# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 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_sb1527_hy
_database_code_depnum_ccdc_archive 'CCDC 2329624'
loop_
_audit_author_name
_audit_author_address
'Martin Nieger'
;University of Helsinki
Finland
;
_audit_update_record             
;
2024-01-30 deposited with the CCDC.	2024-05-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
;
5-phenyl-2-(phenylamino)-6H-1,3,4-thiadiazin-3-ium
;

_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C15 H14 N3 S, Br'
_chemical_formula_sum            'C15 H14 Br N3 S'
_chemical_formula_weight         348.26

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 '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/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   8.9077(1)
_cell_length_b                   9.1847(1)
_cell_length_c                   18.1367(2)
_cell_angle_alpha                90
_cell_angle_beta                 93.364(1)
_cell_angle_gamma                90
_cell_volume                     1481.29(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    133(2)
_cell_measurement_reflns_used    14033
_cell_measurement_theta_min      2.3
_cell_measurement_theta_max      78.8

_exptl_crystal_description       blocks
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_F_000             704
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.183
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.131
_exptl_absorpt_coefficient_mu    5.035
_shelx_estimated_absorpt_T_min   0.459
_shelx_estimated_absorpt_T_max   0.558
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.76337
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?




_diffrn_ambient_temperature      133(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_detector_area_resol_mean 10.0000

_diffrn_measurement_method       'omega scans, 0.5 deg.'

