# Electronic Supplementary Material (ESI) for Faraday Discussions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1528817'
_audit_update_record             
;
2017-01-20 deposited with the CCDC.
2017-02-17 downloaded from the CCDC.
;

_audit_creation_date             2017-01-20T11:48:46-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.3
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic

#----------------------------------------------------------------------------#
#                   CHEMICAL INFORMATION                                     #
#----------------------------------------------------------------------------#

_chemical_formula_moiety         'C13 H11 Br1 N2 O3 S'
_chemical_formula_sum            'C13 H11 Br N2 O3 S'
_chemical_formula_weight         355.21
_chemical_compound_source        'synthesis as described'

#----------------------------------------------------------------------------#
#                   UNIT CELL INFORMATION                                    #
#----------------------------------------------------------------------------#

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_Int_Tables_number      2
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   6.9455(13)
_cell_length_b                   8.1993(14)
_cell_length_c                   13.825(2)
_cell_angle_alpha                97.886(7)
_cell_angle_beta                 97.939(8)
_cell_angle_gamma                109.479(8)
_cell_volume                     720.8(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    5516
_cell_measurement_theta_min      2.69
_cell_measurement_theta_max      27.42
_cell_measurement_wavelength     0.71073

#----------------------------------------------------------------------------#
#                   CRYSTAL INFORMATION                                      #
#----------------------------------------------------------------------------#

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.02
_exptl_crystal_density_diffrn    1.637
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             356

#----------------------------------------------------------------------------#
#                   ABSORPTION CORRECTION                                    #
#----------------------------------------------------------------------------#

_exptl_absorpt_coefficient_mu    3.003
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
  [Sheldrick, G.M. (2002). SADABS Bruker AXS Inc., Madison, Wisconsin, USA]
;
_exptl_absorpt_correction_T_min  0.730
_exptl_absorpt_correction_T_max  0.942

#------------------------------- Remark -------------------------------------#
# SADABS output:                                                             #
# Estimated minimum and maximum transmission:  0.6014  0.7456                #
# The ratio of these values is more reliable than their absolute values!     #
#----------------------------------------------------------------------------#


#----------------------------------------------------------------------------#
#                   DATA COLLECTION                                          #
#----------------------------------------------------------------------------#

_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_probe          x-ray
_diffrn_detector                 'CCD plate'
_diffrn_orient_matrix_ub_11      0.074261
_diffrn_orient_matrix_ub_12      0.054063
_diffrn_orient_matrix_ub_13      0.070388
_diffrn_orient_matrix_ub_21      -0.136918
_diffrn_orient_matrix_ub_22      -0.02325
_diffrn_orient_matrix_ub_23      0.021359
_diffrn_orient_matrix_ub_31      -0.001559
_diffrn_orient_matrix_ub_32      -0.118079
_diffrn_orient_matrix_ub_33      0.011689
_diffrn_measurement_device_type  'APEXII, Bruker-AXS'
_diffrn_measurement_method       'CCD rotation images, thick slices'
_diffrn_standards_number         0
_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_decay_%        ?
_diffrn_reflns_av_R_equivalents  0.0242
_diffrn_reflns_av_unetI/netI     0.0259
_diffrn_reflns_number            9513
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.034
_diffrn_reflns_theta_max         27.609
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.972
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.972
_reflns_Friedel_coverage         0
_reflns_number_total             3245
_reflns_number_gt                2870
_reflns_threshold_expression     'I > 2σ(I)'

#----------------------------------------------------------------------------#
#                   COMPUTER PROGRAMS USED                                   #
#----------------------------------------------------------------------------#

_computing_data_collection       'Bruker APEX2 (Bruker, 2006)'
_computing_cell_refinement       'Bruker APEX2 (Bruker, 2006)'
_computing_data_reduction        'Bruker APEX2 (Bruker, 2006)'
_computing_structure_solution    'SIR-92 (Altomare et al., 1994)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'

