# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 2020

####################################################################### 
# 
# 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_mx8050b
_database_code_depnum_ccdc_archive 'CCDC 1960652'
loop_
_audit_author_name
_audit_author_address
ZYA
;Qingdao University of Science and Technology
China
;
_audit_update_record             
;
2019-10-22 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
_audit_creation_date             2019-07-25
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C17 H14 N2 S2'
_chemical_formula_sum            'C17 H14 N2 S2'
_chemical_formula_weight         310.42
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         CHNS
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'
S S 0.1246 0.1234 '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      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 1 21 1'
_space_group_name_Hall           'P 2yb'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   7.3669(2)
_cell_length_b                   5.94050(10)
_cell_length_c                   17.4582(4)
_cell_angle_alpha                90
_cell_angle_beta                 91.628(2)
_cell_angle_gamma                90
_cell_volume                     763.72(3)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    16097
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      30.0150
_cell_measurement_theta_min      2.2690
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.342
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76489
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.45i (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             324
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0433
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            21477
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.364
_diffrn_reflns_theta_min         2.334
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.930
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -84.00  94.00   0.50    8.00    --    5.00  45.00 150.00  356
  2  ω    -84.00  94.00   0.50    8.00    --    5.00  45.00 120.00  356
  3  ω   -103.00  75.00   0.50    8.00    --  -14.20  45.00 120.00  356
  4  ω   -103.00  75.00   0.50    8.00    --  -14.20  45.00  60.00  356
  5  ω     -9.00  17.00   0.50    8.00    --  -14.20  45.00  60.00   52
  6  ω   -102.00  71.00   0.50    8.00    --  -14.20  45.00 -14.92  346
  7  ω    -22.00  75.00   0.50    8.00    --  -14.20  45.00 150.00  194
  8  ω    -26.00   0.00   0.50    8.00    --  -14.20  45.00   0.00   52
  9  ω   -103.00 -28.00   0.50    8.00    --  -14.20  45.00 150.00  150
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0467969000
_diffrn_orient_matrix_UB_12      -0.0413239000
_diffrn_orient_matrix_UB_13      0.0321033000
_diffrn_orient_matrix_UB_21      0.0611264000
_diffrn_orient_matrix_UB_22      0.0589944000
_diffrn_orient_matrix_UB_23      0.0248802000
_diffrn_orient_matrix_UB_31      -0.0579261000
_diffrn_orient_matrix_UB_32      0.0951893000
_diffrn_orient_matrix_UB_33      -0.0015545000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_reflns_Friedel_coverage         0.744
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.827
_reflns_number_gt                3747
_reflns_number_total             4069
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.009
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details 
;
 Flack x determined using 1506 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         4069
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0446
_refine_ls_restrained_S_all      1.063
_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)+(0.0714P)²+0.2044P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1175
_refine_ls_wR_factor_ref         0.1198
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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
S1 S 0.81262(10) 0.69015(13) 0.67102(5) 0.0370(2) Uani 1 1 d . . . . .
S2 S 0.30903(10) 0.55114(15) 0.79564(5) 0.0379(2) Uani 1 1 d . . . . .
N1 N 0.5688(4) 0.3049(5) 0.85812(15) 0.0365(6) Uani 1 1 d . . . . .
N2 N 0.8101(4) 1.1635(6) 0.6836(2) 0.0459(7) Uani 1 1 d . . . . .
C1 C 0.5718(4) 0.6205(5) 0.69163(18) 0.0324(6) Uani 1 1 d . . . . .
H1 H 0.554809 0.460453 0.679924 0.039 Uiso 1 1 calc R . . . .
C2 C 0.5385(4) 0.6499(6) 0.77736(18) 0.0348(6) Uani 1 1 d . . . . .
H2 H 0.550361 0.808901 0.791611 0.042 Uiso 1 1 calc R . . . .
C3 C 0.3980(4) 0.3143(5) 0.84683(15) 0.0291(6) Uani 1 1 d . . . . .
