          0.0414
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_restrained_S_all      1.077
_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
Bi1 Bi 0.500000 0.500000 0.500000 0.01035(6) Uani 1 4 d S T P . .
Br1 Br 0.64987(3) 0.500000 0.35446(4) 0.01898(8) Uani 1 2 d S T P . .
Br2 Br 0.40356(2) 0.28374(3) 0.30735(3) 0.02199(7) Uani 1 1 d . . . . .
S1 S 0.87463(7) 0.500000 1.01071(11) 0.0347(3) Uani 1 2 d S T P . .
C1 C 0.7621(3) 0.500000 1.0538(5) 0.0415(14) Uani 1 2 d S T P A .
H1D H 0.758155 0.418038 1.117433 0.062 Uiso 0.5 1 calc R U P . .
H1E H 0.753547 0.591201 1.102057 0.062 Uiso 0.5 1 calc R U P . .
H1F H 0.712669 0.490761 0.965640 0.062 Uiso 1 2 calc R U P . .
C2 C 0.86718(17) 0.6431(2) 0.9051(3) 0.0219(4) Uani 0.5 1 d . . P A 1
H2A H 0.871240 0.731889 0.962636 0.033 Uiso 0.5 1 calc R U P A 1
H2B H 0.918992 0.641207 0.855758 0.033 Uiso 0.5 1 calc R U P A 1
H2C H 0.806888 0.641210 0.834195 0.033 Uiso 0.5 1 calc R U P A 1
O1 O 0.86718(17) 0.6431(2) 0.9051(3) 0.0219(4) Uani 0.5 1 d . . P A 2
N1 N 0.8884(3) 0.500000 0.5762(5) 0.0316(9) Uani 0.5 2 d DS T P B 1
H1A H 0.9439(15) 0.500000 0.629(4) 0.038 Uiso 1 2 d DS U P C 1
H1B H 0.889(3) 0.500000 0.4880(16) 0.038 Uiso 1 2 d DS U P D 1
H1C H 0.857(4) 0.572(6) 0.597(4) 0.038 Uiso 0.5 1 d D U P E 1
C3 C 0.8324(4) 0.6233(5) 0.6028(5) 0.0167(9) Uani 0.25 1 d . . P B 1
H3A H 0.767130 0.610918 0.548963 0.025 Uiso 0.5 1 calc R U P B 1
H3B H 0.858241 0.712921 0.571939 0.025 Uiso 0.5 1 calc R U P B 1
H3C H 0.834250 0.629244 0.705457 0.025 Uiso 0.5 1 calc R U P B 1
N1X N 0.8324(4) 0.6233(5) 0.6028(5) 0.0167(9) Uani 0.25 1 d . . P F 2
C3X C 0.8884(3) 0.500000 0.5762(5) 0.0316(9) Uani 0.5 2 d S T P F 2
N2 N 0.500000 0.500000 0.000000 0.0405(16) Uani 0.5 4 d S T P . .
C4 C 0.4936(8) 0.3597(9) 0.0276(9) 0.0111(18) Uani 0.125 1 d . . P G -1
H4A H 0.556349 0.315509 0.045607 0.017 Uiso 0.25 1 calc R U P G -1
H4B H 0.452197 0.312084 -0.054759 0.017 Uiso 0.25 1 calc R U P G -1
H4C H 0.467491 0.347791 0.112377 0.017 Uiso 0.25 1 calc R U P G -1
C4X C 0.500000 0.500000 0.000000 0.0405(16) Uani 0.5 4 d S T P . .
N2X N 0.4936(8) 0.3597(9) 0.0276(9) 0.0111(18) Uani 0.125 1 d . . P G -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
Bi1 Br1 2.8520(4) . ?
Bi1 Br1 2.8520(4) 5_666 ?
Bi1 Br2 2.8554(3) . ?
Bi1 Br2 2.8554(3) 5_666 ?
Bi1 Br2 2.8555(3) 6_565 ?
Bi1 Br2 2.8555(3) 2_656 ?
S1 O1 1.649(2) . ?
S1 C2 1.649(2) . ?
S1 C2 1.649(2) 6_565 ?
S1 C1 1.783(4) . ?
C1 H1D 0.9800 . ?
C1 H1E 0.9800 . ?
C1 H1F 0.9800 . ?
C1 H1D 0.9800 6_565 ?
C1 H1E 0.9800 6_565 ?
C1 H1F 0.9800 6_565 ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
N1 C3 1.454(6) 6_565 ?
N1 C3 1.454(6) . ?
N1 H1A 0.852(10) . ?
N1 H1B 0.849(10) . ?
N1 H1C 0.854(10) . ?
N1 H1C 0.854(10) 6_565 ?
C3 H1C 0.603(12) . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
