# Supplementary Information (SI) for Dalton Transactions.
# 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_S2_a
_database_code_depnum_ccdc_archive 'CCDC 2322294'
loop_
_audit_author_name
_audit_author_address
'K. Srinivasan'
;Bharathiar university 
India
;
_audit_update_record             
;
2023-12-28 deposited with the CCDC.	2024-09-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H14 Br N3 O2 S'
_chemical_formula_sum            'C14 H14 Br N3 O2 S'
_chemical_formula_weight         368.25

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'
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'

_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                   8.0540(19)
_cell_length_b                   10.596(2)
_cell_length_c                   10.613(3)
_cell_angle_alpha                104.764(6)
_cell_angle_beta                 109.118(6)
_cell_angle_gamma                106.152(6)
_cell_volume                     759.9(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9875
_cell_measurement_theta_min      2.43
_cell_measurement_theta_max      27.22

_exptl_crystal_description       ' Rectangular Block'
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.609
_exptl_crystal_F_000             372
_exptl_transmission_factor_min   0.7840
_exptl_transmission_factor_max   0.8710
_exptl_crystal_size_max          0.030
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    2.849
_shelx_estimated_absorpt_T_min   0.919
_shelx_estimated_absorpt_T_max   0.972
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   'R.H.Blessing,Acta Crystallogr A1995,51,33'
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Shielded Microfocus tube'
_diffrn_measurement_device_type  'Bruker APEX-III CMOS Photon detector'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            27052
_diffrn_reflns_av_unetI/netI     0.0927
_diffrn_reflns_av_R_equivalents  0.2695
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_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         2.197
_diffrn_reflns_theta_max         27.402
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3442
_reflns_number_gt                2799
_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       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and Encifer'

