# Electronic Supplementary Material (ESI) for Chemical Science.
# 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_d2132_b
_database_code_depnum_ccdc_archive 'CCDC 2180022'
loop_
_audit_author_name
_audit_author_address
'Alan J. Lough'
;University of Toronto
Canada
;
_audit_update_record             
;
2022-06-18 deposited with the CCDC.	2022-09-28 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         'C12 H10 F N2 S, Br'
_chemical_formula_sum            'C12 H10 Br F N2 S'
_chemical_formula_weight         313.19

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'
F F 0.0171 0.0103 '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      triclinic
_space_group_IT_number           1
_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'

_cell_length_a                   4.5926(3)
_cell_length_b                   5.6626(4)
_cell_length_c                   12.1650(8)
_cell_angle_alpha                86.311(2)
_cell_angle_beta                 88.909(2)
_cell_angle_gamma                81.003(2)
_cell_volume                     311.81(4)
_cell_formula_units_Z            1
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    2926
_cell_measurement_theta_min      3.36
_cell_measurement_theta_max      27.46

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.668
_exptl_crystal_F_000             156
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.190
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.070
_exptl_absorpt_coefficient_mu    3.453
_shelx_estimated_absorpt_T_min   0.560
_shelx_estimated_absorpt_T_max   0.794
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6118
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   'SADABS (Krause et al., 2015)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube with Bruker Triumph monochromator'
_diffrn_measurement_device_type  'Bruker Kappa APEX-DUO CMOS PHOTON II'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4945
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_av_R_equivalents  0.0276
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.678
_diffrn_reflns_theta_max         27.602
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.786
_diffrn_reflns_point_group_measured_fraction_full 0.823
_reflns_number_total             2260
_reflns_number_gt                2181
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.580
_reflns_Friedel_fraction_max     0.577
_reflns_Friedel_fraction_full    0.648

_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. 
;