#----------------------------------------------------------------------------#
#                   STRUCTURE SOLUTION                                       #
#----------------------------------------------------------------------------#

_atom_sites_solution_hydrogens   geom

#----------------------------------------------------------------------------#
#                   REFINEMENT INFORMATION                                   #
#----------------------------------------------------------------------------#

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0353P)²+0.4342P] where P=(Fo²+2Fc²)/3'
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_number_reflns         3245
_refine_ls_number_parameters     182
_refine_ls_number_restraints     0
_refine_ls_number_constraints    0
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0261
_refine_ls_wR_factor_ref         0.0694
_refine_ls_wR_factor_gt          0.0661
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_restrained_S_all      1.062
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0
_refine_diff_density_max         0.546
_refine_diff_density_min         -0.455
_refine_diff_density_rms         0.071

#----------------------------------------------------------------------------#
#                   CONSTRAINTS AND RESTRAINTS                               #
#----------------------------------------------------------------------------#


#----------------------------------------------------------------------------#
#                   ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS         #
#----------------------------------------------------------------------------#

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 0 '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 0.006 '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'

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
C1 C 0.7115(3) 0.6050(3) 0.78330(15) 0.0239(4) Uani 1 1 d . . . . .
C2 C 0.7170(3) 0.6586(3) 0.68396(16) 0.0221(4) Uani 1 1 d . . . . .
C3 C 0.6801(4) 0.8027(3) 0.65564(17) 0.0264(5) Uani 1 1 d . . . . .
H3 H 0.6463 0.8821 0.701 0.032 Uiso 1 1 calc R U . . .
C4 C 0.6940(4) 0.8282(3) 0.55898(17) 0.0294(5) Uani 1 1 d . . . . .
H4 H 0.6693 0.9263 0.5381 0.035 Uiso 1 1 calc R U . . .
C5 C 0.7437(4) 0.7113(3) 0.49226(17) 0.0284(5) Uani 1 1 d . . . . .
H5 H 0.7521 0.7315 0.4267 0.034 Uiso 1 1 calc R U . . .
C6 C 0.7810(3) 0.5663(3) 0.51976(16) 0.0247(4) Uani 1 1 d . . . . .
H6 H 0.8141 0.4862 0.4746 0.03 Uiso 1 1 calc R U . . .
C7 C 0.7675(3) 0.5444(3) 0.61662(15) 0.0213(4) Uani 1 1 d . . . . .
C8 C 0.7659(3) 0.0297(3) 1.00370(17) 0.0273(5) Uani 1 1 d . . . . .
H8 H 0.7669 -0.0238 0.9384 0.033 Uiso 1 1 calc R U . . .
C9 C 0.7658(4) -0.0629(3) 1.07906(18) 0.0306(5) Uani 1 1 d . . . . .
H9 H 0.7657 -0.1797 1.0656 0.037 Uiso 1 1 calc R U . . .
C10 C 0.7659(3) 0.0145(3) 1.17556(17) 0.0298(5) Uani 1 1 d . . . . .
C11 C 0.7617(4) 0.1836(3) 1.19020(16) 0.0301(5) Uani 1 1 d . . . . .
H11 H 0.7601 0.2398 1.2548 0.036 Uiso 1 1 calc R U . . .
C12 C 0.7599(3) 0.2712(3) 1.11202(16) 0.0255(5) Uani 1 1 d . . . . .
H12 H 0.7553 0.3867 1.123 0.031 Uiso 1 1 calc R U . . .
C13 C 0.7688(4) -0.0822(4) 1.2599(2) 0.0441(7) Uani 1 1 d . . . . .
H13A H 0.8407 0.0027 1.3222 0.066 Uiso 1 1 calc R U . . .
H13B H 0.8421 -0.1641 1.2476 0.066 Uiso 1 1 calc R U . . .
H13C H 0.6255 -0.1483 1.2652 0.066 Uiso 1 1 calc R U . . .
N1 N 0.7575(3) 0.4540(2) 0.78128(13) 0.0247(4) Uani 1 1 d . . . . .
N2 N 0.7646(3) 0.1946(2) 1.02026(13) 0.0230(4) Uani 1 1 d . . . . .
O1 O 0.6652(3) 0.2073(2) 0.63195(12) 0.0329(4) Uani 1 1 d . . . . .
O2 O 1.0285(3) 0.4004(2) 0.68874(12) 0.0312(4) Uani 1 1 d . . . . .
O3 O 0.6718(3) 0.6829(2) 0.85466(12) 0.0337(4) Uani 1 1 d . . . . .
S002 S 0.81267(9) 0.38012(7) 0.67614(4) 0.02272(12) Uani 1 1 d . . . . .
Br1 Br 0.76410(3) 0.32713(3) 0.90079(2) 0.02282(8) Uani 1 1 d . . . . .