_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)+(0.0549P)²+0.3697P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3442
_refine_ls_number_parameters     192
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0688
_refine_ls_R_factor_gt           0.0551
_refine_ls_wR_factor_ref         0.1509
_refine_ls_wR_factor_gt          0.1371
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_restrained_S_all      1.041
_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 0.04311(5) 0.39626(4) -0.21352(3) 0.05336(18) Uani 1 1 d . . . . .
S1 S 0.80409(15) 1.10548(10) 0.95093(9) 0.0531(3) Uani 1 1 d . . . . .
O1 O 0.6163(4) 0.3506(2) 0.2819(2) 0.0372(5) Uani 1 1 d . . . . .
O2 O 0.7824(4) 0.4077(3) 0.5122(2) 0.0502(7) Uani 1 1 d . . . . .
N1 N 0.6947(4) 0.7720(3) 0.6266(3) 0.0365(6) Uani 1 1 d . . . . .
N2 N 0.7888(4) 0.8842(3) 0.7579(3) 0.0398(7) Uani 1 1 d . . . . .
H2A H 0.900955 0.899242 0.818076 0.048 Uiso 1 1 calc R U . . .
N3 N 0.5311(5) 0.9422(3) 0.6877(3) 0.0442(7) Uani 1 1 d . . . . .
H3 H 0.491773 0.875768 0.605447 0.053 Uiso 1 1 calc R U . . .
C4 C 0.4882(5) 0.3669(3) 0.1717(3) 0.0341(7) Uani 1 1 d . . . . .
C12 C 0.6984(5) 0.9708(3) 0.7897(3) 0.0377(7) Uani 1 1 d . . . . .
C7 C 0.5426(5) 0.5926(3) 0.3382(3) 0.0360(7) Uani 1 1 d . . . . .
H7 H 0.519505 0.675142 0.355963 0.043 Uiso 1 1 calc R U . . .
C9 C 0.6973(5) 0.4450(3) 0.4220(3) 0.0350(7) Uani 1 1 d . . . . .
C8 C 0.6689(4) 0.5777(3) 0.4468(3) 0.0314(6) Uani 1 1 d . . . . .
C10 C 0.7786(5) 0.6919(3) 0.5947(3) 0.0340(7) Uani 1 1 d . . . . .
C2 C 0.3083(5) 0.4934(4) 0.0786(3) 0.0377(7) Uani 1 1 d . . . . .
H2 H 0.276263 0.572085 0.090899 0.045 Uiso 1 1 calc R U . . .
C3 C 0.4422(5) 0.4843(3) 0.1952(3) 0.0325(6) Uani 1 1 d . . . . .
C1 C 0.2243(5) 0.3852(4) -0.0546(3) 0.0379(7) Uani 1 1 d . . . . .
C5 C 0.4060(6) 0.2581(4) 0.0359(3) 0.0442(8) Uani 1 1 d . . . . .
H5 H 0.441020 0.180943 0.021830 0.053 Uiso 1 1 calc R U . . .
C6 C 0.2719(6) 0.2683(4) -0.0763(3) 0.0459(9) Uani 1 1 d . . . . .
H6 H 0.212787 0.196162 -0.167419 0.055 Uiso 1 1 calc R U . . .
C13 C 0.4091(6) 1.0166(4) 0.7067(4) 0.0587(11) Uani 1 1 d . . . . .
H13A H 0.482467 1.118363 0.745182 0.070 Uiso 1 1 calc R U . . .
H13B H 0.362525 0.994484 0.775193 0.070 Uiso 1 1 calc R U . . .
C11 C 0.9731(5) 0.7093(4) 0.6884(4) 0.0527(10) Uani 1 1 d . . . . .
H11A H 1.054826 0.808566 0.736900 0.079 Uiso 1 1 calc R U . . .
H11B H 1.024218 0.662050 0.630479 0.079 Uiso 1 1 calc R U . . .
H11C H 0.966194 0.668481 0.758566 0.079 Uiso 1 1 calc R U . . .
C14 C 0.2427(7) 0.9741(5) 0.5655(5) 0.0707(14) Uani 1 1 d . . . . .
H14A H 0.288453 1.003953 0.500675 0.106 Uiso 1 1 calc R U . . .
H14B H 0.158206 1.018286 0.580958 0.106 Uiso 1 1 calc R U . . .
H14C H 0.175057 0.872638 0.524501 0.106 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
Br1 C1 1.890(3) . ?
S1 C12 1.678(3) . ?
O1 C4 1.369(4) . ?
O1 C9 1.371(4) . ?
O2 C9 1.207(4) . ?
N1 C10 1.271(4) . ?
N1 N2 1.376(3) . ?
N2 C12 1.364(4) . ?
N2 H2A 0.8600 . ?
N3 C12 1.315(4) . ?
N3 C13 1.452(5) . ?
N3 H3 0.8600 . ?
C4 C3 1.381(5) . ?
C4 C5 1.395(4) . ?
C7 C8 1.342(4) . ?
C7 C3 1.437(4) . ?
C7 H7 0.9300 . ?
C9 C8 1.459(5) . ?
C8 C10 1.496(4) . ?
C10 C11 1.484(5) . ?
C2 C1 1.373(4) . ?
C2 C3 1.396(4) . ?
C2 H2 0.9300 . ?
C1 C6 1.382(5) . ?
C5 C6 1.372(5) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C13 C14 1.499(6) . ?
C13 H13A 0.9700 . ?
C13 H13B 0.9700 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?

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
C4 O1 C9 122.1(2) . . ?
C10 N1 N2 118.5(3) . . ?
C12 N2 N1 117.9(3) . . ?
C12 N2 H2A 121.1 . . ?
N1 N2 H2A 121.1 . . ?
C12 N3 C13 123.5(3) . . ?
C12 N3 H3 118.2 . . ?
C13 N3 H3 118.2 . . ?
O1 C4 C3 121.3(2) . . ?
O1 C4 C5 116.4(3) . . ?
C3 C4 C5 122.2(3) . . ?
N3 C12 N2 116.2(3) . . ?
N3 C12 S1 124.3(3) . . ?
N2 C12 S1 119.6(2) . . ?
C8 C7 C3 121.8(3) . . ?
C8 C7 H7 119.1 . . ?
C3 C7 H7 119.1 . . ?
O2 C9 O1 115.9(3) . . ?
O2 C9 C8 126.9(3) . . ?
O1 C9 C8 117.2(3) . . ?
C7 C8 C9 119.4(3) . . ?
C7 C8 C10 122.0(3) . . ?
C9 C8 C10 118.5(3) . . ?
N1 C10 C11 125.2(3) . . ?
N1 C10 C8 114.4(3) . . ?
C11 C10 C8 120.4(3) . . ?
C1 C2 C3 119.4(3) . . ?
C1 C2 H2 120.3 . . ?
C3 C2 H2 120.3 . . ?
C4 C3 C2 118.4(3) . . ?
C4 C3 C7 117.2(3) . . ?
C2 C3 C7 124.3(3) . . ?
C2 C1 C6 121.4(3) . . ?
C2 C1 Br1 119.9(3) . . ?
C6 C1 Br1 118.7(2) . . ?
C6 C5 C4 118.1(3) . . ?
C6 C5 H5 120.9 . . ?
C4 C5 H5 120.9 . . ?
C5 C6 C1 120.3(3) . . ?
C5 C6 H6 119.8 . . ?
C1 C6 H6 119.8 . . ?
N3 C13 C14 110.4(3) . . ?
N3 C13 H13A 109.6 . . ?
C14 C13 H13A 109.6 . . ?
N3 C13 H13B 109.6 . . ?
C14 C13 H13B 109.6 . . ?
H13A C13 H13B 108.1 . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?