_computing_data_collection       'APEX3 (Bruker, 2018)'
_computing_cell_refinement       APEX3
_computing_data_reduction        'SAINT (Bruker, 2014)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015b)'
_computing_molecular_graphics    'PLATON (Spek, 2009)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'
_refine_special_details          
; 
 Refined as a 2-component inversion twin. 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0035P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
; 
 Refined as an inversion twin. 
;
_refine_ls_abs_structure_Flack   0.371(7)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         2260
_refine_ls_number_parameters     161
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0249
_refine_ls_R_factor_gt           0.0228
_refine_ls_wR_factor_ref         0.0334
_refine_ls_wR_factor_gt          0.0332
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_restrained_S_all      1.052
_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
Br1 Br 1.22605(3) 0.25929(3) 0.09750(3) 0.02393(10) Uani 1 1 d . . . . .
S1 S 0.64934(19) 0.42419(16) 0.37876(8) 0.0250(2) Uani 1 1 d . . . . .
F1 F -0.2306(5) 0.4054(4) 0.76952(19) 0.0331(8) Uani 0.836(5) 1 d . . P A 1
C9 C 0.2670(9) -0.1478(7) 0.7592(3) 0.0238(9) Uani 0.836(5) 1 d . . P A 1
H9A H 0.425453 -0.225795 0.717028 0.029 Uiso 0.836(5) 1 calc R U P A 1
C12 C -0.0930(8) 0.1799(6) 0.7942(3) 0.0236(8) Uani 0.836(5) 1 d . . P A 1
F1A F 0.503(3) -0.230(2) 0.7083(10) 0.035(4) Uiso 0.164(5) 1 d . . P A 2
C9A C 0.2670(9) -0.1478(7) 0.7592(3) 0.0238(9) Uani 0.164(5) 1 d . . P A 2
C12A C -0.0930(8) 0.1799(6) 0.7942(3) 0.0236(8) Uani 0.164(5) 1 d . . P A 2
H12A H -0.192760 0.337015 0.775762 0.028 Uiso 0.164(5) 1 calc R U P A 2
N1 N 0.6177(6) 0.7166(5) 0.1076(2) 0.0230(6) Uani 1 1 d . . . . .
H1C H 0.741515 0.728361 0.048862 0.035 Uiso 1 1 calc R U . . .
H1D H 0.454855 0.830068 0.098593 0.035 Uiso 1 1 calc R U . . .
H1E H 0.562901 0.568592 0.112485 0.035 Uiso 1 1 calc R U . . .
N2 N -0.0542(7) -0.1651(5) 0.9151(2) 0.0217(8) Uani 1 1 d . . . . .
C1 C 0.7722(7) 0.7540(6) 0.2109(2) 0.0221(7) Uani 1 1 d . . . . .
H1A H 0.964692 0.647106 0.214592 0.026 Uiso 1 1 calc R U . . .
H1B H 0.810290 0.921480 0.209261 0.026 Uiso 1 1 calc R U . . .
C2 C 0.5932(8) 0.7036(6) 0.3110(3) 0.0190(8) Uani 1 1 d . . . . .
C3 C 0.3750(8) 0.8529(6) 0.3598(3) 0.0221(9) Uani 1 1 d . . . . .
H3A H 0.313081 1.014376 0.333688 0.027 Uiso 1 1 calc R U . . .
C4 C 0.2494(9) 0.7441(7) 0.4530(3) 0.0259(9) Uani 1 1 d . . . . .
H4A H 0.095093 0.823854 0.496486 0.031 Uiso 1 1 calc R U . . .
C5 C 0.3762(9) 0.5099(7) 0.4735(3) 0.0225(9) Uani 1 1 d . . . . .
C6 C 0.3007(9) 0.3503(7) 0.5605(3) 0.0233(9) Uani 1 1 d . . . . .
C7 C 0.2302(9) 0.2229(7) 0.6348(3) 0.0245(9) Uani 1 1 d . . . . .
C8 C 0.1334(9) 0.0864(7) 0.7277(3) 0.0206(9) Uani 1 1 d . . . . .
C10 C 0.1653(8) -0.2641(6) 0.8527(3) 0.0232(9) Uani 1 1 d . . . . .
H10A H 0.257535 -0.422628 0.872921 0.028 Uiso 1 1 calc R U . A 1
C11 C -0.1826(7) 0.0574(6) 0.8860(3) 0.0254(8) Uani 1 1 d . . . . .
H11A H -0.339278 0.132378 0.929989 0.031 Uiso 1 1 calc R U . 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
S1 C2 1.721(4) . ?
S1 C5 1.722(4) . ?
F1 C12 1.351(4) . ?
C9 C10 1.387(5) . ?
C9 C8 1.404(5) . ?
C9 H9A 0.9500 . ?
C12 C8 1.366(5) . ?
C12 C11 1.368(5) . ?
F1A C9A 1.278(13) . ?
C9A C10 1.387(5) . ?
C9A C8 1.404(5) . ?
C12A C8 1.366(5) . ?
C12A C11 1.368(5) . ?
C12A H12A 0.9500 . ?
N1 C1 1.498(4) . ?
N1 H1C 0.9100 . ?
N1 H1D 0.9100 . ?
N1 H1E 0.9100 . ?
N2 C10 1.325(5) . ?
N2 C11 1.334(4) . ?
C1 C2 1.494(5) . ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 C3 1.359(5) . ?
C3 C4 1.413(5) . ?
C3 H3A 0.9500 . ?
C4 C5 1.371(6) . ?
C4 H4A 0.9500 . ?
C5 C6 1.421(5) . ?
C6 C7 1.192(4) . ?
C7 C8 1.431(5) . ?
C10 H10A 0.9500 . ?
C11 H11A 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
C2 S1 C5 91.60(19) . . ?
C10 C9 C8 119.3(4) . . ?
C10 C9 H9A 120.3 . . ?
C8 C9 H9A 120.3 . . ?
F1 C12 C8 118.6(3) . . ?
F1 C12 C11 118.4(3) . . ?
C8 C12 C11 123.0(3) . . ?
F1A C9A C10 122.8(6) . . ?
F1A C9A C8 117.2(6) . . ?
C10 C9A C8 119.3(4) . . ?
C8 C12A C11 123.0(3) . . ?
C8 C12A H12A 118.5 . . ?
C11 C12A H12A 118.5 . . ?
C1 N1 H1C 109.5 . . ?
C1 N1 H1D 109.5 . . ?
H1C N1 H1D 109.5 . . ?
C1 N1 H1E 109.5 . . ?
H1C N1 H1E 109.5 . . ?
H1D N1 H1E 109.5 . . ?
C10 N2 C11 117.9(3) . . ?
C2 C1 N1 111.5(2) . . ?
C2 C1 H1A 109.3 . . ?
N1 C1 H1A 109.3 . . ?
C2 C1 H1B 109.3 . . ?
N1 C1 H1B 109.3 . . ?
H1A C1 H1B 108.0 . . ?
C3 C2 C1 128.5(3) . . ?
C3 C2 S1 111.4(3) . . ?
C1 C2 S1 120.1(3) . . ?
C2 C3 C4 113.3(3) . . ?
C2 C3 H3A 123.3 . . ?
C4 C3 H3A 123.3 . . ?
C5 C4 C3 112.2(4) . . ?
C5 C4 H4A 123.9 . . ?
C3 C4 H4A 123.9 . . ?
C4 C5 C6 126.4(4) . . ?
C4 C5 S1 111.5(3) . . ?
C6 C5 S1 122.1(3) . . ?
C7 C6 C5 177.7(4) . . ?
C6 C7 C8 175.5(4) . . ?
C12 C8 C9 115.2(3) . . ?
C12A C8 C9A 115.2(3) . . ?
C12A C8 C7 121.6(4) . . ?
C12 C8 C7 121.6(4) . . ?
C9 C8 C7 123.2(4) . . ?
C9A C8 C7 123.2(4) . . ?
N2 C10 C9 123.3(3) . . ?
N2 C10 C9A 123.3(3) . . ?
N2 C10 H10A 118.4 . . ?
C9 C10 H10A 118.4 . . ?
N2 C11 C12 121.3(3) . . ?
N2 C11 C12A 121.3(3) . . ?
N2 C11 H11A 119.4 . . ?
C12 C11 H11A 119.4 . . ?