_diffrn_reflns_number            16484
_diffrn_reflns_av_unetI/netI     0.0099
_diffrn_reflns_av_R_equivalents  0.0162
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         5.401
_diffrn_reflns_theta_max         79.309
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             3177
_reflns_number_gt                3161
_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 1.171.42.89a (Rigaku OD, 2023)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_structure_solution    SHELXT
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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)+(0.0219P)²+1.1270P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014)'
_refine_ls_extinction_coef       0.00182(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3177
_refine_ls_number_parameters     188
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0203
_refine_ls_R_factor_gt           0.0202
_refine_ls_wR_factor_ref         0.0513
_refine_ls_wR_factor_gt          0.0512
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_restrained_S_all      1.089
_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 0.25957(2) 0.31608(2) 0.44651(2) 0.01901(7) Uani 1 1 d . . . . .
S1 S 0.87653(4) 0.32924(4) 0.46049(2) 0.01815(9) Uani 1 1 d . . . . .
C2 C 0.68364(16) 0.34164(16) 0.46581(8) 0.0162(3) Uani 1 1 d . . . . .
N3 N 0.59958(13) 0.40419(14) 0.41130(6) 0.0174(2) Uani 1 1 d D . . . .
H3 H 0.5028(16) 0.395(2) 0.4142(10) 0.021 Uiso 1 1 d D U . . .
N4 N 0.64107(13) 0.42265(14) 0.33889(6) 0.0173(2) Uani 1 1 d . . . . .
C5 C 0.78026(15) 0.45212(16) 0.33009(8) 0.0165(3) Uani 1 1 d . . . . .
C6 C 0.89042(16) 0.47704(17) 0.39483(8) 0.0188(3) Uani 1 1 d . . . . .
H6A H 0.8683 0.5708 0.4189 0.023 Uiso 1 1 calc R U . . .
H6B H 0.9938 0.4817 0.3777 0.023 Uiso 1 1 calc R U . . .
N21 N 0.61397(14) 0.28836(14) 0.52253(7) 0.0174(2) Uani 1 1 d D . . . .
H21 H 0.5178(17) 0.291(2) 0.5179(10) 0.021 Uiso 1 1 d D U . . .
C21 C 0.68529(16) 0.23158(16) 0.58919(8) 0.0179(3) Uani 1 1 d . . . . .
C22 C 0.79148(17) 0.12128(17) 0.58685(9) 0.0227(3) Uani 1 1 d . . . . .
H22 H 0.8188 0.0830 0.5409 0.027 Uiso 1 1 calc R U . . .
C23 C 0.85738(18) 0.06763(19) 0.65280(10) 0.0291(4) Uani 1 1 d . . . . .
H23 H 0.9317 -0.0065 0.6520 0.035 Uiso 1 1 calc R U . . .
C24 C 0.81487(19) 0.12212(19) 0.71968(9) 0.0295(4) Uani 1 1 d . . . . .
H24 H 0.8608 0.0858 0.7646 0.035 Uiso 1 1 calc R U . . .
C25 C 0.7058(2) 0.22914(18) 0.72140(9) 0.0269(3) Uani 1 1 d . . . . .
H25 H 0.6756 0.2646 0.7675 0.032 Uiso 1 1 calc R U . . .
C26 C 0.64039(18) 0.28487(17) 0.65599(8) 0.0208(3) Uani 1 1 d . . . . .
H26 H 0.5658 0.3586 0.6570 0.025 Uiso 1 1 calc R U . . .
C51 C 0.82514(16) 0.46556(16) 0.25336(8) 0.0174(3) Uani 1 1 d . . . . .
C52 C 0.94752(17) 0.55150(17) 0.23639(9) 0.0209(3) Uani 1 1 d . . . . .
H52 H 1.0068 0.5978 0.2748 0.025 Uiso 1 1 calc R U . . .
C53 C 0.98283(18) 0.56951(18) 0.16333(9) 0.0254(3) Uani 1 1 d . . . . .
H53 H 1.0652 0.6293 0.1518 0.030 Uiso 1 1 calc R U . . .
C54 C 0.89789(19) 0.50030(19) 0.10735(9) 0.0272(3) Uani 1 1 d . . . . .
H54 H 0.9223 0.5129 0.0575 0.033 Uiso 1 1 calc R U . . .
C55 C 0.77736(19) 0.41260(19) 0.12366(9) 0.0267(3) Uani 1 1 d . . . . .
H55 H 0.7200 0.3646 0.0851 0.032 Uiso 1 1 calc R U . . .
C56 C 0.74090(17) 0.39518(18) 0.19642(8) 0.0221(3) Uani 1 1 d . . . . .
H56 H 0.6584 0.3352 0.2076 0.027 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 1.7304(14) . ?
S1 C6 1.8148(15) . ?
C2 N21 1.3259(19) . ?
C2 N3 1.3346(18) . ?
N3 N4 1.3954(16) . ?
N3 H3 0.871(14) . ?
N4 C5 1.2880(18) . ?
C5 C51 1.4753(19) . ?
C5 C6 1.5029(19) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
N21 C21 1.4306(18) . ?
N21 H21 0.857(15) . ?
C21 C26 1.387(2) . ?
C21 C22 1.388(2) . ?
C22 C23 1.391(2) . ?
C22 H22 0.9500 . ?
C23 C24 1.385(3) . ?
C23 H23 0.9500 . ?
C24 C25 1.384(3) . ?
C24 H24 0.9500 . ?
C25 C26 1.388(2) . ?
C25 H25 0.9500 . ?
C26 H26 0.9500 . ?
C51 C52 1.395(2) . ?
C51 C56 1.399(2) . ?
C52 C53 1.390(2) . ?
C52 H52 0.9500 . ?
C53 C54 1.385(3) . ?
C53 H53 0.9500 . ?
C54 C55 1.388(2) . ?
C54 H54 0.9500 . ?
C55 C56 1.386(2) . ?
C55 H55 0.9500 . ?
C56 H56 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 C6 95.36(7) . . ?
N21 C2 N3 117.77(13) . . ?
N21 C2 S1 122.04(11) . . ?
N3 C2 S1 120.19(11) . . ?
C2 N3 N4 125.55(12) . . ?
C2 N3 H3 115.5(12) . . ?
N4 N3 H3 112.7(12) . . ?
C5 N4 N3 116.88(12) . . ?
N4 C5 C51 116.78(12) . . ?
N4 C5 C6 121.62(13) . . ?
C51 C5 C6 121.57(12) . . ?
C5 C6 S1 109.41(10) . . ?
C5 C6 H6A 109.8 . . ?
S1 C6 H6A 109.8 . . ?
C5 C6 H6B 109.8 . . ?
S1 C6 H6B 109.8 . . ?
H6A C6 H6B 108.2 . . ?
C2 N21 C21 125.83(12) . . ?
C2 N21 H21 115.1(12) . . ?
C21 N21 H21 119.0(12) . . ?
C26 C21 C22 121.06(14) . . ?
C26 C21 N21 118.22(13) . . ?
C22 C21 N21 120.65(13) . . ?
C21 C22 C23 119.08(15) . . ?
C21 C22 H22 120.5 . . ?
C23 C22 H22 120.5 . . ?
C24 C23 C22 120.11(16) . . ?
C24 C23 H23 119.9 . . ?
C22 C23 H23 119.9 . . ?
C25 C24 C23 120.32(15) . . ?
C25 C24 H24 119.8 . . ?
C23 C24 H24 119.8 . . ?
C24 C25 C26 120.17(16) . . ?
C24 C25 H25 119.9 . . ?
C26 C25 H25 119.9 . . ?
C21 C26 C25 119.22(15) . . ?
C21 C26 H26 120.4 . . ?
C25 C26 H26 120.4 . . ?
C52 C51 C56 119.39(14) . . ?
C52 C51 C5 120.94(13) . . ?
C56 C51 C5 119.63(13) . . ?
C53 C52 C51 120.10(15) . . ?
C53 C52 H52 120.0 . . ?
C51 C52 H52 120.0 . . ?
C54 C53 C52 120.00(15) . . ?
C54 C53 H53 120.0 . . ?
C52 C53 H53 120.0 . . ?
C53 C54 C55 120.42(14) . . ?
C53 C54 H54 119.8 . . ?
C55 C54 H54 119.8 . . ?
C56 C55 C54 119.82(15) . . ?
C56 C55 H55 120.1 . . ?
C54 C55 H55 120.1 . . ?
C55 C56 C51 120.26(15) . . ?
C55 C56 H56 119.9 . . ?
C51 C56 H56 119.9 . . ?