#----------------------------------------------------------------------------#
#                   MOLECULAR GEOMETRY                                       #
#----------------------------------------------------------------------------#

_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
C1 O3 1.216(3) . ?
C1 N1 1.376(3) . ?
C1 C2 1.500(3) . ?
C2 C3 1.384(3) . ?
C2 C7 1.391(3) . ?
C3 C4 1.392(3) . ?
C3 H3 0.95 . ?
C4 C5 1.398(3) . ?
C4 H4 0.95 . ?
C5 C6 1.388(3) . ?
C5 H5 0.95 . ?
C6 C7 1.387(3) . ?
C6 H6 0.95 . ?
C7 S002 1.762(2) . ?
C8 N2 1.343(3) . ?
C8 C9 1.371(3) . ?
C8 H8 0.95 . ?
C9 C10 1.396(3) . ?
C9 H9 0.95 . ?
C10 C11 1.384(4) . ?
C10 C13 1.499(3) . ?
C11 C12 1.378(3) . ?
C11 H11 0.95 . ?
C12 N2 1.346(3) . ?
C12 H12 0.95 . ?
C13 H13A 0.98 . ?
C13 H13B 0.98 . ?
C13 H13C 0.98 . ?
N1 S002 1.6412(18) . ?
N1 Br1 2.0727(18) . ?
N2 Br1 2.0982(18) . ?
O1 S002 1.4326(17) . ?
O2 S002 1.4348(17) . ?

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
O3 C1 N1 125.2(2) . . ?
O3 C1 C2 125.1(2) . . ?
N1 C1 C2 109.71(18) . . ?
C3 C2 C7 120.0(2) . . ?
C3 C2 C1 127.7(2) . . ?
C7 C2 C1 112.30(19) . . ?
C2 C3 C4 118.2(2) . . ?
C2 C3 H3 120.9 . . ?
C4 C3 H3 120.9 . . ?
C3 C4 C5 120.9(2) . . ?
C3 C4 H4 119.6 . . ?
C5 C4 H4 119.6 . . ?
C6 C5 C4 121.4(2) . . ?
C6 C5 H5 119.3 . . ?
C4 C5 H5 119.3 . . ?
C7 C6 C5 116.5(2) . . ?
C7 C6 H6 121.7 . . ?
C5 C6 H6 121.7 . . ?
C6 C7 C2 122.9(2) . . ?
C6 C7 S002 128.17(17) . . ?
C2 C7 S002 108.92(16) . . ?
N2 C8 C9 121.4(2) . . ?
N2 C8 H8 119.3 . . ?
C9 C8 H8 119.3 . . ?
C8 C9 C10 120.0(2) . . ?
C8 C9 H9 120 . . ?
C10 C9 H9 120 . . ?
C11 C10 C9 117.4(2) . . ?
C11 C10 C13 121.2(2) . . ?
C9 C10 C13 121.4(2) . . ?
C12 C11 C10 120.6(2) . . ?
C12 C11 H11 119.7 . . ?
C10 C11 H11 119.7 . . ?
N2 C12 C11 120.6(2) . . ?
N2 C12 H12 119.7 . . ?
C11 C12 H12 119.7 . . ?
C10 C13 H13A 109.5 . . ?
C10 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C10 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C1 N1 S002 114.93(14) . . ?
C1 N1 Br1 123.89(14) . . ?
S002 N1 Br1 121.17(10) . . ?
C8 N2 C12 120.00(19) . . ?
C8 N2 Br1 119.00(14) . . ?
C12 N2 Br1 120.99(15) . . ?
O1 S002 O2 116.40(11) . . ?
O1 S002 N1 110.43(10) . . ?
O2 S002 N1 110.94(10) . . ?
O1 S002 C7 112.42(10) . . ?
O2 S002 C7 110.39(10) . . ?
N1 S002 C7 94.07(10) . . ?
N1 Br1 N2 178.77(7) . . ?