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
N1 C1 C2 C3 -85.0(4) . . . . ?
N1 C1 C2 S1 94.0(3) . . . . ?
C5 S1 C2 C3 0.0(3) . . . . ?
C5 S1 C2 C1 -179.2(3) . . . . ?
C1 C2 C3 C4 179.2(3) . . . . ?
S1 C2 C3 C4 0.1(4) . . . . ?
C2 C3 C4 C5 -0.2(4) . . . . ?
C3 C4 C5 C6 -179.8(3) . . . . ?
C3 C4 C5 S1 0.2(4) . . . . ?
C2 S1 C5 C4 -0.1(3) . . . . ?
C2 S1 C5 C6 179.9(3) . . . . ?
C11 C12A C8 C9A 0.9(5) . . . . ?
C11 C12A C8 C7 -177.2(3) . . . . ?
F1 C12 C8 C9 179.4(3) . . . . ?
C11 C12 C8 C9 0.9(5) . . . . ?
F1 C12 C8 C7 1.3(5) . . . . ?
C11 C12 C8 C7 -177.2(3) . . . . ?
C10 C9 C8 C12 -0.3(5) . . . . ?
C10 C9 C8 C7 177.8(4) . . . . ?
F1A C9A C8 C12A -171.0(7) . . . . ?
C10 C9A C8 C12A -0.3(5) . . . . ?
F1A C9A C8 C7 7.1(9) . . . . ?
C10 C9A C8 C7 177.8(4) . . . . ?
C11 N2 C10 C9 0.0(5) . . . . ?
C11 N2 C10 C9A 0.0(5) . . . . ?
C8 C9 C10 N2 -0.1(6) . . . . ?
F1A C9A C10 N2 170.0(7) . . . . ?
C8 C9A C10 N2 -0.1(6) . . . . ?
C10 N2 C11 C12 0.5(5) . . . . ?
C10 N2 C11 C12A 0.5(5) . . . . ?
F1 C12 C11 N2 -179.5(3) . . . . ?
C8 C12 C11 N2 -1.1(5) . . . . ?
C8 C12A C11 N2 -1.1(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
N1 H1C N2 0.91 1.97 2.860(4) 165.2 1_664 yes
N1 H1D Br1 0.91 2.49 3.305(3) 149.0 1_465 yes
N1 H1E Br1 0.91 2.53 3.386(2) 157.1 1_455 yes

