# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2024

####################################################################### 
# 
# 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_4BrPEABiI6
_database_code_depnum_ccdc_archive 'CCDC 2343629'
loop_
_audit_author_name
_audit_author_address
'Cheng-Dong Liu'
;Southeast University
China
;
_audit_update_record             
;
2024-03-27 deposited with the CCDC.	2024-06-02 downloaded from the CCDC.
;
_audit_creation_date             2024-03-27
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Bi0.333 I2, C8 H11 Br N'
_chemical_formula_sum            'C8 H11 Bi0.33 Br I2 N'
_chemical_formula_weight         524.63
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Bi I Br C N'
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'
Bi Bi -4.1077 10.2566 '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'
I I -0.4742 1.8119 '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           42
_space_group_name_H-M_alt        'F m m 2'
_space_group_name_Hall           'F 2 -2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, z'
'x, -y, z'
'x, y+1/2, z+1/2'
'-x, -y+1/2, z+1/2'
'-x, y+1/2, z+1/2'
'x, -y+1/2, z+1/2'
'x+1/2, y, z+1/2'
'-x+1/2, -y, z+1/2'
'-x+1/2, y, z+1/2'
'x+1/2, -y, z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z'
'-x+1/2, y+1/2, z'
'x+1/2, -y+1/2, z'