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
C6 S1 C2 N21 -159.15(13) . . . . ?
C6 S1 C2 N3 21.95(13) . . . . ?
N21 C2 N3 N4 -157.72(13) . . . . ?
S1 C2 N3 N4 21.2(2) . . . . ?
C2 N3 N4 C5 -36.6(2) . . . . ?
N3 N4 C5 C51 177.54(12) . . . . ?
N3 N4 C5 C6 -4.6(2) . . . . ?
N4 C5 C6 S1 50.04(17) . . . . ?
C51 C5 C6 S1 -132.24(12) . . . . ?
C2 S1 C6 C5 -51.66(11) . . . . ?
N3 C2 N21 C21 -173.04(14) . . . . ?
S1 C2 N21 C21 8.0(2) . . . . ?
C2 N21 C21 C26 128.30(16) . . . . ?
C2 N21 C21 C22 -54.7(2) . . . . ?
C26 C21 C22 C23 -2.4(2) . . . . ?
N21 C21 C22 C23 -179.32(14) . . . . ?
C21 C22 C23 C24 1.3(2) . . . . ?
C22 C23 C24 C25 0.6(2) . . . . ?
C23 C24 C25 C26 -1.4(2) . . . . ?
C22 C21 C26 C25 1.6(2) . . . . ?
N21 C21 C26 C25 178.65(14) . . . . ?
C24 C25 C26 C21 0.3(2) . . . . ?
N4 C5 C51 C52 153.46(14) . . . . ?
C6 C5 C51 C52 -24.4(2) . . . . ?
N4 C5 C51 C56 -24.4(2) . . . . ?
C6 C5 C51 C56 157.81(14) . . . . ?
C56 C51 C52 C53 1.5(2) . . . . ?
C5 C51 C52 C53 -176.31(14) . . . . ?
C51 C52 C53 C54 -1.0(2) . . . . ?
C52 C53 C54 C55 -0.1(2) . . . . ?
C53 C54 C55 C56 0.6(2) . . . . ?
C54 C55 C56 C51 0.0(2) . . . . ?
C52 C51 C56 C55 -1.0(2) . . . . ?
C5 C51 C56 C55 176.84(14) . . . . ?

