# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 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 1518916'
_audit_update_record             
;
2016-11-23 deposited with the CCDC.
2017-02-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15 H13 N5 S'
_chemical_formula_weight         295.36

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'

_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                   10.4365(14)
_cell_length_b                   15.482(2)
_cell_length_c                   9.3960(12)
_cell_angle_alpha                90
_cell_angle_beta                 110.5890(10)
_cell_angle_gamma                90
_cell_volume                     1421.2(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    5455
_cell_measurement_theta_min      2.47
_cell_measurement_theta_max      28.34

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_F_000             616
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.515
_exptl_crystal_size_mid          0.268
_exptl_crystal_size_min          0.220
_exptl_absorpt_coefficient_mu    0.228
_shelx_estimated_absorpt_T_min   0.892
_shelx_estimated_absorpt_T_max   0.952
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6963
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_process_details   'SADABS, Bruker (2003)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17260
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.085
_diffrn_reflns_theta_max         29.130
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.946
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3627
_reflns_number_gt                2936
_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       'APEX II, Bruker (2009)'
_computing_cell_refinement       'APEX II, Bruker (2009)'
_computing_data_reduction        'XPREP, Bruker (2009)'
_computing_structure_solution    'SHELXS-03 (Sheldrick, 2003)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury (Macrae et al., 2008)'
_computing_publication_material  'CIFTAB (Sheldrick, 1997)'