_cell_length_a                   8.5646(5)
_cell_length_b                   35.477(5)
_cell_length_c                   8.5649(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2602.4(4)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    5898
_cell_measurement_temperature    292(2)
_cell_measurement_theta_max      31.0070
_cell_measurement_theta_min      2.3180
_shelx_estimated_absorpt_T_max   0.790
_shelx_estimated_absorpt_T_min   0.371
_exptl_absorpt_coefficient_mu    12.357
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54435
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.41.109a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.678
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1878
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            6692
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.297
_diffrn_reflns_theta_min         2.296
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     -7.00  19.00   0.50    1.00    --    4.87  19.00 -30.00   52
  2  ω     44.00  76.00   0.50    1.00    --    4.87  19.00 -30.00   64
  3  ω    -63.00  18.00   0.50    1.00    --    4.87 -38.00 150.00  162
  4  ω    -10.00  20.00   0.50    1.00    --   -5.57 -99.00 120.00   60
  5  ω    -75.00   8.00   0.50    1.00    --   -5.57 -38.00   0.00  166
  6  ω    -76.00 -16.00   0.50    1.00    --   -5.57 -57.00 -90.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1036581000
_diffrn_orient_matrix_UB_12      -0.0485142000
_diffrn_orient_matrix_UB_13      0.0047058000
_diffrn_orient_matrix_UB_21      0.0524330000
_diffrn_orient_matrix_UB_22      -0.0688304000
_diffrn_orient_matrix_UB_23      0.0133643000
_diffrn_orient_matrix_UB_31      -0.0150493000
_diffrn_orient_matrix_UB_32      0.0814343000
_diffrn_orient_matrix_UB_33      0.0140978000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_reflns_Friedel_coverage         0.832
_reflns_Friedel_fraction_full    0.970
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                1296
_reflns_number_total             1418
_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       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_refine_diff_density_max         1.836
_refine_diff_density_min         -1.490
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.012(12)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     86
_refine_ls_number_reflns         1418
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0281
_refine_ls_R_factor_gt           0.0248
_refine_ls_restrained_S_all      1.081
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0281P)²+4.3082P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0576
_refine_ls_wR_factor_ref         0.0584
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 1.012(12)
 -0.012(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
3. Restrained distances
 C6-C5
 1.53 with sigma of 0.02
 N1-C6
 1.47 with sigma of 0.02
4. Others
 Sof(I2B)=0.5*(1-FVAR(2))
 Sof(I2A)=0.5*FVAR(2)
 Fixed Sof: Bi1(0.16666) H5A(0.5) H5B(0.5) N1(0.5) H1A(0.5) H1B(0.5) H1C(0.5)
 C6(0.5) H6A(0.5) H6B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
5.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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
Bi1 Bi 0.500000 0.500000 0.62936(12) 0.0353(2) Uani 0.6666 4 d S T P . .
I1 I 0.500000 0.58913(2) 0.64227(13) 0.0502(2) Uani 1 2 d S T P A .
I2A I 0.28174(19) 0.500000 0.34532(17) 0.0487(6) Uani 0.657(4) 2 d S T P A 1
I2B I 0.1921(3) 0.500000 0.4370(4) 0.0475(12) Uani 0.343(4) 2 d S T P A 2
Br1 Br 0.000000 0.73642(4) 0.1342(3) 0.0813(4) Uani 1 2 d S T P . .
C1 C 0.000000 0.7034(3) 0.3075(14) 0.049(3) Uani 1 2 d S T P . .
C2 C 0.1403(11) 0.6920(2) 0.3692(11) 0.052(2) Uani 1 1 d . . . . .
H2 H 0.234092 0.699834 0.325195 0.062 Uiso 1 1 calc R U . . .
C3 C 0.1388(11) 0.6686(2) 0.4983(11) 0.052(2) Uani 1 1 d . . . . .
H3 H 0.232693 0.661012 0.542798 0.062 Uiso 1 1 calc R U . . .
C4 C 0.000000 0.6564(3) 0.5618(15) 0.047(3) Uani 1 2 d S T P . .
C5 C 0.000000 0.6313(4) 0.7016(15) 0.064(4) Uani 1 2 d DS T P . .
H5A H -0.081180 0.639729 0.772401 0.077 Uiso 0.5 1 calc R U P B .
H5B H 0.099187 0.634080 0.755021 0.077 Uiso 0.5 1 calc R U P . .
N1 N 0.0825(19) 0.5738(4) 0.553(2) 0.055(4) Uani 0.5 1 d D . P B -1
H1A H 0.053745 0.580499 0.457159 0.066 Uiso 0.5 1 calc R U P B -1
H1B H 0.080095 0.548776 0.561241 0.066 Uiso 0.5 1 calc R U P B -1
H1C H 0.179023 0.581969 0.571455 0.066 Uiso 0.5 1 calc R U P B -1
C6 C -0.025(5) 0.5904(4) 0.667(2) 0.056(9) Uani 0.5 1 d D . P B -1
H6A H -0.016248 0.576497 0.764481 0.067 Uiso 0.5 1 calc R U P B -1
H6B H -0.131109 0.587196 0.629589 0.067 Uiso 0.5 1 calc R U P B -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 I1 3.1640(8) . ?
Bi1 I1 3.1639(8) 2_665 ?
Bi1 I2A 3.0404(15) 9 ?
Bi1 I2A 3.0404(15) 10_565 ?
Bi1 I2A 3.0680(16) 2_665 ?
Bi1 I2A 3.0680(16) . ?
Bi1 I2B 3.109(2) 2_665 ?
Bi1 I2B 3.106(3) 10_565 ?
Bi1 I2B 3.106(3) 9 ?
Bi1 I2B 3.109(2) . ?
Br1 C1 1.892(12) . ?
C1 C2 1.373(11) . ?
C1 C2 1.373(11) 3 ?
C2 H2 0.9300 . ?
C2 C3 1.383(12) . ?
C3 H3 0.9300 . ?
C3 C4 1.377(12) . ?
C4 C5 1.491(17) . ?
C5 H5A 0.9700 . ?
C5 H5A 0.9700 3 ?
C5 H5B 0.9700 . ?
C5 H5B 0.9700 3 ?
C5 C6 1.494(17) . ?
N1 H1A 0.8900 . ?
N1 H1B 0.8900 . ?
N1 H1C 0.8900 . ?
N1 C6 1.47(2) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?