_refine_diff_density_max         0.322
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.064

####################################################################### 
# 
# 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_d2233_a
_database_code_depnum_ccdc_archive 'CCDC 2180023'
loop_
_audit_author_name
_audit_author_address
'Alan J. Lough'
;University of Toronto
Canada
;
_audit_update_record             
;
2022-06-18 deposited with the CCDC.	2022-09-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2019/1
_shelx_SHELXL_version_number     2019/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H11 F N2 S, 2(Br)'
_chemical_formula_sum            'C12 H11 Br2 F N2 S'
_chemical_formula_weight         394.11

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'
F F 0.0171 0.0103 '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      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                   4.5711(10)
_cell_length_b                   12.769(3)
_cell_length_c                   13.073(3)
_cell_angle_alpha                69.971(6)
_cell_angle_beta                 89.227(6)
_cell_angle_gamma                85.826(6)
_cell_volume                     714.9(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    2875
_cell_measurement_theta_min      3.17
_cell_measurement_theta_max      24.41

_exptl_crystal_description       Shard
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.831
_exptl_crystal_F_000             384
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    5.810
_shelx_estimated_absorpt_T_min   0.421
_shelx_estimated_absorpt_T_max   0.801
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6228
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_process_details   'SADABS (Krause et al., 2015)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube with Bruker Triumph monochromator'
_diffrn_measurement_device_type  'Bruker Kappa APEX-DUO CMOS PHOTON II'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16185
_diffrn_reflns_av_unetI/netI     0.0572
_diffrn_reflns_av_R_equivalents  0.0615
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.658
_diffrn_reflns_theta_max         27.478
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3253
_reflns_number_gt                2350
_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       'APEX4 (Bruker AXS, 2021)'
_computing_cell_refinement       APEX4
_computing_data_reduction        APEX4
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL-2019/1 (Sheldrick, 2015b)'
_computing_molecular_graphics    'PLATON (Spek, 2009)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'
_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)+(0.0208P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_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         3253
_refine_ls_number_parameters     179
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0563
_refine_ls_R_factor_gt           0.0309
_refine_ls_wR_factor_ref         0.0581
_refine_ls_wR_factor_gt          0.0539
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_restrained_S_all      1.010
_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
Br1 Br 1.34722(6) 1.11918(2) 0.56098(2) 0.02203(9) Uani 1 1 d . . . . .
Br2 Br -0.54606(7) -0.08269(3) 0.86815(2) 0.02620(10) Uani 1 1 d . . . . .
S1 S 0.75319(17) 0.63639(6) 0.67942(6) 0.02296(18) Uani 1 1 d . . . . .