_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)+(0.0638P)²+0.2874P] 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         3627
_refine_ls_number_parameters     190
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0531
_refine_ls_R_factor_gt           0.0418
_refine_ls_wR_factor_ref         0.1157
_refine_ls_wR_factor_gt          0.1088
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_restrained_S_all      1.034
_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
S1 S 0.39241(4) 0.84256(2) 0.49738(4) 0.03165(12) Uani 1 1 d . . . . .
N3 N 0.51743(12) 0.70292(7) 0.39323(14) 0.0292(3) Uani 1 1 d . . . . .
N5 N 0.55622(13) 0.84251(8) 0.51485(15) 0.0329(3) Uani 1 1 d . . . . .
N1 N 0.34148(13) 0.74114(8) 0.49250(15) 0.0335(3) Uani 1 1 d . . . . .
N11 N 0.22596(14) 0.58481(9) 0.41119(18) 0.0464(4) Uani 1 1 d . . . . .
N17 N 0.82029(14) 0.83483(10) 0.53748(17) 0.0449(4) Uani 1 1 d . . . . .
C4 C 0.59241(14) 0.77399(9) 0.45451(15) 0.0273(3) Uani 1 1 d . . . . .
C6 C 0.34211(14) 0.60033(9) 0.38553(16) 0.0301(3) Uani 1 1 d . . . . .
C2 C 0.40288(14) 0.68871(9) 0.42463(15) 0.0277(3) Uani 1 1 d . . . . .
C12 C 0.73801(14) 0.77097(10) 0.46100(16) 0.0307(3) Uani 1 1 d . . . . .
C18 C 0.31048(14) 0.87801(9) 0.30856(18) 0.0338(3) Uani 1 1 d . . . . .
H18 H 0.3311 0.8464 0.2263 0.041 Uiso 1 1 calc R U . . .
C13 C 0.78190(16) 0.70448(11) 0.39126(19) 0.0401(4) Uani 1 1 d . . . . .
H13 H 0.7192 0.6621 0.3337 0.048 Uiso 1 1 calc R U . . .
C7 C 0.40478(18) 0.53974(10) 0.32478(19) 0.0399(4) Uani 1 1 d . . . . .
H7 H 0.4878 0.5530 0.3093 0.048 Uiso 1 1 calc R U . . .
C19 C 0.28211(18) 0.97348(10) 0.2879(2) 0.0479(4) Uani 1 1 d . . . . .
H19A H 0.3141 1.0105 0.3795 0.057 Uiso 1 1 calc R U . . .
H19B H 0.2858 1.0007 0.1941 0.057 Uiso 1 1 calc R U . . .
C20 C 0.16823(17) 0.91258(11) 0.2727(2) 0.0485(4) Uani 1 1 d . . . . .
H20A H 0.1011 0.9021 0.1695 0.058 Uiso 1 1 calc R U . . .
H20B H 0.1294 0.9119 0.3549 0.058 Uiso 1 1 calc R U . . .
C14 C 0.91872(18) 0.70068(13) 0.4066(2) 0.0520(5) Uani 1 1 d . . . . .
H14 H 0.9516 0.6553 0.3606 0.062 Uiso 1 1 calc R U . . .
C9 C 0.2255(2) 0.44197(11) 0.3116(2) 0.0499(4) Uani 1 1 d . . . . .
H9 H 0.1814 0.3875 0.2862 0.060 Uiso 1 1 calc R U . . .
C15 C 1.00623(18) 0.76368(15) 0.4896(2) 0.0560(5) Uani 1 1 d . . . . .
H15 H 1.1011 0.7621 0.5049 0.067 Uiso 1 1 calc R U . . .
C8 C 0.3446(2) 0.45884(11) 0.2864(2) 0.0508(4) Uani 1 1 d . . . . .
H8 H 0.3854 0.4160 0.2435 0.061 Uiso 1 1 calc R U . . .
C10 C 0.1715(2) 0.50595(13) 0.3745(2) 0.0560(5) Uani 1 1 d . . . . .
H10 H 0.0898 0.4935 0.3933 0.067 Uiso 1 1 calc R U . . .
C16 C 0.95195(19) 0.82911(15) 0.5499(2) 0.0591(5) Uani 1 1 d . . . . .
H16 H 1.0122 0.8735 0.6043 0.071 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S1 N1 1.6531(13) . ?
S1 N5 1.6590(13) . ?
S1 C18 1.7644(16) . ?
N3 C2 1.3463(17) . ?
N3 C4 1.3555(18) . ?
N5 C4 1.3192(18) . ?
N1 C2 1.3280(18) . ?
N11 C6 1.3382(19) . ?
N11 C10 1.340(2) . ?
N17 C16 1.340(2) . ?
N17 C12 1.341(2) . ?
C4 C12 1.5000(19) . ?
C6 C7 1.377(2) . ?
C6 C2 1.4985(19) . ?
C12 C13 1.382(2) . ?
C18 C20 1.501(2) . ?
C18 C19 1.506(2) . ?
C18 H18 1.0000 . ?
C13 C14 1.385(2) . ?
C13 H13 0.9500 . ?
C7 C8 1.391(2) . ?
C7 H7 0.9500 . ?
C19 C20 1.484(2) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C14 C15 1.376(3) . ?
C14 H14 0.9500 . ?
C9 C8 1.370(3) . ?
C9 C10 1.371(3) . ?
C9 H9 0.9500 . ?
C15 C16 1.376(3) . ?
C15 H15 0.9500 . ?
C8 H8 0.9500 . ?
C10 H10 0.9500 . ?
C16 H16 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 S1 N5 108.20(6) . . ?
N1 S1 C18 103.31(7) . . ?
N5 S1 C18 102.58(7) . . ?
C2 N3 C4 117.64(12) . . ?
C4 N5 S1 113.49(10) . . ?
C2 N1 S1 112.90(10) . . ?
C6 N11 C10 116.51(15) . . ?
C16 N17 C12 116.22(16) . . ?
N5 C4 N3 128.72(13) . . ?
N5 C4 C12 116.53(12) . . ?
N3 C4 C12 114.66(12) . . ?
N11 C6 C7 123.01(14) . . ?
N11 C6 C2 116.87(13) . . ?
C7 C6 C2 120.12(13) . . ?
N1 C2 N3 128.39(13) . . ?
N1 C2 C6 116.21(12) . . ?
N3 C2 C6 115.30(12) . . ?
N17 C12 C13 123.15(14) . . ?
N17 C12 C4 116.59(13) . . ?
C13 C12 C4 120.26(13) . . ?
C20 C18 C19 59.15(11) . . ?
C20 C18 S1 115.34(12) . . ?
C19 C18 S1 116.02(12) . . ?
C20 C18 H18 117.7 . . ?
C19 C18 H18 117.7 . . ?
S1 C18 H18 117.7 . . ?
C12 C13 C14 118.92(17) . . ?
C12 C13 H13 120.5 . . ?
C14 C13 H13 120.5 . . ?
C6 C7 C8 118.95(15) . . ?
C6 C7 H7 120.5 . . ?
C8 C7 H7 120.5 . . ?
C20 C19 C18 60.23(10) . . ?
C20 C19 H19A 117.7 . . ?
C18 C19 H19A 117.7 . . ?
C20 C19 H19B 117.7 . . ?
C18 C19 H19B 117.7 . . ?
H19A C19 H19B 114.9 . . ?
C19 C20 C18 60.62(11) . . ?
C19 C20 H20A 117.7 . . ?
C18 C20 H20A 117.7 . . ?
C19 C20 H20B 117.7 . . ?
C18 C20 H20B 117.7 . . ?
H20A C20 H20B 114.8 . . ?
C15 C14 C13 118.93(18) . . ?
C15 C14 H14 120.5 . . ?
C13 C14 H14 120.5 . . ?
C8 C9 C10 118.14(16) . . ?
C8 C9 H9 120.9 . . ?
C10 C9 H9 120.9 . . ?
C16 C15 C14 117.90(16) . . ?
C16 C15 H15 121.1 . . ?
C14 C15 H15 121.1 . . ?
C9 C8 C7 118.77(16) . . ?
C9 C8 H8 120.6 . . ?
C7 C8 H8 120.6 . . ?
N11 C10 C9 124.61(17) . . ?
N11 C10 H10 117.7 . . ?
C9 C10 H10 117.7 . . ?
N17 C16 C15 124.78(18) . . ?
N17 C16 H16 117.6 . . ?
C15 C16 H16 117.6 . . ?