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
C10 N1 N2 C12 178.9(3) . . . . ?
C9 O1 C4 C3 3.7(5) . . . . ?
C9 O1 C4 C5 -175.6(3) . . . . ?
C13 N3 C12 N2 175.3(4) . . . . ?
C13 N3 C12 S1 -5.4(6) . . . . ?
N1 N2 C12 N3 -2.9(5) . . . . ?
N1 N2 C12 S1 177.8(3) . . . . ?
C4 O1 C9 O2 168.1(3) . . . . ?
C4 O1 C9 C8 -10.6(5) . . . . ?
C3 C7 C8 C9 -3.7(5) . . . . ?
C3 C7 C8 C10 178.0(3) . . . . ?
O2 C9 C8 C7 -168.1(4) . . . . ?
O1 C9 C8 C7 10.6(5) . . . . ?
O2 C9 C8 C10 10.3(6) . . . . ?
O1 C9 C8 C10 -171.0(3) . . . . ?
N2 N1 C10 C11 -0.2(5) . . . . ?
N2 N1 C10 C8 -177.0(3) . . . . ?
C7 C8 C10 N1 27.4(5) . . . . ?
C9 C8 C10 N1 -150.9(3) . . . . ?
C7 C8 C10 C11 -149.5(4) . . . . ?
C9 C8 C10 C11 32.1(5) . . . . ?
O1 C4 C3 C2 -179.0(3) . . . . ?
C5 C4 C3 C2 0.2(5) . . . . ?
O1 C4 C3 C7 3.6(5) . . . . ?
C5 C4 C3 C7 -177.2(3) . . . . ?
C1 C2 C3 C4 1.1(5) . . . . ?
C1 C2 C3 C7 178.3(3) . . . . ?
C8 C7 C3 C4 -3.4(5) . . . . ?
C8 C7 C3 C2 179.4(3) . . . . ?
C3 C2 C1 C6 -1.1(6) . . . . ?
C3 C2 C1 Br1 -179.9(3) . . . . ?
O1 C4 C5 C6 177.8(3) . . . . ?
C3 C4 C5 C6 -1.5(6) . . . . ?
C4 C5 C6 C1 1.5(6) . . . . ?
C2 C1 C6 C5 -0.2(6) . . . . ?
Br1 C1 C6 C5 178.6(3) . . . . ?
C12 N3 C13 C14 171.9(4) . . . . ?

_refine_diff_density_max         1.215
_refine_diff_density_min         -0.940
_refine_diff_density_rms         0.107



####################################################################### 
# 
# 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_IOD1052_Br5_MONOP_a
_database_code_depnum_ccdc_archive 'CCDC 2322295'
loop_
_audit_author_name
_audit_author_address
'K. Srinivasan'
;Bharathiar university 
India
;
_audit_update_record             
;
2023-12-28 deposited with the CCDC.	2024-09-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H14 Br N3 O2 S'
_chemical_formula_sum            'C18 H14 Br N3 O2 S'
_chemical_formula_weight         416.29

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'
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'