F1 F 0.0775(4) 0.39745(16) 0.60643(15) 0.0420(5) Uani 1 1 d . . . . .
N1 N 0.9084(6) 0.9130(2) 0.6631(2) 0.0211(6) Uani 1 1 d . . . . .
H1N H 1.024(9) 0.973(4) 0.644(3) 0.081(15) Uiso 1 1 d . . . . .
H2N H 0.791(7) 0.915(3) 0.725(3) 0.041(10) Uiso 1 1 d . . . . .
H3N H 0.773(7) 0.921(2) 0.608(2) 0.022(9) Uiso 1 1 d . . . . .
N2 N -0.2398(6) 0.1543(2) 0.7736(2) 0.0288(7) Uani 1 1 d . . . . .
H4N H -0.357(7) 0.104(3) 0.771(3) 0.038(10) Uiso 1 1 d . . . . .
C1 C 1.1025(6) 0.8089(2) 0.6823(2) 0.0206(7) Uani 1 1 d . . . . .
H1A H 1.278482 0.811811 0.724269 0.025 Uiso 1 1 calc R U . . .
H1B H 1.168388 0.804132 0.611421 0.025 Uiso 1 1 calc R U . . .
C2 C 0.9476(6) 0.7075(2) 0.7430(2) 0.0184(7) Uani 1 1 d . . . . .
C3 C 0.9347(6) 0.6599(3) 0.8536(2) 0.0240(7) Uani 1 1 d . . . . .
H3A H 1.028757 0.687707 0.902391 0.029 Uiso 1 1 calc R U . . .
C4 C 0.7685(6) 0.5656(3) 0.8884(3) 0.0247(7) Uani 1 1 d . . . . .
H4A H 0.738159 0.523353 0.962672 0.030 Uiso 1 1 calc R U . . .
C5 C 0.6552(6) 0.5417(2) 0.8030(2) 0.0204(7) Uani 1 1 d . . . . .
C6 C 0.4740(7) 0.4558(2) 0.8053(2) 0.0234(7) Uani 1 1 d . . . . .
C7 C 0.3193(7) 0.3848(3) 0.8029(3) 0.0255(7) Uani 1 1 d . . . . .
C8 C 0.1304(6) 0.3044(2) 0.7960(2) 0.0195(7) Uani 1 1 d . . . . .
C9 C 0.0102(7) 0.3128(3) 0.6960(3) 0.0258(7) Uani 1 1 d . . . . .
C10 C -0.1751(7) 0.2383(3) 0.6842(3) 0.0297(8) Uani 1 1 d . . . . .
H10A H -0.254836 0.245949 0.615089 0.036 Uiso 1 1 calc R U . . .
C11 C -0.1311(7) 0.1401(3) 0.8713(3) 0.0303(8) Uani 1 1 d . . . . .
H11A H -0.182363 0.078213 0.932127 0.036 Uiso 1 1 calc R U . . .
C12 C 0.0555(7) 0.2141(2) 0.8856(3) 0.0256(7) Uani 1 1 d . . . . .
H12A H 0.132337 0.203684 0.955805 0.031 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
S1 C2 1.720(3) . ?
S1 C5 1.730(3) . ?
F1 C9 1.344(3) . ?
N1 C1 1.491(4) . ?
N1 H1N 0.93(4) . ?
N1 H2N 0.97(3) . ?
N1 H3N 0.93(3) . ?
N2 C11 1.326(4) . ?
N2 C10 1.334(4) . ?
N2 H4N 0.88(3) . ?
C1 C2 1.491(4) . ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 C3 1.365(4) . ?
C3 C4 1.408(4) . ?
C3 H3A 0.9500 . ?
C4 C5 1.371(4) . ?
C4 H4A 0.9500 . ?
C5 C6 1.414(4) . ?
C6 C7 1.198(4) . ?
C7 C8 1.415(4) . ?
C8 C12 1.392(4) . ?
C8 C9 1.392(4) . ?
C9 C10 1.367(4) . ?
C10 H10A 0.9500 . ?
C11 C12 1.378(4) . ?
C11 H11A 0.9500 . ?
C12 H12A 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
C2 S1 C5 91.69(15) . . ?
C1 N1 H1N 109(3) . . ?
C1 N1 H2N 115.1(19) . . ?
H1N N1 H2N 108(3) . . ?
C1 N1 H3N 110.0(18) . . ?
H1N N1 H3N 111(3) . . ?
H2N N1 H3N 105(3) . . ?
C11 N2 C10 123.1(3) . . ?
C11 N2 H4N 115(2) . . ?
C10 N2 H4N 122(2) . . ?
N1 C1 C2 111.4(2) . . ?
N1 C1 H1A 109.4 . . ?
C2 C1 H1A 109.4 . . ?
N1 C1 H1B 109.4 . . ?
C2 C1 H1B 109.4 . . ?
H1A C1 H1B 108.0 . . ?
C3 C2 C1 125.9(3) . . ?
C3 C2 S1 111.2(2) . . ?
C1 C2 S1 122.9(2) . . ?
C2 C3 C4 113.5(3) . . ?
C2 C3 H3A 123.3 . . ?
C4 C3 H3A 123.3 . . ?
C5 C4 C3 112.5(3) . . ?
C5 C4 H4A 123.8 . . ?
C3 C4 H4A 123.8 . . ?
C4 C5 C6 129.0(3) . . ?
C4 C5 S1 111.2(2) . . ?
C6 C5 S1 119.8(2) . . ?
C7 C6 C5 177.4(3) . . ?
C6 C7 C8 177.5(4) . . ?
C12 C8 C9 116.6(3) . . ?
C12 C8 C7 123.3(3) . . ?
C9 C8 C7 120.1(3) . . ?
F1 C9 C10 117.9(3) . . ?
F1 C9 C8 119.2(3) . . ?
C10 C9 C8 122.8(3) . . ?
N2 C10 C9 117.5(3) . . ?
N2 C10 H10A 121.3 . . ?
C9 C10 H10A 121.3 . . ?
N2 C11 C12 120.7(3) . . ?
N2 C11 H11A 119.7 . . ?
C12 C11 H11A 119.7 . . ?
C11 C12 C8 119.4(3) . . ?
C11 C12 H12A 120.3 . . ?
C8 C12 H12A 120.3 . . ?