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
N3 H3 Br1 0.871(14) 2.391(15) 3.2346(12) 163.3(17) .
N21 H21 Br1 0.857(15) 2.583(15) 3.3795(12) 155.2(16) .

_refine_diff_density_max         0.331
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.050


####################################################################### 
# 
# 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_sb1532_hy
_database_code_depnum_ccdc_archive 'CCDC 2329625'
loop_
_audit_author_name
_audit_author_address
'Martin Nieger'
;University of Helsinki
Finland
;
_audit_update_record             
;
2024-01-30 deposited with the CCDC.	2024-05-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
'(Z)-N-(5-phenyl-3,6-dihydro-2H-1,3,4-thiadiazin-2-ylidene)prop-2-en-1-aminium bromide'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H14 N3 S, Br'
_chemical_formula_sum            'C12 H14 Br N3 S'
_chemical_formula_weight         312.23

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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'

_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+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                   7.4414(3)
_cell_length_b                   18.2272(7)
_cell_length_c                   19.6573(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2666.24(18)
_cell_formula_units_Z            8
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    9842
_cell_measurement_theta_min      3.3
_cell_measurement_theta_max      72.0

_exptl_crystal_description       blocks
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.556
_exptl_crystal_F_000             1264
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    5.514
_shelx_estimated_absorpt_T_min   0.216
_shelx_estimated_absorpt_T_max   0.405
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2802
_exptl_absorpt_correction_T_max  0.4244
_exptl_absorpt_process_details   'SADABD (Sheldrick, 2014)'
_exptl_absorpt_special_details   ?

_exptl_special_details           
;
 dx = 40 mm, 1 deg., 5+1 runs, 1079 frames, 5/20 sec./frame
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   'fine-focus sealed tube, I\mS microfocus'
_diffrn_measurement_device_type  'Bruker D8 VENTURE with PhotonII CPAD detector'
_diffrn_measurement_method       'rotation in φ and ω, 1°, shutterless'