C4 C 0.6614(4) 0.5038(7) 0.83067(19) 0.0417(8) Uani 1 1 d . . . . .
H4A H 0.767668 0.457670 0.803128 0.050 Uiso 1 1 calc R . . . .
H4B H 0.702335 0.593519 0.874242 0.050 Uiso 1 1 calc R . . . .
C5 C 0.8079(4) 0.9734(6) 0.67928(17) 0.0323(6) Uani 1 1 d . . . . .
C6 C 0.4410(4) 0.7494(6) 0.63972(17) 0.0324(6) Uani 1 1 d . . . . .
C7 C 0.3932(5) 0.6517(8) 0.5701(2) 0.0449(8) Uani 1 1 d . . . . .
H7 H 0.442590 0.514139 0.556146 0.054 Uiso 1 1 calc R . . . .
C8 C 0.2689(6) 0.7632(11) 0.5206(2) 0.0646(15) Uani 1 1 d . . . . .
H8 H 0.236094 0.698650 0.473669 0.078 Uiso 1 1 calc R . . . .
C9 C 0.1958(5) 0.9653(10) 0.5407(3) 0.0649(14) Uani 1 1 d . . . . .
H9 H 0.113865 1.037513 0.507450 0.078 Uiso 1 1 calc R . . . .
C10 C 0.2423(5) 1.0612(8) 0.6092(3) 0.0546(10) Uani 1 1 d . . . . .
H10 H 0.191237 1.198081 0.622852 0.066 Uiso 1 1 calc R . . . .
C11 C 0.3663(5) 0.9553(7) 0.6588(2) 0.0406(7) Uani 1 1 d . . . . .
H11 H 0.399251 1.023092 0.705194 0.049 Uiso 1 1 calc R . . . .
C12 C 0.2716(4) 0.1476(5) 0.87736(16) 0.0288(6) Uani 1 1 d . . . . .
C13 C 0.3288(4) 0.0063(5) 0.93735(17) 0.0335(6) Uani 1 1 d . . . . .
H13 H 0.447608 0.014946 0.956552 0.040 Uiso 1 1 calc R . . . .
C14 C 0.2094(5) -0.1464(6) 0.96832(18) 0.0372(7) Uani 1 1 d . . . . .
H14 H 0.248725 -0.241265 1.007774 0.045 Uiso 1 1 calc R . . . .
C15 C 0.0311(5) -0.1583(6) 0.94068(19) 0.0376(7) Uani 1 1 d . . . . .
H15 H -0.049508 -0.259789 0.961796 0.045 Uiso 1 1 calc R . . . .
C16 C -0.0257(4) -0.0177(6) 0.88137(19) 0.0377(7) Uani 1 1 d . . . . .
H16 H -0.144948 -0.025714 0.862631 0.045 Uiso 1 1 calc R . . . .
C17 C 0.0926(4) 0.1340(5) 0.84981(18) 0.0329(6) Uani 1 1 d . . . . .
H17 H 0.052774 0.227410 0.810033 0.040 Uiso 1 1 calc R . . . .


_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 C1 1.867(3) . ?
S1 C5 1.689(3) . ?
S2 C2 1.826(3) . ?
S2 C3 1.782(3) . ?
N1 C3 1.269(4) . ?
N1 C4 1.452(5) . ?
N2 C5 1.132(5) . ?
C1 C2 1.533(4) . ?
C1 C6 1.512(4) . ?
C2 C4 1.547(4) . ?
C3 C12 1.470(4) . ?
C6 C7 1.384(5) . ?
C6 C11 1.386(5) . ?
C7 C8 1.407(6) . ?
C8 C9 1.366(8) . ?
C9 C10 1.359(7) . ?
C10 C11 1.392(5) . ?
C12 C13 1.398(4) . ?
C12 C17 1.393(4) . ?
C13 C14 1.384(5) . ?
C14 C15 1.388(4) . ?
C15 C16 1.386(5) . ?
C16 C17 1.379(5) . ?

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 S1 C1 100.50(15) . . ?