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
N1 S1 N5 C4 28.93(13) . . . . ?
C18 S1 N5 C4 -79.83(12) . . . . ?
N5 S1 N1 C2 -33.61(12) . . . . ?
C18 S1 N1 C2 74.65(12) . . . . ?
S1 N5 C4 N3 -5.7(2) . . . . ?
S1 N5 C4 C12 177.88(9) . . . . ?
C2 N3 C4 N5 -16.3(2) . . . . ?
C2 N3 C4 C12 160.18(12) . . . . ?
C10 N11 C6 C7 0.0(2) . . . . ?
C10 N11 C6 C2 179.32(15) . . . . ?
S1 N1 C2 N3 16.50(19) . . . . ?
S1 N1 C2 C6 -167.36(10) . . . . ?
C4 N3 C2 N1 9.8(2) . . . . ?
C4 N3 C2 C6 -166.36(12) . . . . ?
N11 C6 C2 N1 5.2(2) . . . . ?
C7 C6 C2 N1 -175.41(13) . . . . ?
N11 C6 C2 N3 -178.13(13) . . . . ?
C7 C6 C2 N3 1.2(2) . . . . ?
C16 N17 C12 C13 -3.1(2) . . . . ?
C16 N17 C12 C4 176.45(14) . . . . ?
N5 C4 C12 N17 4.89(19) . . . . ?
N3 C4 C12 N17 -172.00(13) . . . . ?
N5 C4 C12 C13 -175.53(13) . . . . ?
N3 C4 C12 C13 7.58(19) . . . . ?
N1 S1 C18 C20 86.81(12) . . . . ?
N5 S1 C18 C20 -160.76(11) . . . . ?
N1 S1 C18 C19 153.21(12) . . . . ?
N5 S1 C18 C19 -94.35(13) . . . . ?
N17 C12 C13 C14 3.3(2) . . . . ?
C4 C12 C13 C14 -176.30(14) . . . . ?
N11 C6 C7 C8 0.7(2) . . . . ?
C2 C6 C7 C8 -178.60(15) . . . . ?
S1 C18 C19 C20 -105.25(14) . . . . ?
S1 C18 C20 C19 106.41(14) . . . . ?
C12 C13 C14 C15 -0.6(3) . . . . ?
C13 C14 C15 C16 -1.8(3) . . . . ?
C10 C9 C8 C7 -0.3(3) . . . . ?
C6 C7 C8 C9 -0.5(3) . . . . ?
C6 N11 C10 C9 -0.9(3) . . . . ?
C8 C9 C10 N11 1.1(3) . . . . ?
C12 N17 C16 C15 0.4(3) . . . . ?
C14 C15 C16 N17 2.0(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C18 H18 N1 1.00 2.62 3.606(2) 170.5 4_575
C19 H19A N5 0.99 2.65 3.493(2) 142.5 3_676
C15 H15 N1 0.95 2.57 3.507(2) 168.0 1_655
C18 H18 N1 1.00 2.62 3.606(2) 170.5 4_575
C19 H19A N5 0.99 2.65 3.493(2) 142.5 3_676
C15 H15 N1 0.95 2.57 3.507(2) 168.0 1_655