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
N1 C1 C2 C3 -88.4(4) . . . . ?
N1 C1 C2 S1 90.5(3) . . . . ?
C5 S1 C2 C3 -0.2(2) . . . . ?
C5 S1 C2 C1 -179.1(2) . . . . ?
C1 C2 C3 C4 179.0(3) . . . . ?
S1 C2 C3 C4 0.1(3) . . . . ?
C2 C3 C4 C5 0.1(4) . . . . ?
C3 C4 C5 C6 -178.6(3) . . . . ?
C3 C4 C5 S1 -0.3(3) . . . . ?
C2 S1 C5 C4 0.3(2) . . . . ?
C2 S1 C5 C6 178.8(2) . . . . ?
C12 C8 C9 F1 -179.2(3) . . . . ?
C7 C8 C9 F1 0.5(4) . . . . ?
C12 C8 C9 C10 0.8(5) . . . . ?
C7 C8 C9 C10 -179.5(3) . . . . ?
C11 N2 C10 C9 -0.6(5) . . . . ?
F1 C9 C10 N2 179.8(3) . . . . ?
C8 C9 C10 N2 -0.2(5) . . . . ?
C10 N2 C11 C12 0.8(5) . . . . ?
N2 C11 C12 C8 -0.2(5) . . . . ?
C9 C8 C12 C11 -0.6(4) . . . . ?
C7 C8 C12 C11 179.7(3) . . . . ?

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 H1N Br1 0.93(4) 2.41(4) 3.321(3) 168(3) . yes
N1 H2N Br2 0.97(3) 2.41(3) 3.382(3) 174(3) 1_665 yes
N1 H3N Br1 0.93(3) 2.51(3) 3.332(3) 148(2) 2_776 yes
N2 H4N Br2 0.88(3) 2.49(3) 3.263(3) 147(3) . yes

_refine_diff_density_max         0.464
_refine_diff_density_min         -0.534
_refine_diff_density_rms         0.099