_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                   6.886(3)
_cell_length_b                   12.995(5)
_cell_length_c                   19.157(7)
_cell_angle_alpha                90
_cell_angle_beta                 93.108(11)
_cell_angle_gamma                90
_cell_volume                     1711.7(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9539
_cell_measurement_theta_min      2.64
_cell_measurement_theta_max      27.19
_exptl_crystal_description       'Rectangular Block'
_exptl_crystal_colour            Orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_F_000             840
_exptl_transmission_factor_min   0.4510
_exptl_transmission_factor_max   0.6480
_exptl_crystal_size_max          0.373
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.187
_exptl_absorpt_coefficient_mu    2.541
_shelx_estimated_absorpt_T_min   0.451
_shelx_estimated_absorpt_T_max   0.648
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   'R.H.Blessing,Acta Crystallogr A1995,51,33'
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Shielded Microfocus tube'
_diffrn_measurement_device_type  'Bruker APEX-III CMOS Photon detector'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            101740
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_av_R_equivalents  0.0466
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         2.644
_diffrn_reflns_theta_max         27.189
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3800
_reflns_number_gt                2976
_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       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and Encifer'
_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)+(0.0362P)²+0.9299P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_extinction_coef       0.0011(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3800
_refine_ls_number_parameters     236
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0329
_refine_ls_wR_factor_ref         0.0838
_refine_ls_wR_factor_gt          0.0766
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_restrained_S_all      1.019
_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 1.48833(4) 0.68141(2) 0.75047(2) 0.07368(13) Uani 1 1 d . . . . .
S1 S -0.09059(10) 0.90554(5) 0.41216(3) 0.06172(19) Uani 1 1 d . . . . .
O1 O 0.8772(2) 0.63550(12) 0.51917(8) 0.0500(4) Uani 1 1 d . . . . .
O2 O 0.5866(2) 0.65744(14) 0.47127(9) 0.0639(5) Uani 1 1 d . . . . .
N3 N 0.1696(3) 0.74977(15) 0.41385(10) 0.0478(5) Uani 1 1 d . . . . .
N2 N 0.2294(3) 0.87882(16) 0.49107(10) 0.0496(5) Uani 1 1 d . . . . .
N1 N 0.3943(3) 0.82384(14) 0.50618(10) 0.0486(4) Uani 1 1 d . . . . .
C6 C 0.9979(3) 0.72716(16) 0.62021(10) 0.0402(4) Uani 1 1 d . . . . .
C7 C 0.8289(3) 0.79107(17) 0.61304(11) 0.0445(5) Uani 1 1 d . . . . .
H7 H 0.816289 0.844852 0.644501 0.053 Uiso 1 1 calc R U . . .
C13 C 0.0895(3) 0.68038(16) 0.36356(10) 0.0437(5) Uani 1 1 d . . . . .
C10 C 0.5174(3) 0.84633(17) 0.55571(11) 0.0436(5) Uani 1 1 d . . . . .
C5 C 1.0201(3) 0.65165(16) 0.57023(11) 0.0417(5) Uani 1 1 d . . . . .
C9 C 0.7039(3) 0.68928(17) 0.51429(11) 0.0453(5) Uani 1 1 d . . . . .
C8 C 0.6876(3) 0.77675(17) 0.56279(10) 0.0413(5) Uani 1 1 d . . . . .
C2 C 1.3009(3) 0.67361(16) 0.67450(12) 0.0466(5) Uani 1 1 d . . . . .
C3 C 1.3245(3) 0.60140(17) 0.62275(12) 0.0487(5) Uani 1 1 d . . . . .
H13 H 1.435713 0.560699 0.623551 0.058 Uiso 1 1 calc R U . . .
C1 C 1.1428(3) 0.73743(17) 0.67364(11) 0.0465(5) Uani 1 1 d . . . . .
H1 H 1.131889 0.787017 0.708217 0.056 Uiso 1 1 calc R U . . .
C15 C -0.1653(4) 0.60460(19) 0.29121(12) 0.0541(6) Uani 1 1 d . . . . .
H15 H -0.294952 0.603639 0.274905 0.065 Uiso 1 1 calc R U . . .
C12 C 0.1085(3) 0.83938(17) 0.43860(11) 0.0436(5) Uani 1 1 d . . . . .
C4 C 1.1830(3) 0.59011(17) 0.57020(12) 0.0491(5) Uani 1 1 d . . . . .
H4 H 1.196751 0.541679 0.535075 0.059 Uiso 1 1 calc R U . . .
C16 C -0.0404(4) 0.53242(19) 0.26753(12) 0.0577(6) Uani 1 1 d . . . . .
H16 H -0.083619 0.483520 0.234820 0.069 Uiso 1 1 calc R U . . .
C14 C -0.1030(3) 0.67900(18) 0.33889(11) 0.0502(5) Uani 1 1 d . . . . .
H14 H -0.189855 0.727759 0.354261 0.060 Uiso 1 1 calc R U . . .
C18 C 0.2153(4) 0.60648(18) 0.34057(13) 0.0555(6) Uani 1 1 d . . . . .
H18 H 0.344550 0.606046 0.357359 0.067 Uiso 1 1 calc R U . . .
C11 C 0.4994(4) 0.9345(2) 0.60505(15) 0.0689(8) Uani 1 1 d . . . . .
H11A H 0.624827 0.965329 0.614393 0.103 Uiso 1 1 calc R U . . .
H11B H 0.450325 0.910059 0.647980 0.103 Uiso 1 1 calc R U . . .
H11C H 0.411557 0.984716 0.584468 0.103 Uiso 1 1 calc R U . . .
C17 C 0.1495(4) 0.5333(2) 0.29277(14) 0.0648(7) Uani 1 1 d . . . . .
H17 H 0.235271 0.483955 0.277473 0.078 Uiso 1 1 calc R U . . .
H2 H 0.195(4) 0.932(2) 0.5125(14) 0.063(8) Uiso 1 1 d . . . . .
H12 H 0.274(4) 0.734(2) 0.4326(13) 0.055(7) Uiso 1 1 d . . . . .