C3 S2 C2 90.70(15) . . ?
C3 N1 C4 112.7(3) . . ?
C2 C1 S1 110.0(2) . . ?
C6 C1 S1 111.4(2) . . ?
C6 C1 C2 114.2(3) . . ?
C1 C2 S2 108.0(2) . . ?
C1 C2 C4 114.6(3) . . ?
C4 C2 S2 104.1(2) . . ?
N1 C3 S2 117.5(2) . . ?
N1 C3 C12 123.3(3) . . ?
C12 C3 S2 119.1(2) . . ?
N1 C4 C2 112.5(3) . . ?
N2 C5 S1 177.7(3) . . ?
C7 C6 C1 117.2(3) . . ?
C7 C6 C11 119.3(3) . . ?
C11 C6 C1 123.6(3) . . ?
C6 C7 C8 119.2(4) . . ?
C9 C8 C7 120.7(4) . . ?
C10 C9 C8 120.2(4) . . ?
C9 C10 C11 120.2(4) . . ?
C6 C11 C10 120.5(4) . . ?
C13 C12 C3 119.7(2) . . ?
C17 C12 C3 121.1(3) . . ?
C17 C12 C13 119.1(3) . . ?
C14 C13 C12 120.3(3) . . ?
C13 C14 C15 120.2(3) . . ?
C16 C15 C14 119.5(3) . . ?
C17 C16 C15 120.8(3) . . ?
C16 C17 C12 120.2(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 1.447
_oxdiff_exptl_absorpt_empirical_full_min 0.802
####################################################################### 
# 
# 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_tx1455_pl
_database_code_depnum_ccdc_archive 'CCDC 1960653'
loop_
_audit_author_name
_audit_author_address
ZYa
;Qingdao University of Science and Technology
China
;
_audit_update_record             
;
2019-10-22 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
_audit_creation_date             2019-10-12
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C19 H15 Br N2 S2'
_chemical_formula_sum            'C19 H15 Br N2 S2'
_chemical_formula_weight         415.36
_chemical_melting_point          ?
_chemical_oxdiff_formula         CHNS
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'

_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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/n 1'
_space_group_name_Hall           '-P 2yn'
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                   9.8886(2)
_cell_length_b                   16.8537(2)
_cell_length_c                   11.1408(2)
_cell_angle_alpha                90
_cell_angle_beta                 108.661(2)
_cell_angle_gamma                90
_cell_volume                     1759.11(6)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    13196
_cell_measurement_temperature    169.99(11)
_cell_measurement_theta_max      73.3770
_cell_measurement_theta_min      4.9120
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    5.413
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61243
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.14e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'metallic light colourless'
_exptl_crystal_density_diffrn    1.568
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0469
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            32094
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.009
_diffrn_reflns_theta_min         4.944
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.965
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -77.00  26.00   0.50    0.20    --  -46.95  92.00 149.00  206
  2  ω    -25.00  77.00   0.50    0.20    --   46.95 -92.00  36.00  204
  3  ω   -168.00 -77.00   0.50    0.51    --  -99.00 -92.00  36.00  182
  4  ω   -108.00 -26.00   0.50    0.51    --  -99.00  92.00 149.00  164
  5  ω     84.00 169.00   0.50    0.51    --  103.25  92.00 149.00  170
  6  ω     31.00 108.00   0.50    0.51    --  103.25 -92.00  36.00  154
  7  ω   -119.00 -71.00   0.50    0.20    --  -46.95-125.00  90.00   96
  8  ω   -119.00 -71.00   0.50    0.20    --  -46.95-125.00 -90.00   96
  9  ω    -95.00 -10.00   0.50    0.20    --  -46.95 125.00 -30.00  170