N1X C3X 1.454(6) . ?
N2 C4 1.326(8) . ?
C4 H4A 0.9800 . ?
C4 H4B 0.9800 . ?
C4 H4C 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
Br1 Bi1 Br1 180.0 . 5_666 ?
Br1 Bi1 Br2 90.137(8) . . ?
Br1 Bi1 Br2 89.863(8) 5_666 . ?
Br1 Bi1 Br2 89.863(8) . 5_666 ?
Br1 Bi1 Br2 90.137(8) 5_666 5_666 ?
Br2 Bi1 Br2 180.0 . 5_666 ?
Br1 Bi1 Br2 90.137(8) . 6_565 ?
Br1 Bi1 Br2 89.863(8) 5_666 6_565 ?
Br2 Bi1 Br2 88.370(11) . 6_565 ?
Br2 Bi1 Br2 91.630(12) 5_666 6_565 ?
Br1 Bi1 Br2 89.863(8) . 2_656 ?
Br1 Bi1 Br2 90.137(8) 5_666 2_656 ?
Br2 Bi1 Br2 91.630(11) . 2_656 ?
Br2 Bi1 Br2 88.370(12) 5_666 2_656 ?
Br2 Bi1 Br2 180.0 6_565 2_656 ?
C2 S1 C2 105.96(18) . 6_565 ?
O1 S1 C1 102.03(13) . . ?
C2 S1 C1 102.03(13) . . ?
C2 S1 C1 102.03(13) 6_565 . ?
S1 C1 H1D 109.5 . . ?
S1 C1 H1E 109.5 . . ?
H1D C1 H1E 109.5 . . ?
S1 C1 H1F 109.5 . . ?
H1D C1 H1F 109.5 . . ?
H1E C1 H1F 109.5 . . ?
S1 C1 H1D 109.47(9) . 6_565 ?
H1D C1 H1D 100.6 . 6_565 ?
H1E C1 H1D 10.0 . 6_565 ?
H1F C1 H1D 117.8 . 6_565 ?
S1 C1 H1E 109.47(7) . 6_565 ?
H1D C1 H1E 10.0 . 6_565 ?
H1E C1 H1E 117.8 . 6_565 ?
H1F C1 H1E 100.6 . 6_565 ?
H1D C1 H1E 109.5 6_565 6_565 ?
S1 C1 H1F 109.47(16) . 6_565 ?
H1D C1 H1F 117.8 . 6_565 ?
H1E C1 H1F 100.6 . 6_565 ?
H1F C1 H1F 10.0 . 6_565 ?
H1D C1 H1F 109.5 6_565 6_565 ?
H1E C1 H1F 109.5 6_565 6_565 ?
S1 C2 H2A 109.5 . . ?
S1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
S1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
C3 N1 C3 102.6(5) 6_565 . ?
C3 N1 H1A 113.0(17) 6_565 . ?
C3 N1 H1A 113.0(17) . . ?
C3 N1 H1B 108.3(18) 6_565 . ?
C3 N1 H1B 108.3(18) . . ?
H1A N1 H1B 111(2) . . ?
C3 N1 H1C 102(6) 6_565 . ?
C3 N1 H1C 3(3) . . ?
H1A N1 H1C 111(2) . . ?
H1B N1 H1C 111(2) . . ?
C3 N1 H1C 3(3) 6_565 6_565 ?
C3 N1 H1C 102(6) . 6_565 ?
H1A N1 H1C 111(2) . 6_565 ?
H1B N1 H1C 111(2) . 6_565 ?
H1C N1 H1C 101(10) . 6_565 ?
N1 C3 H1C 4(4) . . ?
N1 C3 H3A 109.5 . . ?
H1C C3 H3A 112.1 . . ?
N1 C3 H3B 109.5 . . ?
H1C C3 H3B 111.0 . . ?
H3A C3 H3B 109.5 . . ?
N1 C3 H3C 109.5 . . ?
H1C C3 H3C 105.3 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N2 C4 H4A 109.5 . . ?
N2 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
N2 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?

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
C1 H1D Br2 0.98 3.08 3.831(4) 134.5 8_556 yes
C1 H1E Br2 0.98 3.13 3.831(4) 129.4 3_556 yes
C2 H2C Br2 0.98 3.13 4.061(2) 158.3 5_666 yes
C3 H1C N1 0.603(12) 0.854(10) 1.454(6) 173(6) . yes
C3 H3A Br1 0.98 2.44 3.336(5) 151.0 . yes
C3 H3B Br1 0.98 2.74 3.493(5) 133.6 7_666 yes
C3 H3B Br2 0.98 2.84 3.555(5) 130.3 3 yes
C4 H4C Br2 0.98 2.35 3.322(7) 171.8 . yes

_refine_diff_density_max         1.525
_refine_diff_density_min         -1.543
_refine_diff_density_rms         0.132



_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: butyrolactone/dimethylsufoxide'