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
O3 C1 C2 C3 0.4(4) . . . . ?
N1 C1 C2 C3 -179.9(2) . . . . ?
O3 C1 C2 C7 179.9(2) . . . . ?
N1 C1 C2 C7 -0.4(3) . . . . ?
C7 C2 C3 C4 0.4(3) . . . . ?
C1 C2 C3 C4 179.8(2) . . . . ?
C2 C3 C4 C5 0.0(4) . . . . ?
C3 C4 C5 C6 0.0(4) . . . . ?
C4 C5 C6 C7 -0.3(3) . . . . ?
C5 C6 C7 C2 0.7(3) . . . . ?
C5 C6 C7 S002 -177.96(17) . . . . ?
C3 C2 C7 C6 -0.8(3) . . . . ?
C1 C2 C7 C6 179.7(2) . . . . ?
C3 C2 C7 S002 178.14(17) . . . . ?
C1 C2 C7 S002 -1.4(2) . . . . ?
N2 C8 C9 C10 -0.5(4) . . . . ?
C8 C9 C10 C11 1.3(3) . . . . ?
C8 C9 C10 C13 -179.1(2) . . . . ?
C9 C10 C11 C12 -0.7(3) . . . . ?
C13 C10 C11 C12 179.8(2) . . . . ?
C10 C11 C12 N2 -0.8(4) . . . . ?
O3 C1 N1 S002 -178.05(19) . . . . ?
C2 C1 N1 S002 2.2(2) . . . . ?
O3 C1 N1 Br1 0.8(3) . . . . ?
C2 C1 N1 Br1 -178.95(14) . . . . ?
C9 C8 N2 C12 -1.0(3) . . . . ?
C9 C8 N2 Br1 -179.86(17) . . . . ?
C11 C12 N2 C8 1.6(3) . . . . ?
C11 C12 N2 Br1 -179.55(17) . . . . ?
C1 N1 S002 O1 -118.40(17) . . . . ?
Br1 N1 S002 O1 62.70(15) . . . . ?
C1 N1 S002 O2 111.02(17) . . . . ?
Br1 N1 S002 O2 -67.89(14) . . . . ?
C1 N1 S002 C7 -2.64(18) . . . . ?
Br1 N1 S002 C7 178.46(12) . . . . ?
C6 C7 S002 O1 -64.8(2) . . . . ?
C2 C7 S002 O1 116.35(16) . . . . ?
C6 C7 S002 O2 67.0(2) . . . . ?
C2 C7 S002 O2 -111.84(16) . . . . ?
C6 C7 S002 N1 -178.9(2) . . . . ?
C2 C7 S002 N1 2.27(17) . . . . ?