 10  ω     32.00 118.00   0.50    0.20    --   46.95  57.00-150.00  172
 11  ω    -27.00  60.00   0.50    0.20    --   46.95 -19.00  60.00  174
 12  ω   -168.00 -86.00   0.50    0.51    --  -99.00 -45.00  60.00  164
 13  ω   -122.00 -26.00   0.50    0.51    --  -99.00  77.00  60.00  192
 14  ω   -168.00 -86.00   0.50    0.51    --  -99.00 -30.00-120.00  164
 15  ω   -115.00 -26.00   0.50    0.51    --  -99.00  61.00 -60.00  178
 16  ω   -168.00 -86.00   0.50    0.51    --  -99.00 -30.00  90.00  164
 17  ω   -168.00 -85.00   0.50    0.51    --  -99.00 -15.00 120.00  166
 18  ω   -168.00 -86.00   0.50    0.51    --  -99.00 -45.00 -60.00  164
 19  ω   -168.00 -81.00   0.50    0.51    --  -99.00 -94.00  90.00  174
 20  ω   -168.00 -86.00   0.50    0.51    --  -99.00 -45.00 -90.00  164
 21  ω   -115.00 -26.00   0.50    0.51    --  -99.00  61.00 150.00  178
 22  ω     31.00 117.00   0.50    0.51    --  103.25-125.00-180.00  172
 23  ω     81.00 169.00   0.50    0.51    --  103.25  77.00-180.00  176
 24  ω     31.00 126.00   0.50    0.51    --  103.25 -77.00   0.00  190
 25  ω     31.00 109.00   0.50    0.51    --  103.25 -94.00-150.00  156
 26  ω     31.00 120.00   0.50    0.51    --  103.25 -61.00  60.00  178
 27  ω     24.00 119.00   0.50    0.20    --   46.95  77.00 120.00  190
 28  ω     24.00 119.00   0.50    0.20    --   46.95  77.00 -60.00  190
 29  ω     24.00 119.00   0.50    0.20    --   46.95  77.00-120.00  190
 30  ω     24.00 104.00   0.50    0.20    --   46.95  77.00  60.00  160
 31  ω     24.00 119.00   0.50    0.20    --   46.95  77.00  30.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1481461000
_diffrn_orient_matrix_UB_12      -0.0041498000
_diffrn_orient_matrix_UB_13      0.1017384000
_diffrn_orient_matrix_UB_21      -0.0217701000
_diffrn_orient_matrix_UB_22      0.0840281000
_diffrn_orient_matrix_UB_23      0.0451611000
_diffrn_orient_matrix_UB_31      -0.0679628000
_diffrn_orient_matrix_UB_32      -0.0357776000
_diffrn_orient_matrix_UB_33      0.0943604000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3200
_reflns_number_total             3544
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.583
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.067
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         3544
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0326
_refine_ls_restrained_S_all      1.048
_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)+(0.0548P)²+0.6964P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0852
_refine_ls_wR_factor_ref         0.0890
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C15(H15), C16(H16), C18(H18), C19(H19)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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
Br1 Br 0.50009(3) -0.18130(2) 0.36216(2) 0.04630(11) Uani 1 1 d . . . . .
S1 S 0.72613(5) 0.21586(3) 0.38733(5) 0.03800(14) Uani 1 1 d . . . . .
S2 S 0.59979(7) 0.20073(4) -0.01411(6) 0.05681(18) Uani 1 1 d . . . . .
N1 N 0.43401(16) 0.22118(10) 0.28060(15) 0.0312(3) Uani 1 1 d . . . . .
N2 N 0.58988(19) 0.32203(9) 0.14865(16) 0.0337(4) Uani 1 1 d . . . . .
C1 C 0.57118(19) 0.34723(11) 0.26714(17) 0.0296(4) Uani 1 1 d . . . . .
C2 C 0.7037(2) 0.32293(11) 0.3769(2) 0.0331(4) Uani 1 1 d . . . . .
H2 H 0.786977 0.344923 0.358979 0.040 Uiso 1 1 calc R . . . .
C3 C 0.7002(2) 0.35971(14) 0.50077(19) 0.0428(5) Uani 1 1 d . . . . .
H3A H 0.779532 0.339851 0.570497 0.051 Uiso 1 1 calc R . . . .