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
I1 Bi1 I1 175.99(5) 2_665 . ?
I2A Bi1 I1 91.59(2) . . ?
I2A Bi1 I1 91.59(2) . 2_665 ?
I2A Bi1 I1 88.782(16) 10_565 2_665 ?
I2A Bi1 I1 91.59(2) 2_665 2_665 ?
I2A Bi1 I1 88.782(16) 10_565 . ?
I2A Bi1 I1 88.782(16) 9 . ?
I2A Bi1 I1 88.782(16) 9 2_665 ?
I2A Bi1 I1 91.59(2) 2_665 . ?
I2A Bi1 I2A 89.934(9) 9 2_665 ?
I2A Bi1 I2A 105.06(8) 9 10_565 ?
I2A Bi1 I2A 75.07(8) 2_665 . ?
I2A Bi1 I2A 165.01(8) 10_565 2_665 ?
I2A Bi1 I2A 165.01(8) 9 . ?
I2A Bi1 I2A 89.934(9) 10_565 . ?
I2A Bi1 I2B 110.47(5) 2_665 9 ?
I2A Bi1 I2B 84.52(10) 9 10_565 ?
I2A Bi1 I2B 69.48(5) 9 2_665 ?
I2A Bi1 I2B 95.53(10) . 2_665 ?
I2A Bi1 I2B 110.47(5) . 10_565 ?
I2A Bi1 I2B 174.45(10) . 9 ?
I2A Bi1 I2B 84.52(10) 10_565 9 ?
I2A Bi1 I2B 20.46(5) 2_665 2_665 ?
I2A Bi1 I2B 20.54(5) 10_565 10_565 ?
I2A Bi1 I2B 20.54(5) 9 9 ?
I2A Bi1 I2B 174.45(10) 2_665 10_565 ?
I2A Bi1 I2B 174.53(10) 10_565 2_665 ?
I2B Bi1 I1 88.30(2) 9 . ?
I2B Bi1 I1 91.061(14) . . ?
I2B Bi1 I1 88.30(2) 10_565 . ?
I2B Bi1 I1 91.061(14) 2_665 . ?
I2B Bi1 I2B 154.00(14) 9 . ?
I2B Bi1 I2B 90.02(2) 10_565 . ?
Bi1 I2A Bi1 165.01(8) 9_454 . ?
Bi1 I2B Bi1 154.00(13) 9_454 . ?
C2 C1 Br1 119.0(6) . . ?
C2 C1 Br1 119.0(6) 3 . ?
C2 C1 C2 122.1(11) 3 . ?
C1 C2 H2 120.8 . . ?
C1 C2 C3 118.4(9) . . ?
C3 C2 H2 120.8 . . ?
C2 C3 H3 119.6 . . ?
C4 C3 C2 120.9(9) . . ?
C4 C3 H3 119.6 . . ?
C3 C4 C3 119.3(12) 3 . ?
C3 C4 C5 120.3(6) 3 . ?
C3 C4 C5 120.3(6) . . ?
C4 C5 H5A 108.5(4) . 3 ?
C4 C5 H5A 108.5 . . ?
C4 C5 H5B 108.5 . . ?
C4 C5 H5B 108.5(2) . 3 ?
C4 C5 C6 114.9(11) . . ?
H5A C5 H5A 91.6 . 3 ?
H5A C5 H5B 107.5 . . ?
H5A C5 H5B 107.5 3 3 ?
H5A C5 H5B 17.4 . 3 ?
H5B C5 H5A 17.4 . 3 ?
H5B C5 H5B 122.3 . 3 ?
C6 C5 H5A 121.7(14) . 3 ?
C6 C5 H5A 108.5 . . ?
C6 C5 H5B 108.5 . . ?
C6 C5 H5B 93.7(13) . 3 ?
H1A N1 H1B 109.5 . . ?
H1A N1 H1C 109.5 . . ?
H1B N1 H1C 109.5 . . ?
C6 N1 H1A 109.5 . . ?
C6 N1 H1B 109.5 . . ?
C6 N1 H1C 109.5 . . ?
C5 C6 H6A 108.4 . . ?
C5 C6 H6B 108.4 . . ?
N1 C6 C5 115.4(19) . . ?
N1 C6 H6A 108.4 . . ?
N1 C6 H6B 108.4 . . ?
H6A C6 H6B 107.5 . . ?

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
Br1 C1 C2 C3 178.4(7) . . . . ?
C1 C2 C3 C4 1.3(15) . . . . ?
C2 C1 C2 C3 -0.6(18) 3 . . . ?
C2 C3 C4 C3 -1.9(17) . . . 3 ?
C2 C3 C4 C5 -179.7(9) . . . . ?
C3 C4 C5 C6 -100.3(18) . . . . ?
C3 C4 C5 C6 82.0(19) 3 . . . ?
C4 C5 C6 N1 54(3) . . . . ?

_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 1.658
_oxdiff_exptl_absorpt_empirical_full_min 0.722
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 1.012(12)
2 -0.012(12)