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1528818'
_audit_update_record             
;
2017-01-20 deposited with the CCDC.
2017-02-17 downloaded from the CCDC.
;

_audit_creation_date             2017-01-20T11:45:13-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.3
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic

#----------------------------------------------------------------------------#
#                   CHEMICAL INFORMATION                                     #
#----------------------------------------------------------------------------#

_chemical_formula_moiety         'C7 H4 N O3 S, C7 H10 Br N2'
_chemical_formula_sum            'C14 H14 Br N3 O3 S'
_chemical_formula_weight         384.25
_chemical_compound_source        'synthesis as described'

#----------------------------------------------------------------------------#
#                   UNIT CELL INFORMATION                                    #
#----------------------------------------------------------------------------#

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_Int_Tables_number      2
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.2107(3)
_cell_length_b                   8.5679(4)
_cell_length_c                   12.2391(5)
_cell_angle_alpha                86.641(2)
_cell_angle_beta                 79.084(2)
_cell_angle_gamma                87.121(2)
_cell_volume                     740.59(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    6294
_cell_measurement_theta_min      2.86
_cell_measurement_theta_max      27.44
_cell_measurement_wavelength     0.71073

#----------------------------------------------------------------------------#
#                   CRYSTAL INFORMATION                                      #
#----------------------------------------------------------------------------#

_exptl_crystal_description       prism
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.09
_exptl_crystal_density_diffrn    1.723
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             388

#----------------------------------------------------------------------------#
#                   ABSORPTION CORRECTION                                    #
#----------------------------------------------------------------------------#

_exptl_absorpt_coefficient_mu    2.932
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
  [Sheldrick, G.M. (2002). SADABS Bruker AXS Inc., Madison, Wisconsin, USA]
;
_exptl_absorpt_correction_T_min  0.639
_exptl_absorpt_correction_T_max  0.768

#------------------------------- Remark -------------------------------------#
# SADABS output:                                                             #
# Estimated minimum and maximum transmission:  0.5874  0.7456                #
# The ratio of these values is more reliable than their absolute values!     #
#----------------------------------------------------------------------------#


#----------------------------------------------------------------------------#
#                   DATA COLLECTION                                          #
#----------------------------------------------------------------------------#

_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_probe          x-ray
_diffrn_detector                 'CCD plate'
_diffrn_orient_matrix_ub_11      -0.059039
_diffrn_orient_matrix_ub_12      -0.053765
_diffrn_orient_matrix_ub_13      0.071999
_diffrn_orient_matrix_ub_21      0.011237
_diffrn_orient_matrix_ub_22      0.09655
_diffrn_orient_matrix_ub_23      0.040017
_diffrn_orient_matrix_ub_31      -0.127938
_diffrn_orient_matrix_ub_32      0.038452
_diffrn_orient_matrix_ub_33      -0.012499
_diffrn_measurement_device_type  'APEXII, Bruker-AXS'
_diffrn_measurement_method       'CCD rotation images, thick slices'
_diffrn_standards_number         0
_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_decay_%        ?
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_number            12345
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.057
_diffrn_reflns_theta_max         27.498
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_reflns_Friedel_coverage         0
_reflns_number_total             3364
_reflns_number_gt                3076
_reflns_threshold_expression     'I > 2σ(I)'

#----------------------------------------------------------------------------#
#                   COMPUTER PROGRAMS USED                                   #
#----------------------------------------------------------------------------#

_computing_data_collection       'Bruker APEX2 (Bruker, 2006)'
_computing_cell_refinement       'Bruker APEX2 (Bruker, 2006)'
_computing_data_reduction        'Bruker APEX2 (Bruker, 2006)'
_computing_structure_solution    'SIR-92 (Altomare et al., 1994)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'

#----------------------------------------------------------------------------#
#                   STRUCTURE SOLUTION                                       #
#----------------------------------------------------------------------------#

_atom_sites_solution_hydrogens   geom

#----------------------------------------------------------------------------#
#                   REFINEMENT INFORMATION                                   #
#----------------------------------------------------------------------------#