H3B H 0.612246 0.345129 0.516082 0.051 Uiso 1 1 calc R . . . .
C4 C 0.7100(3) 0.44977(14) 0.4933(2) 0.0488(6) Uani 1 1 d . . . . .
H4A H 0.686140 0.473085 0.563562 0.059 Uiso 1 1 calc R . . . .
H4B H 0.807749 0.464245 0.502527 0.059 Uiso 1 1 calc R . . . .
C5 C 0.6128(2) 0.48440(12) 0.3709(2) 0.0370(4) Uani 1 1 d . . . . .
C6 C 0.5868(2) 0.56579(13) 0.3619(2) 0.0440(5) Uani 1 1 d . . . . .
H6 H 0.626296 0.597507 0.432798 0.053 Uiso 1 1 calc R . . . .
C7 C 0.5038(2) 0.60060(13) 0.2504(2) 0.0432(5) Uani 1 1 d . . . . .
H7 H 0.488566 0.655128 0.246440 0.052 Uiso 1 1 calc R . . . .
C8 C 0.4435(2) 0.55398(13) 0.1447(2) 0.0407(5) Uani 1 1 d . . . . .
H8 H 0.387419 0.577036 0.069365 0.049 Uiso 1 1 calc R . . . .
C9 C 0.4669(2) 0.47281(12) 0.15122(19) 0.0350(4) Uani 1 1 d . . . . .
H9 H 0.425957 0.441588 0.080000 0.042 Uiso 1 1 calc R . . . .
C10 C 0.55155(19) 0.43719(11) 0.26379(18) 0.0308(4) Uani 1 1 d . . . . .
C11 C 0.43441(19) 0.30750(12) 0.27648(19) 0.0317(4) Uani 1 1 d . . . . .
H11A H 0.417197 0.327187 0.352113 0.038 Uiso 1 1 calc R . . . .
H11B H 0.354940 0.324486 0.204362 0.038 Uiso 1 1 calc R . . . .
C12 C 0.5479(2) 0.18134(11) 0.32450(18) 0.0302(4) Uani 1 1 d . . . . .
C13 C 0.5944(2) 0.26746(13) 0.08371(19) 0.0354(4) Uani 1 1 d . . . . .
C14 C 0.5381(2) 0.09302(12) 0.32736(17) 0.0312(4) Uani 1 1 d . . . . .
C15 C 0.6506(2) 0.04367(13) 0.3274(2) 0.0376(4) Uani 1 1 d . . . . .
H15 H 0.734973 0.065589 0.322610 0.045 Uiso 1 1 calc R . . . .
C16 C 0.6381(2) -0.03823(13) 0.3346(2) 0.0388(5) Uani 1 1 d . . . . .
H16 H 0.713284 -0.071178 0.334012 0.047 Uiso 1 1 calc R . . . .
C17 C 0.5127(2) -0.07002(12) 0.34276(18) 0.0341(4) Uani 1 1 d . . . . .
C18 C 0.3980(2) -0.02244(12) 0.3406(2) 0.0364(4) Uani 1 1 d . . . . .
H18 H 0.313505 -0.044790 0.344481 0.044 Uiso 1 1 calc R . . . .
C19 C 0.4110(2) 0.05915(13) 0.33250(19) 0.0353(4) Uani 1 1 d . . . . .
H19 H 0.334389 0.091699 0.330477 0.042 Uiso 1 1 calc R . . . .


_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 C17 1.897(2) . ?
S1 C2 1.8173(19) . ?
S1 C12 1.7731(19) . ?
S2 C13 1.579(2) . ?
N1 C11 1.455(2) . ?
N1 C12 1.268(2) . ?
N2 C1 1.454(3) . ?
N2 C13 1.180(3) . ?
C1 C2 1.535(3) . ?
C1 C10 1.527(3) . ?
C1 C11 1.542(3) . ?
C2 H2 0.9800 . ?
C2 C3 1.523(3) . ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
C3 C4 1.525(3) . ?
C4 H4A 0.9700 . ?