_refine_diff_density_max         0.305
_refine_diff_density_min         -0.203
_refine_diff_density_rms         0.048

####################################################################### 
# 
# 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 1518917'
_audit_update_record             
;
2016-11-23 deposited with the CCDC.
2017-02-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C36 H40 Cl4 N10 S2'
_chemical_formula_weight         818.70

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

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

_cell_length_a                   18.9919(12)
_cell_length_b                   14.2910(8)
_cell_length_c                   16.4594(16)
_cell_angle_alpha                90
_cell_angle_beta                 122.227(3)
_cell_angle_gamma                90
_cell_volume                     3779.1(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    1992
_cell_measurement_theta_min      2.54
_cell_measurement_theta_max      25.78

_exptl_crystal_description       plate
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.439
_exptl_crystal_F_000             1704
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.715
_exptl_crystal_size_mid          0.441
_exptl_crystal_size_min          0.280
_exptl_absorpt_coefficient_mu    0.467
_shelx_estimated_absorpt_T_min   0.731
_shelx_estimated_absorpt_T_max   0.880
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6129
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_process_details   'SADABS, Bruker (2003)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7805
_diffrn_reflns_av_unetI/netI     0.0639
_diffrn_reflns_av_R_equivalents  0.0381
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.907
_diffrn_reflns_theta_max         25.239
_diffrn_reflns_theta_full        25.239
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measured_fraction_theta_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_point_group_measured_fraction_full 0.988
_reflns_number_total             3374
_reflns_number_gt                2241
_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       'APEX II, Bruker (2009)'
_computing_cell_refinement       'APEX II, Bruker (2009)'
_computing_data_reduction        'XPREP, Bruker (2009)'
_computing_structure_solution    'SHELXS-03 (Sheldrick, 2003)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury (Macrae et al., 2008)'
_computing_publication_material  'CIFTAB (Sheldrick, 1997)'