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0413P)²+1.5731P] where P=(Fo²+2Fc²)/3'
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_number_reflns         3364
_refine_ls_number_parameters     202
_refine_ls_number_restraints     0
_refine_ls_number_constraints    0
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0346
_refine_ls_wR_factor_ref         0.0957
_refine_ls_wR_factor_gt          0.0939
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_restrained_S_all      1.078
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_diff_density_max         0.609
_refine_diff_density_min         -0.531
_refine_diff_density_rms         0.096

#----------------------------------------------------------------------------#
#                   CONSTRAINTS AND RESTRAINTS                               #
#----------------------------------------------------------------------------#


#----------------------------------------------------------------------------#
#                   ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS         #
#----------------------------------------------------------------------------#

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 0 '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 0.006 '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'

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
C1 C 0.6983(4) 0.4166(3) 0.3448(2) 0.0143(5) Uani 1 1 d . . . . .
C2 C 0.6736(4) 0.3183(3) 0.2506(2) 0.0123(5) Uani 1 1 d . . . . .
C3 C 0.6475(4) 0.1585(3) 0.2526(2) 0.0139(5) Uani 1 1 d . . . . .
H3 H 0.6474 0.0946 0.3187 0.017 Uiso 1 1 calc R U . . .
C4 C 0.6214(4) 0.0947(3) 0.1545(2) 0.0163(6) Uani 1 1 d . . . . .
H4 H 0.6022 -0.0141 0.1539 0.02 Uiso 1 1 calc R U . . .
C5 C 0.6232(4) 0.1888(3) 0.0575(2) 0.0161(6) Uani 1 1 d . . . . .
H5 H 0.6036 0.1429 -0.008 0.019 Uiso 1 1 calc R U . . .
C6 C 0.6532(4) 0.3486(3) 0.0543(2) 0.0148(5) Uani 1 1 d . . . . .
H6 H 0.6574 0.4124 -0.0122 0.018 Uiso 1 1 calc R U . . .
C7 C 0.6766(4) 0.4100(3) 0.1529(2) 0.0130(5) Uani 1 1 d . . . . .
C8 C 0.2115(4) 0.1577(3) 0.3899(2) 0.0138(5) Uani 1 1 d . . . . .
C9 C 0.2419(4) 0.2736(3) 0.4569(2) 0.0165(6) Uani 1 1 d . . . . .
H9 H 0.2712 0.2451 0.5281 0.02 Uiso 1 1 calc R U . . .
C11 C 0.1934(4) 0.4688(4) 0.3231(3) 0.0192(6) Uani 1 1 d . . . . .
H11 H 0.1883 0.5767 0.3004 0.023 Uiso 1 1 calc R U . . .
C12 C 0.1624(4) 0.3603(3) 0.2525(2) 0.0165(6) Uani 1 1 d . . . . .
H12 H 0.1375 0.3942 0.1812 0.02 Uiso 1 1 calc R U . . .
C13 C 0.1663(4) 0.1966(3) 0.2826(2) 0.0135(5) Uani 1 1 d . . . . .
C14 C 0.0791(5) -0.0671(4) 0.2381(3) 0.0274(7) Uani 1 1 d . . . . .
H14A H 0.1926 -0.1365 0.2263 0.041 Uiso 1 1 calc R U . . .
H14B H -0.0073 -0.0962 0.1905 0.041 Uiso 1 1 calc R U . . .
H14C H 0.0162 -0.0772 0.3164 0.041 Uiso 1 1 calc R U . . .
C15 C 0.1253(4) 0.1505(4) 0.0951(2) 0.0202(6) Uani 1 1 d . . . . .
H15A H 0.0085 0.2137 0.094 0.03 Uiso 1 1 calc R U . . .
H15B H 0.1282 0.0606 0.0488 0.03 Uiso 1 1 calc R U . . .
H15C H 0.2344 0.2144 0.0658 0.03 Uiso 1 1 calc R U . . .
N1 N 0.7154(4) 0.5696(3) 0.3155(2) 0.0173(5) Uani 1 1 d . . . . .
N2 N 0.2314(4) 0.4261(3) 0.4246(2) 0.0185(5) Uani 1 1 d . . . . .
H2 H 0.2492 0.4979 0.4697 0.022 Uiso 1 1 calc R U . . .
N3 N 0.1326(3) 0.0949(3) 0.2101(2) 0.0158(5) Uani 1 1 d . . . . .
O1 O 0.7013(3) 0.3579(2) 0.43982(16) 0.0191(4) Uani 1 1 d . . . . .
O2 O 0.5484(4) 0.7034(2) 0.16931(19) 0.0273(5) Uani 1 1 d . . . . .
O3 O 0.8900(4) 0.6563(3) 0.12508(19) 0.0286(5) Uani 1 1 d . . . . .
S1 S 0.71039(11) 0.60402(8) 0.18493(6) 0.01701(16) Uani 1 1 d . . . . .
Br1 Br 0.26254(4) -0.04790(3) 0.44773(3) 0.02199(11) Uani 1 1 d . . . . .