C4 H4B 0.9700 . ?
C4 C5 1.512(3) . ?
C5 C6 1.393(3) . ?
C5 C10 1.400(3) . ?
C6 H6 0.9300 . ?
C6 C7 1.382(3) . ?
C7 H7 0.9300 . ?
C7 C8 1.382(3) . ?
C8 H8 0.9300 . ?
C8 C9 1.386(3) . ?
C9 H9 0.9300 . ?
C9 C10 1.401(3) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 C14 1.493(3) . ?
C14 C15 1.389(3) . ?
C14 C19 1.398(3) . ?
C15 H15 0.9300 . ?
C15 C16 1.390(3) . ?
C16 H16 0.9300 . ?
C16 C17 1.380(3) . ?
C17 C18 1.383(3) . ?
C18 H18 0.9300 . ?
C18 C19 1.387(3) . ?
C19 H19 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
C12 S1 C2 102.43(9) . . ?
C12 N1 C11 122.05(16) . . ?
C13 N2 C1 145.62(18) . . ?
N2 C1 C2 108.75(16) . . ?
N2 C1 C10 108.66(15) . . ?
N2 C1 C11 107.67(15) . . ?
C2 C1 C11 111.97(16) . . ?
C10 C1 C2 110.71(15) . . ?
C10 C1 C11 108.99(15) . . ?
S1 C2 H2 107.2 . . ?
C1 C2 S1 111.79(13) . . ?
C1 C2 H2 107.2 . . ?
C3 C2 S1 112.59(15) . . ?
C3 C2 C1 110.62(17) . . ?
C3 C2 H2 107.2 . . ?
C2 C3 H3A 109.8 . . ?
C2 C3 H3B 109.8 . . ?
C2 C3 C4 109.60(18) . . ?
H3A C3 H3B 108.2 . . ?
C4 C3 H3A 109.8 . . ?
C4 C3 H3B 109.8 . . ?
C3 C4 H4A 108.8 . . ?
C3 C4 H4B 108.8 . . ?
H4A C4 H4B 107.7 . . ?
C5 C4 C3 113.59(18) . . ?
C5 C4 H4A 108.8 . . ?
C5 C4 H4B 108.8 . . ?
C6 C5 C4 119.61(19) . . ?
C6 C5 C10 118.61(19) . . ?
C10 C5 C4 121.74(19) . . ?
C5 C6 H6 119.2 . . ?
C7 C6 C5 121.7(2) . . ?
C7 C6 H6 119.2 . . ?
C6 C7 H7 120.2 . . ?
C6 C7 C8 119.7(2) . . ?
C8 C7 H7 120.2 . . ?
C7 C8 H8 120.1 . . ?
C7 C8 C9 119.8(2) . . ?
C9 C8 H8 120.1 . . ?
C8 C9 H9 119.6 . . ?
C8 C9 C10 120.8(2) . . ?
C10 C9 H9 119.6 . . ?
C5 C10 C1 121.76(17) . . ?
C5 C10 C9 119.40(19) . . ?
C9 C10 C1 118.82(17) . . ?
N1 C11 C1 116.58(16) . . ?
N1 C11 H11A 108.1 . . ?
N1 C11 H11B 108.1 . . ?
C1 C11 H11A 108.1 . . ?
C1 C11 H11B 108.1 . . ?
H11A C11 H11B 107.3 . . ?
N1 C12 S1 128.81(15) . . ?
N1 C12 C14 118.72(16) . . ?
C14 C12 S1 112.47(13) . . ?
N2 C13 S2 174.19(19) . . ?
C15 C14 C12 122.66(18) . . ?
C15 C14 C19 119.05(19) . . ?
C19 C14 C12 118.28(17) . . ?
C14 C15 H15 119.7 . . ?
C14 C15 C16 120.58(19) . . ?
C16 C15 H15 119.7 . . ?
C15 C16 H16 120.4 . . ?
C17 C16 C15 119.17(19) . . ?
C17 C16 H16 120.4 . . ?