_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)+(0.1393P)²+7.7477P] 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         3374
_refine_ls_number_parameters     245
_refine_ls_number_restraints     17
_refine_ls_R_factor_all          0.1292
_refine_ls_R_factor_gt           0.0872
_refine_ls_wR_factor_ref         0.2481
_refine_ls_wR_factor_gt          0.2195
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_restrained_S_all      1.089
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C2 C 0.7371(3) 0.4907(4) 0.8971(4) 0.0393(14) Uani 1 1 d . . . . .
H2 H 0.7779 0.4468 0.9392 0.047 Uiso 1 1 calc R U . . .
C3 C 0.6742(4) 0.5129(4) 0.9116(4) 0.0489(16) Uani 1 1 d . . . . .
H3 H 0.6701 0.4830 0.9606 0.059 Uiso 1 1 calc R U . . .
C4 C 0.6178(4) 0.5789(5) 0.8540(5) 0.0582(18) Uani 1 1 d . . . . .
H4 H 0.5740 0.5964 0.8625 0.070 Uiso 1 1 calc R U . . .
C5 C 0.6250(4) 0.6200(4) 0.7832(4) 0.0412(14) Uani 1 1 d . . . . .
H5 H 0.5860 0.6659 0.7421 0.049 Uiso 1 1 calc R U . . .
C6 C 0.6886(3) 0.5943(3) 0.7727(3) 0.0273(11) Uani 1 1 d . . . . .
C7 C 0.6998(3) 0.6392(3) 0.6974(3) 0.0239(11) Uani 1 1 d . . . . .
C9 C 0.6449(3) 0.7498(3) 0.5753(3) 0.0244(11) Uani 1 1 d . . . . .
C10 C 0.5727(3) 0.8133(3) 0.5168(3) 0.0212(10) Uani 1 1 d . . . . .
C11 C 0.5090(3) 0.8201(4) 0.5343(4) 0.0332(12) Uani 1 1 d . . . . .
H11 H 0.5120 0.7870 0.5861 0.040 Uiso 1 1 calc R U . . .
C12 C 0.4413(3) 0.8757(4) 0.4751(4) 0.0387(14) Uani 1 1 d . . . . .
H12 H 0.3962 0.8806 0.4844 0.046 Uiso 1 1 calc R U . . .
C13 C 0.4402(3) 0.9241(4) 0.4022(4) 0.0392(14) Uani 1 1 d . . . . .
H13 H 0.3945 0.9630 0.3600 0.047 Uiso 1 1 calc R U . . .
C14 C 0.5066(3) 0.9146(4) 0.3923(4) 0.0354(13) Uani 1 1 d . . . . .
H14 H 0.5059 0.9492 0.3426 0.042 Uiso 1 1 calc R U . . .
C18 C 0.8583(3) 0.7399(3) 0.6882(3) 0.0260(11) Uani 1 1 d . . . . .
H18A H 0.9098 0.7020 0.7234 0.031 Uiso 1 1 calc R U . . .
H18B H 0.8659 0.7849 0.6478 0.031 Uiso 1 1 calc R U . . .
C19 C 0.8504(3) 0.7953(3) 0.7615(3) 0.0263(11) Uani 1 1 d . . . . .
H19A H 0.8439 0.7519 0.8039 0.032 Uiso 1 1 calc R U . . .
H19B H 0.8002 0.8355 0.7281 0.032 Uiso 1 1 calc R U . . .
C20 C 0.9278(3) 0.8565(4) 0.8222(3) 0.0285(11) Uani 1 1 d . . . . .
H20A H 0.9780 0.8165 0.8508 0.034 Uiso 1 1 calc R U . . .
H20B H 0.9316 0.9027 0.7799 0.034 Uiso 1 1 calc R U . . .
C21 C 0.9264(3) 0.9084(3) 0.9024(3) 0.0269(11) Uani 1 1 d . . . . .
H21A H 0.9260 0.8620 0.9467 0.032 Uiso 1 1 calc R U . . .
H21B H 0.8743 0.9451 0.8739 0.032 Uiso 1 1 calc R U . . .
C22 C 1.0001(3) 0.9743(4) 0.9598(3) 0.0309(12) Uani 1 1 d . . . . .
H22A H 1.0522 0.9376 0.9876 0.037 Uiso 1 1 calc R U . . .
H22B H 1.0002 1.0209 0.9154 0.037 Uiso 1 1 calc R U . . .
N1 N 0.7440(3) 0.5272(3) 0.8275(3) 0.0314(10) Uani 1 1 d . . . . .
N8 N 0.6482(2) 0.7121(3) 0.6531(3) 0.0263(9) Uani 1 1 d . . . . .
N15 N 0.5724(3) 0.8605(3) 0.4469(3) 0.0328(11) Uani 1 1 d . . . . .
N16 N 0.7551(2) 0.6030(3) 0.6827(3) 0.0286(10) Uani 1 1 d . . . . .
N17 N 0.6938(2) 0.7341(3) 0.5433(3) 0.0271(10) Uani 1 1 d . . . . .
S1 S 0.77355(7) 0.66192(8) 0.60890(8) 0.0236(4) Uani 1 1 d . . . . .
C23 C 0.6875(5) 0.8800(5) 0.8144(6) 0.075(2) Uani 1 1 d D U . . .
H23A H 0.7123 0.9430 0.8240 0.090 Uiso 1 1 calc R U . A 1
H23B H 0.6809 0.8532 0.7553 0.090 Uiso 1 1 calc R U . A 1
Cl1 Cl 0.75570(17) 0.80850(18) 0.91315(19) 0.0978(9) Uani 1 1 d D U . . .
Cl2 Cl 0.5909(9) 0.8903(13) 0.7994(14) 0.136(4) Uani 0.57(4) 1 d D U P B 1
Cl2' Cl 0.6138(9) 0.9287(16) 0.8307(12) 0.095(5) Uani 0.43(4) 1 d D U P B 2