#----------------------------------------------------------------------------#
#                   MOLECULAR GEOMETRY                                       #
#----------------------------------------------------------------------------#

_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
C1 O1 1.244(3) . ?
C1 N1 1.344(4) . ?
C1 C2 1.509(4) . ?
C2 C7 1.389(4) . ?
C2 C3 1.390(4) . ?
C3 C4 1.395(4) . ?
C3 H3 0.95 . ?
C4 C5 1.394(4) . ?
C4 H4 0.95 . ?
C5 C6 1.394(4) . ?
C5 H5 0.95 . ?
C6 C7 1.386(4) . ?
C6 H6 0.95 . ?
C7 S1 1.769(3) . ?
C8 C9 1.375(4) . ?
C8 C13 1.430(4) . ?
C8 Br1 1.904(3) . ?
C9 N2 1.346(4) . ?
C9 H9 0.95 . ?
C11 N2 1.348(4) . ?
C11 C12 1.360(4) . ?
C11 H11 0.95 . ?
C12 C13 1.429(4) . ?
C12 H12 0.95 . ?
C13 N3 1.341(4) . ?
C14 N3 1.464(4) . ?
C14 H14A 0.98 . ?
C14 H14B 0.98 . ?
C14 H14C 0.98 . ?
C15 N3 1.468(4) . ?
C15 H15A 0.98 . ?
C15 H15B 0.98 . ?
C15 H15C 0.98 . ?
N1 S1 1.614(2) . ?
N2 H2 0.88 . ?
O2 S1 1.446(2) . ?
O3 S1 1.441(2) . ?

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
O1 C1 N1 124.6(3) . . ?
O1 C1 C2 121.6(2) . . ?
N1 C1 C2 113.7(2) . . ?
C7 C2 C3 120.5(2) . . ?
C7 C2 C1 110.8(2) . . ?
C3 C2 C1 128.7(2) . . ?
C2 C3 C4 118.0(3) . . ?
C2 C3 H3 121 . . ?
C4 C3 H3 121 . . ?
C5 C4 C3 120.7(3) . . ?
C5 C4 H4 119.6 . . ?
C3 C4 H4 119.6 . . ?
C6 C5 C4 121.6(3) . . ?
C6 C5 H5 119.2 . . ?
C4 C5 H5 119.2 . . ?
C7 C6 C5 116.8(3) . . ?
C7 C6 H6 121.6 . . ?
C5 C6 H6 121.6 . . ?
C6 C7 C2 122.4(3) . . ?
C6 C7 S1 130.9(2) . . ?
C2 C7 S1 106.6(2) . . ?
C9 C8 C13 120.4(3) . . ?
C9 C8 Br1 113.6(2) . . ?
C13 C8 Br1 125.7(2) . . ?
N2 C9 C8 121.9(3) . . ?
N2 C9 H9 119 . . ?
C8 C9 H9 119 . . ?
N2 C11 C12 121.1(3) . . ?
N2 C11 H11 119.4 . . ?
C12 C11 H11 119.4 . . ?
C11 C12 C13 121.9(3) . . ?
C11 C12 H12 119.1 . . ?
C13 C12 H12 119.1 . . ?
N3 C13 C12 119.2(3) . . ?
N3 C13 C8 126.1(3) . . ?
C12 C13 C8 114.6(2) . . ?
N3 C14 H14A 109.5 . . ?
N3 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
N3 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
N3 C15 H15A 109.5 . . ?
N3 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
N3 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C1 N1 S1 111.37(19) . . ?
C9 N2 C11 120.0(3) . . ?
C9 N2 H2 120 . . ?
C11 N2 H2 120 . . ?
C13 N3 C14 125.3(2) . . ?
C13 N3 C15 119.3(2) . . ?
C14 N3 C15 114.9(2) . . ?
O3 S1 O2 115.26(15) . . ?
O3 S1 N1 110.97(14) . . ?
O2 S1 N1 111.40(14) . . ?
O3 S1 C7 110.38(14) . . ?
O2 S1 C7 109.98(13) . . ?
N1 S1 C7 97.44(13) . . ?