_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
Br1 C2 1.895(2) . ?
S1 C12 1.673(2) . ?
O1 C5 1.366(2) . ?
O1 C9 1.381(3) . ?
O2 C9 1.196(3) . ?
N3 C12 1.334(3) . ?
N3 C13 1.410(3) . ?
N3 H12 0.81(3) . ?
N2 N1 1.359(3) . ?
N2 C12 1.369(3) . ?
N2 H2 0.85(3) . ?
N1 C10 1.272(3) . ?
C6 C5 1.385(3) . ?
C6 C1 1.396(3) . ?
C6 C7 1.430(3) . ?
C7 C8 1.344(3) . ?
C7 H7 0.9300 . ?
C13 C18 1.381(3) . ?
C13 C14 1.383(3) . ?
C10 C8 1.480(3) . ?
C10 C11 1.495(3) . ?
C5 C4 1.378(3) . ?
C9 C8 1.476(3) . ?
C2 C1 1.368(3) . ?
C2 C3 1.381(3) . ?
C3 C4 1.370(3) . ?
C3 H13 0.9300 . ?
C1 H1 0.9300 . ?
C15 C16 1.367(4) . ?
C15 C14 1.382(3) . ?
C15 H15 0.9300 . ?
C4 H4 0.9300 . ?
C16 C17 1.369(4) . ?
C16 H16 0.9300 . ?
C14 H14 0.9300 . ?
C18 C17 1.379(4) . ?
C18 H18 0.9300 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C17 H17 0.9300 . ?

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
C5 O1 C9 123.84(16) . . ?
C12 N3 C13 132.99(19) . . ?
C12 N3 H12 110.4(18) . . ?
C13 N3 H12 116.6(18) . . ?
N1 N2 C12 115.27(19) . . ?
N1 N2 H2 125.5(19) . . ?
C12 N2 H2 119.2(19) . . ?
C10 N1 N2 123.61(19) . . ?
C5 C6 C1 118.25(19) . . ?
C5 C6 C7 117.67(18) . . ?
C1 C6 C7 124.07(19) . . ?
C8 C7 C6 122.84(19) . . ?
C8 C7 H7 118.6 . . ?
C6 C7 H7 118.6 . . ?
C18 C13 C14 119.2(2) . . ?
C18 C13 N3 115.7(2) . . ?
C14 C13 N3 125.0(2) . . ?
N1 C10 C8 114.85(19) . . ?
N1 C10 C11 125.0(2) . . ?
C8 C10 C11 120.17(19) . . ?
O1 C5 C4 117.76(18) . . ?
O1 C5 C6 120.13(18) . . ?
C4 C5 C6 122.10(19) . . ?
O2 C9 O1 114.85(19) . . ?
O2 C9 C8 128.9(2) . . ?
O1 C9 C8 116.23(18) . . ?
C7 C8 C9 118.70(19) . . ?
C7 C8 C10 121.32(19) . . ?
C9 C8 C10 119.97(18) . . ?
C1 C2 C3 121.9(2) . . ?
C1 C2 Br1 119.03(16) . . ?
C3 C2 Br1 119.07(16) . . ?
C4 C3 C2 119.6(2) . . ?
C4 C3 H13 120.2 . . ?
C2 C3 H13 120.2 . . ?
C2 C1 C6 119.17(19) . . ?
C2 C1 H1 120.4 . . ?
C6 C1 H1 120.4 . . ?
C16 C15 C14 121.4(2) . . ?
C16 C15 H15 119.3 . . ?
C14 C15 H15 119.3 . . ?
N3 C12 N2 113.38(19) . . ?
N3 C12 S1 127.59(17) . . ?
N2 C12 S1 119.02(17) . . ?
C3 C4 C5 119.0(2) . . ?
C3 C4 H4 120.5 . . ?
C5 C4 H4 120.5 . . ?
C15 C16 C17 118.9(2) . . ?
C15 C16 H16 120.6 . . ?
C17 C16 H16 120.6 . . ?
C15 C14 C13 119.5(2) . . ?
C15 C14 H14 120.3 . . ?
C13 C14 H14 120.3 . . ?
C17 C18 C13 120.1(2) . . ?
C17 C18 H18 119.9 . . ?
C13 C18 H18 119.9 . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C16 C17 C18 120.9(2) . . ?
C16 C17 H17 119.6 . . ?
C18 C17 H17 119.6 . . ?