_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            19426
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         4.852
_diffrn_reflns_theta_max         72.087
_diffrn_reflns_theta_full        67.679
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             2613
_reflns_number_gt                2558
_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 Inc., 2021)'
_computing_cell_refinement       'APEX4 (Bruker AXS Inc., 2021)'
_computing_data_reduction        'SAINT (Bruker AXS Inc., 2021)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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)+(0.0233P)²+1.5642P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014)'
_refine_ls_extinction_coef       0.00056(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2613
_refine_ls_number_parameters     161
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0230
_refine_ls_R_factor_gt           0.0223
_refine_ls_wR_factor_ref         0.0563
_refine_ls_wR_factor_gt          0.0559
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_restrained_S_all      1.051
_refine_ls_shift/su_max          0.002
_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 0.18731(3) 0.61449(2) 0.46365(2) 0.03417(9) Uani 1 1 d . . . . .
S1 S 0.28277(6) 0.31472(2) 0.47597(2) 0.02802(11) Uani 1 1 d . . . . .
C2 C 0.2441(2) 0.40821(8) 0.47334(7) 0.0253(3) Uani 1 1 d . . . . .
N3 N 0.17289(19) 0.43874(7) 0.41805(7) 0.0295(3) Uani 1 1 d D . . . .
H3 H 0.164(3) 0.4853(8) 0.4180(10) 0.035 Uiso 1 1 d D U . . .
N4 N 0.16045(19) 0.40759(7) 0.35338(6) 0.0281(3) Uani 1 1 d . . . . .
C5 C 0.1410(2) 0.33723(8) 0.35004(7) 0.0249(3) Uani 1 1 d . . . . .
C6 C 0.1191(2) 0.29043(8) 0.41218(7) 0.0284(3) Uani 1 1 d . . . . .
H6A H 0.1338 0.2381 0.3997 0.034 Uiso 1 1 calc R U . . .
H6B H -0.0034 0.2970 0.4309 0.034 Uiso 1 1 calc R U . . .
N7 N 0.29116(19) 0.44907(7) 0.52562(7) 0.0283(3) Uani 1 1 d D . . . .
H7 H 0.281(3) 0.4952(9) 0.5193(10) 0.034 Uiso 1 1 d D U . . .
C8 C 0.3429(2) 0.41764(9) 0.59152(8) 0.0323(3) Uani 1 1 d . . . . .
H8A H 0.4627 0.3945 0.5872 0.039 Uiso 1 1 calc R U . . .
H8B H 0.2558 0.3789 0.6041 0.039 Uiso 1 1 calc R U . . .
C9 C 0.3489(3) 0.47359(10) 0.64633(9) 0.0416(4) Uani 1 1 d . . . . .
H9 H 0.2511 0.5068 0.6507 0.050 Uiso 1 1 calc R U . . .
C10 C 0.4840(3) 0.47910(11) 0.68900(11) 0.0527(5) Uani 1 1 d . . . . .
H10A H 0.5831 0.4465 0.6855 0.063 Uiso 1 1 calc R U . . .
H10B H 0.4826 0.5157 0.7234 0.063 Uiso 1 1 calc R U . . .
C11 C 0.1291(2) 0.30449(8) 0.28150(7) 0.0255(3) Uani 1 1 d . . . . .
C12 C 0.1823(2) 0.34442(9) 0.22445(8) 0.0306(3) Uani 1 1 d . . . . .
H12 H 0.2359 0.3913 0.2301 0.037 Uiso 1 1 calc R U . . .
C13 C 0.1575(2) 0.31619(10) 0.15953(8) 0.0360(4) Uani 1 1 d . . . . .
H13 H 0.1918 0.3442 0.1209 0.043 Uiso 1 1 calc R U . . .
C14 C 0.0827(2) 0.24715(10) 0.15112(8) 0.0373(4) Uani 1 1 d . . . . .
H14 H 0.0648 0.2280 0.1067 0.045 Uiso 1 1 calc R U . . .
C15 C 0.0342(2) 0.20606(9) 0.20728(9) 0.0355(4) Uani 1 1 d . . . . .
H15 H -0.0146 0.1583 0.2014 0.043 Uiso 1 1 calc R U . . .
C16 C 0.0568(2) 0.23439(8) 0.27228(8) 0.0308(3) Uani 1 1 d . . . . .
H16 H 0.0229 0.2060 0.3107 0.037 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 1.7290(15) . ?
S1 C6 1.8034(16) . ?
C2 N7 1.316(2) . ?
C2 N3 1.331(2) . ?
N3 N4 1.3954(18) . ?
N3 H3 0.852(15) . ?
N4 C5 1.2923(19) . ?
C5 C11 1.4763(19) . ?
C5 C6 1.4989(19) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
N7 C8 1.468(2) . ?
N7 H7 0.854(15) . ?
C8 C9 1.484(2) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C10 1.313(3) . ?
C9 H9 0.9500 . ?
C10 H10A 0.9500 . ?
C10 H10B 0.9500 . ?
C11 C12 1.394(2) . ?
C11 C16 1.398(2) . ?
C12 C13 1.388(2) . ?
C12 H12 0.9500 . ?
C13 C14 1.386(3) . ?
C13 H13 0.9500 . ?
C14 C15 1.382(3) . ?
C14 H14 0.9500 . ?
C15 C16 1.388(2) . ?
C15 H15 0.9500 . ?
C16 H16 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 C6 96.25(7) . . ?
N7 C2 N3 120.45(14) . . ?
N7 C2 S1 119.33(12) . . ?
N3 C2 S1 120.18(11) . . ?
C2 N3 N4 126.89(13) . . ?
C2 N3 H3 116.6(14) . . ?
N4 N3 H3 113.6(13) . . ?
C5 N4 N3 117.22(12) . . ?
N4 C5 C11 117.02(13) . . ?
N4 C5 C6 122.39(13) . . ?
C11 C5 C6 120.47(12) . . ?
C5 C6 S1 110.68(11) . . ?
C5 C6 H6A 109.5 . . ?
S1 C6 H6A 109.5 . . ?
C5 C6 H6B 109.5 . . ?
S1 C6 H6B 109.5 . . ?
H6A C6 H6B 108.1 . . ?
C2 N7 C8 122.54(13) . . ?
C2 N7 H7 114.9(13) . . ?
C8 N7 H7 122.4(13) . . ?
N7 C8 C9 112.36(14) . . ?
N7 C8 H8A 109.1 . . ?
C9 C8 H8A 109.1 . . ?
N7 C8 H8B 109.1 . . ?
C9 C8 H8B 109.1 . . ?
H8A C8 H8B 107.9 . . ?
C10 C9 C8 122.64(18) . . ?
C10 C9 H9 118.7 . . ?
C8 C9 H9 118.7 . . ?
C9 C10 H10A 120.0 . . ?
C9 C10 H10B 120.0 . . ?
H10A C10 H10B 120.0 . . ?
C12 C11 C16 118.82(14) . . ?
C12 C11 C5 120.39(13) . . ?
C16 C11 C5 120.72(13) . . ?
C13 C12 C11 120.55(15) . . ?
C13 C12 H12 119.7 . . ?
C11 C12 H12 119.7 . . ?
C14 C13 C12 119.97(16) . . ?
C14 C13 H13 120.0 . . ?
C12 C13 H13 120.0 . . ?
C15 C14 C13 120.10(15) . . ?
C15 C14 H14 119.9 . . ?
C13 C14 H14 119.9 . . ?
C14 C15 C16 120.14(16) . . ?
C14 C15 H15 119.9 . . ?
C16 C15 H15 119.9 . . ?
C15 C16 C11 120.38(15) . . ?
C15 C16 H16 119.8 . . ?
C11 C16 H16 119.8 . . ?