_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
C2 N1 1.328(6) . ?
C2 C3 1.375(8) . ?
C2 H2 0.9500 . ?
C3 C4 1.361(8) . ?
C3 H3 0.9500 . ?
C4 C5 1.375(8) . ?
C4 H4 0.9500 . ?
C5 C6 1.358(7) . ?
C5 H5 0.9500 . ?
C6 N1 1.352(6) . ?
C6 C7 1.509(7) . ?
C7 N16 1.305(6) . ?
C7 N8 1.347(6) . ?
C9 N17 1.308(6) . ?
C9 N8 1.359(6) . ?
C9 C10 1.491(7) . ?
C10 N15 1.332(6) . ?
C10 C11 1.388(7) . ?
C11 C12 1.378(7) . ?
C11 H11 0.9500 . ?
C12 C13 1.375(8) . ?
C12 H12 0.9500 . ?
C13 C14 1.361(8) . ?
C13 H13 0.9500 . ?
C14 N15 1.330(6) . ?
C14 H14 0.9500 . ?
C18 C19 1.516(7) . ?
C18 S1 1.815(5) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 C20 1.536(6) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C21 1.526(7) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 C22 1.526(6) . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C22 C22 1.516(10) 5_777 ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?
N16 S1 1.662(4) . ?
N17 S1 1.667(4) . ?
C23 Cl2' 1.707(11) . ?
C23 Cl2 1.720(12) . ?
C23 Cl1 1.765(9) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?