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
C12 N2 N1 C10 -176.2(2) . . . . ?
C5 C6 C7 C8 4.0(3) . . . . ?
C1 C6 C7 C8 -177.1(2) . . . . ?
C12 N3 C13 C18 166.1(2) . . . . ?
C12 N3 C13 C14 -16.7(4) . . . . ?
N2 N1 C10 C8 -179.59(19) . . . . ?
N2 N1 C10 C11 0.9(4) . . . . ?
C9 O1 C5 C4 177.9(2) . . . . ?
C9 O1 C5 C6 -1.5(3) . . . . ?
C1 C6 C5 O1 176.6(2) . . . . ?
C7 C6 C5 O1 -4.4(3) . . . . ?
C1 C6 C5 C4 -2.8(3) . . . . ?
C7 C6 C5 C4 176.2(2) . . . . ?
C5 O1 C9 O2 -171.9(2) . . . . ?
C5 O1 C9 C8 7.5(3) . . . . ?
C6 C7 C8 C9 2.1(3) . . . . ?
C6 C7 C8 C10 -178.2(2) . . . . ?
O2 C9 C8 C7 171.7(2) . . . . ?
O1 C9 C8 C7 -7.6(3) . . . . ?
O2 C9 C8 C10 -8.0(4) . . . . ?
O1 C9 C8 C10 172.68(19) . . . . ?
N1 C10 C8 C7 -179.8(2) . . . . ?
C11 C10 C8 C7 -0.2(3) . . . . ?
N1 C10 C8 C9 0.0(3) . . . . ?
C11 C10 C8 C9 179.5(2) . . . . ?
C1 C2 C3 C4 -2.4(4) . . . . ?
Br1 C2 C3 C4 175.38(18) . . . . ?
C3 C2 C1 C6 2.1(3) . . . . ?
Br1 C2 C1 C6 -175.74(17) . . . . ?
C5 C6 C1 C2 0.5(3) . . . . ?
C7 C6 C1 C2 -178.4(2) . . . . ?
C13 N3 C12 N2 176.4(2) . . . . ?
C13 N3 C12 S1 -4.3(4) . . . . ?
N1 N2 C12 N3 3.5(3) . . . . ?
N1 N2 C12 S1 -175.77(16) . . . . ?
C2 C3 C4 C5 0.2(3) . . . . ?
O1 C5 C4 C3 -177.0(2) . . . . ?
C6 C5 C4 C3 2.4(3) . . . . ?
C14 C15 C16 C17 1.1(4) . . . . ?
C16 C15 C14 C13 -0.3(4) . . . . ?
C18 C13 C14 C15 -0.7(3) . . . . ?
N3 C13 C14 C15 -177.8(2) . . . . ?
C14 C13 C18 C17 1.0(4) . . . . ?
N3 C13 C18 C17 178.3(2) . . . . ?
C15 C16 C17 C18 -0.9(4) . . . . ?
C13 C18 C17 C16 -0.2(4) . . . . ?

_refine_diff_density_max         0.349
_refine_diff_density_min         -0.534
_refine_diff_density_rms         0.044