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
C6 S1 C2 N7 158.81(14) . . . . ?
C6 S1 C2 N3 -23.40(15) . . . . ?
N7 C2 N3 N4 161.73(15) . . . . ?
S1 C2 N3 N4 -16.0(2) . . . . ?
C2 N3 N4 C5 31.9(2) . . . . ?
N3 N4 C5 C11 -179.62(13) . . . . ?
N3 N4 C5 C6 4.4(2) . . . . ?
N4 C5 C6 S1 -46.52(19) . . . . ?
C11 C5 C6 S1 137.59(12) . . . . ?
C2 S1 C6 C5 49.37(12) . . . . ?
N3 C2 N7 C8 169.97(15) . . . . ?
S1 C2 N7 C8 -12.2(2) . . . . ?
C2 N7 C8 C9 -166.69(16) . . . . ?
N7 C8 C9 C10 -132.9(2) . . . . ?
N4 C5 C11 C12 16.0(2) . . . . ?
C6 C5 C11 C12 -167.94(15) . . . . ?
N4 C5 C11 C16 -161.07(15) . . . . ?
C6 C5 C11 C16 15.0(2) . . . . ?
C16 C11 C12 C13 2.4(2) . . . . ?
C5 C11 C12 C13 -174.67(15) . . . . ?
C11 C12 C13 C14 -1.3(2) . . . . ?
C12 C13 C14 C15 -0.6(3) . . . . ?
C13 C14 C15 C16 1.3(3) . . . . ?
C14 C15 C16 C11 -0.2(3) . . . . ?
C12 C11 C16 C15 -1.7(2) . . . . ?
C5 C11 C16 C15 175.41(15) . . . . ?

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
N3 H3 Br1 0.852(15) 2.525(16) 3.3282(13) 157.5(18) .
C6 H6A Br1 0.99 2.90 3.6584(15) 133.7 8_655
C6 H6B Br1 0.99 2.96 3.7628(16) 138.7 5_566
N7 H7 Br1 0.854(15) 2.532(16) 3.3425(14) 158.9(17) .
C8 H8A Br1 0.99 2.79 3.7067(18) 153.4 5_666

_refine_diff_density_max         0.285
_refine_diff_density_min         -0.250
_refine_diff_density_rms         0.049




#==============================================================================