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
O1 C1 C2 C7 -179.5(3) . . . . ?
N1 C1 C2 C7 0.8(3) . . . . ?
O1 C1 C2 C3 1.5(4) . . . . ?
N1 C1 C2 C3 -178.3(3) . . . . ?
C7 C2 C3 C4 -1.1(4) . . . . ?
C1 C2 C3 C4 177.9(3) . . . . ?
C2 C3 C4 C5 0.5(4) . . . . ?
C3 C4 C5 C6 0.8(4) . . . . ?
C4 C5 C6 C7 -1.5(4) . . . . ?
C5 C6 C7 C2 0.9(4) . . . . ?
C5 C6 C7 S1 -178.0(2) . . . . ?
C3 C2 C7 C6 0.4(4) . . . . ?
C1 C2 C7 C6 -178.8(2) . . . . ?
C3 C2 C7 S1 179.5(2) . . . . ?
C1 C2 C7 S1 0.4(3) . . . . ?
C13 C8 C9 N2 -0.3(4) . . . . ?
Br1 C8 C9 N2 173.3(2) . . . . ?
N2 C11 C12 C13 0.7(5) . . . . ?
C11 C12 C13 N3 179.3(3) . . . . ?
C11 C12 C13 C8 -2.1(4) . . . . ?
C9 C8 C13 N3 -179.6(3) . . . . ?
Br1 C8 C13 N3 7.6(4) . . . . ?
C9 C8 C13 C12 1.9(4) . . . . ?
Br1 C8 C13 C12 -170.9(2) . . . . ?
O1 C1 N1 S1 178.6(2) . . . . ?
C2 C1 N1 S1 -1.6(3) . . . . ?
C8 C9 N2 C11 -1.2(4) . . . . ?
C12 C11 N2 C9 1.0(4) . . . . ?
C12 C13 N3 C14 -161.7(3) . . . . ?
C8 C13 N3 C14 19.8(4) . . . . ?
C12 C13 N3 C15 10.6(4) . . . . ?
C8 C13 N3 C15 -167.9(3) . . . . ?
C1 N1 S1 O3 -113.6(2) . . . . ?
C1 N1 S1 O2 116.5(2) . . . . ?
C1 N1 S1 C7 1.6(2) . . . . ?
C6 C7 S1 O3 -66.4(3) . . . . ?
C2 C7 S1 O3 114.6(2) . . . . ?
C6 C7 S1 O2 61.9(3) . . . . ?
C2 C7 S1 O2 -117.2(2) . . . . ?
C6 C7 S1 N1 177.9(3) . . . . ?
C2 C7 S1 N1 -1.1(2) . . . . ?