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
N1 C2 C3 123.7(5) . . ?
N1 C2 H2 118.1 . . ?
C3 C2 H2 118.1 . . ?
C4 C3 C2 118.1(5) . . ?
C4 C3 H3 121.0 . . ?
C2 C3 H3 121.0 . . ?
C3 C4 C5 119.4(6) . . ?
C3 C4 H4 120.3 . . ?
C5 C4 H4 120.3 . . ?
C6 C5 C4 119.2(5) . . ?
C6 C5 H5 120.4 . . ?
C4 C5 H5 120.4 . . ?
N1 C6 C5 122.4(5) . . ?
N1 C6 C7 116.7(4) . . ?
C5 C6 C7 120.9(4) . . ?
N16 C7 N8 129.2(4) . . ?
N16 C7 C6 117.6(4) . . ?
N8 C7 C6 113.2(4) . . ?
N17 C9 N8 128.7(4) . . ?
N17 C9 C10 116.8(4) . . ?
N8 C9 C10 114.4(4) . . ?
N15 C10 C11 122.8(4) . . ?
N15 C10 C9 116.4(4) . . ?
C11 C10 C9 120.8(4) . . ?
C12 C11 C10 118.8(5) . . ?
C12 C11 H11 120.6 . . ?
C10 C11 H11 120.6 . . ?
C13 C12 C11 118.7(6) . . ?
C13 C12 H12 120.6 . . ?
C11 C12 H12 120.6 . . ?
C14 C13 C12 118.1(5) . . ?
C14 C13 H13 121.0 . . ?
C12 C13 H13 121.0 . . ?
N15 C14 C13 125.0(5) . . ?
N15 C14 H14 117.5 . . ?
C13 C14 H14 117.5 . . ?
C19 C18 S1 117.9(3) . . ?
C19 C18 H18A 107.8 . . ?
S1 C18 H18A 107.8 . . ?
C19 C18 H18B 107.8 . . ?
S1 C18 H18B 107.8 . . ?
H18A C18 H18B 107.2 . . ?
C18 C19 C20 110.4(4) . . ?
C18 C19 H19A 109.6 . . ?
C20 C19 H19A 109.6 . . ?
C18 C19 H19B 109.6 . . ?
C20 C19 H19B 109.6 . . ?
H19A C19 H19B 108.1 . . ?
C21 C20 C19 112.8(4) . . ?
C21 C20 H20A 109.0 . . ?
C19 C20 H20A 109.0 . . ?
C21 C20 H20B 109.0 . . ?
C19 C20 H20B 109.0 . . ?
H20A C20 H20B 107.8 . . ?
C20 C21 C22 113.7(4) . . ?
C20 C21 H21A 108.8 . . ?
C22 C21 H21A 108.8 . . ?
C20 C21 H21B 108.8 . . ?
C22 C21 H21B 108.8 . . ?
H21A C21 H21B 107.7 . . ?
C22 C22 C21 114.2(5) 5_777 . ?
C22 C22 H22A 108.7 5_777 . ?
C21 C22 H22A 108.7 . . ?
C22 C22 H22B 108.7 5_777 . ?
C21 C22 H22B 108.7 . . ?
H22A C22 H22B 107.6 . . ?
C2 N1 C6 117.0(5) . . ?
C7 N8 C9 118.1(4) . . ?
C14 N15 C10 116.5(5) . . ?
C7 N16 S1 116.0(3) . . ?
C9 N17 S1 116.1(3) . . ?
N16 S1 N17 108.3(2) . . ?
N16 S1 C18 103.7(2) . . ?
N17 S1 C18 103.7(2) . . ?
Cl2' C23 Cl1 110.6(6) . . ?
Cl2 C23 Cl1 112.6(6) . . ?
Cl2 C23 H23A 109.1 . . ?
Cl1 C23 H23A 109.1 . . ?
Cl2 C23 H23B 109.1 . . ?
Cl1 C23 H23B 109.1 . . ?
H23A C23 H23B 107.8 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N1 C2 C3 C4 -2.8(10) . . . . ?
C2 C3 C4 C5 0.7(10) . . . . ?
C3 C4 C5 C6 -0.4(10) . . . . ?
C4 C5 C6 N1 2.1(9) . . . . ?
C4 C5 C6 C7 -178.6(5) . . . . ?
N1 C6 C7 N16 8.1(6) . . . . ?
C5 C6 C7 N16 -171.3(5) . . . . ?
N1 C6 C7 N8 -173.1(4) . . . . ?
C5 C6 C7 N8 7.6(7) . . . . ?
N17 C9 C10 N15 -11.0(6) . . . . ?
N8 C9 C10 N15 172.2(4) . . . . ?
N17 C9 C10 C11 167.5(4) . . . . ?
N8 C9 C10 C11 -9.3(6) . . . . ?
N15 C10 C11 C12 2.0(7) . . . . ?
C9 C10 C11 C12 -176.4(4) . . . . ?
C10 C11 C12 C13 -1.4(7) . . . . ?
C11 C12 C13 C14 -0.1(8) . . . . ?
C12 C13 C14 N15 1.2(8) . . . . ?
S1 C18 C19 C20 179.6(3) . . . . ?
C18 C19 C20 C21 -175.6(4) . . . . ?
C19 C20 C21 C22 -176.4(4) . . . . ?
C20 C21 C22 C22 -179.5(5) . . . 5_777 ?
C3 C2 N1 C6 4.4(8) . . . . ?
C5 C6 N1 C2 -4.0(7) . . . . ?
C7 C6 N1 C2 176.7(4) . . . . ?
N16 C7 N8 C9 7.4(7) . . . . ?
C6 C7 N8 C9 -171.3(4) . . . . ?
N17 C9 N8 C7 -10.5(7) . . . . ?
C10 C9 N8 C7 165.8(4) . . . . ?
C13 C14 N15 C10 -0.8(8) . . . . ?
C11 C10 N15 C14 -0.9(7) . . . . ?
C9 C10 N15 C14 177.6(4) . . . . ?
N8 C7 N16 S1 8.4(7) . . . . ?
C6 C7 N16 S1 -173.0(3) . . . . ?
N8 C9 N17 S1 -3.1(6) . . . . ?
C10 C9 N17 S1 -179.3(3) . . . . ?
C7 N16 S1 N17 -18.9(4) . . . . ?
C7 N16 S1 C18 90.8(4) . . . . ?
C9 N17 S1 N16 16.6(4) . . . . ?
C9 N17 S1 C18 -93.1(4) . . . . ?
C19 C18 S1 N16 -47.9(4) . . . . ?
C19 C18 S1 N17 65.2(4) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C3 H3 S1 0.95 3.00 3.716(6) 133.4 6_566
C13 H13 N1 0.95 2.62 3.316(7) 130.8 8_465
C14 H14 Cl2' 0.95 2.78 3.520(15) 135.7 6_575
C23 H23A N16 0.99 2.39 3.361(9) 167.9 4_656
C23 H23B N8 0.99 2.48 3.355(8) 146.6 .
C3 H3 S1 0.95 3.00 3.716(6) 133.4 6_566
C13 H13 N1 0.95 2.62 3.316(7) 130.8 8_465
C14 H14 Cl2' 0.95 2.78 3.520(15) 135.7 6_575
C23 H23A N16 0.99 2.39 3.361(9) 167.9 4_656
C23 H23B N8 0.99 2.48 3.355(8) 146.6 .

_refine_diff_density_max         0.756
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.116