C16 C17 Br1 118.97(16) . . ?
C16 C17 C18 121.52(19) . . ?
C18 C17 Br1 119.48(16) . . ?
C17 C18 H18 120.5 . . ?
C17 C18 C19 118.90(19) . . ?
C19 C18 H18 120.5 . . ?
C14 C19 H19 119.6 . . ?
C18 C19 C14 120.74(19) . . ?
C18 C19 H19 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
Br1 C17 C18 C19 176.92(15) . . . . ?
S1 C2 C3 C4 169.23(15) . . . . ?
S1 C12 C14 C15 -25.1(2) . . . . ?
S1 C12 C14 C19 153.69(15) . . . . ?
N1 C12 C14 C15 155.35(19) . . . . ?
N1 C12 C14 C19 -25.8(3) . . . . ?
N2 C1 C2 S1 -62.94(18) . . . . ?
N2 C1 C2 C3 170.73(16) . . . . ?
N2 C1 C10 C5 -140.92(18) . . . . ?
N2 C1 C10 C9 40.7(2) . . . . ?
N2 C1 C11 N1 62.3(2) . . . . ?
C1 C2 C3 C4 -64.9(2) . . . . ?
C2 S1 C12 N1 1.5(2) . . . . ?
C2 S1 C12 C14 -177.97(14) . . . . ?
C2 C1 C10 C5 -21.6(2) . . . . ?
C2 C1 C10 C9 160.10(17) . . . . ?
C2 C1 C11 N1 -57.2(2) . . . . ?
C2 C3 C4 C5 45.8(3) . . . . ?
C3 C4 C5 C6 165.9(2) . . . . ?
C3 C4 C5 C10 -16.5(3) . . . . ?
C4 C5 C6 C7 177.1(2) . . . . ?
C4 C5 C10 C1 4.3(3) . . . . ?
C4 C5 C10 C9 -177.4(2) . . . . ?
C5 C6 C7 C8 0.5(3) . . . . ?
C6 C5 C10 C1 -178.08(18) . . . . ?
C6 C5 C10 C9 0.2(3) . . . . ?
C6 C7 C8 C9 -0.1(3) . . . . ?
C7 C8 C9 C10 -0.2(3) . . . . ?
C8 C9 C10 C1 178.52(18) . . . . ?
C8 C9 C10 C5 0.1(3) . . . . ?
C10 C1 C2 S1 177.75(13) . . . . ?
C10 C1 C2 C3 51.4(2) . . . . ?
C10 C1 C11 N1 179.94(16) . . . . ?
C10 C5 C6 C7 -0.6(3) . . . . ?
C11 N1 C12 S1 -0.5(3) . . . . ?
C11 N1 C12 C14 178.97(17) . . . . ?
C11 C1 C2 S1 55.9(2) . . . . ?
C11 C1 C2 C3 -70.4(2) . . . . ?
C11 C1 C10 C5 102.0(2) . . . . ?
C11 C1 C10 C9 -76.3(2) . . . . ?
C12 S1 C2 C1 -28.84(16) . . . . ?
C12 S1 C2 C3 96.40(15) . . . . ?
C12 N1 C11 C1 27.6(3) . . . . ?
C12 C14 C15 C16 177.73(19) . . . . ?
C12 C14 C19 C18 -177.34(18) . . . . ?
C13 N2 C1 C2 70.9(4) . . . . ?
C13 N2 C1 C10 -168.5(3) . . . . ?
C13 N2 C1 C11 -50.6(4) . . . . ?
C14 C15 C16 C17 -0.5(3) . . . . ?
C15 C14 C19 C18 1.5(3) . . . . ?
C15 C16 C17 Br1 -176.49(16) . . . . ?
C15 C16 C17 C18 1.7(3) . . . . ?
C16 C17 C18 C19 -1.3(3) . . . . ?
C17 C18 C19 C14 -0.4(3) . . . . ?
C19 C14 C15 C16 -1.1(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 1.895
_oxdiff_exptl_absorpt_empirical_full_min 0.703
