# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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 1033196'
_audit_update_record             
;
2014-11-08 deposited with the CCDC.
2015-02-12 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          491-492
_chemical_formula_moiety         ?
_chemical_formula_sum            'C17 H13 Br N4 O S'
_chemical_formula_weight         401.28
_chemical_oxdiff_usercomment     'Imtiaz Khan RXN-25'

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.5733(3)
_cell_length_b                   10.0581(7)
_cell_length_c                   11.2828(6)
_cell_angle_alpha                105.441(5)
_cell_angle_beta                 102.930(4)
_cell_angle_gamma                91.660(4)
_cell_volume                     803.82(8)
_cell_formula_units_Z            2
_cell_measurement_temperature    130.0(2)
_cell_measurement_reflns_used    3429
_cell_measurement_theta_min      2.9668
_cell_measurement_theta_max      29.0569

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_F_000             404
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.5961
_exptl_crystal_size_mid          0.3948
_exptl_crystal_size_min          0.1804
_exptl_absorpt_coefficient_mu    2.699
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_T_min  0.328
_exptl_absorpt_correction_T_max  0.639
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      130.0(2)
_diffrn_radiation_wavelength     0.7107
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_source         'SuperNova (Mo) X-ray Source'
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_reflns_number            6521
_diffrn_reflns_av_unetI/netI     0.0539
_diffrn_reflns_av_R_equivalents  0.0331
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.973
_diffrn_reflns_theta_max         29.121
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.863
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.863
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.863
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3736
_reflns_number_gt                3227
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0298P)²+0.1373P] 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         3736
_refine_ls_number_parameters     218
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0349
_refine_ls_wR_factor_ref         0.0776
_refine_ls_wR_factor_gt          0.0729
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_restrained_S_all      1.028
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C -0.1061(3) 0.4183(2) 0.34710(19) 0.0163(5) Uani 1 1 d . . . . .
C2 C -0.2662(3) 0.4743(3) 0.3693(2) 0.0186(5) Uani 1 1 d . . . . .
H2 H -0.3438 0.4301 0.4032 0.022 Uiso 1 1 calc R U . . .
C3 C -0.3071(3) 0.5960(3) 0.3401(2) 0.0208(5) Uani 1 1 d . . . . .
C4 C -0.1957(3) 0.6647(3) 0.2897(2) 0.0215(5) Uani 1 1 d . . . . .
H4 H -0.2261 0.7468 0.2706 0.026 Uiso 1 1 calc R U . . .
C5 C -0.0370(3) 0.6080(3) 0.2682(2) 0.0224(5) Uani 1 1 d . . . . .
H5 H 0.0398 0.6526 0.2341 0.027 Uiso 1 1 calc R U . . .
C6 C 0.0086(3) 0.4859(3) 0.2967(2) 0.0183(5) Uani 1 1 d . . . . .
H6 H 0.1157 0.4492 0.2822 0.022 Uiso 1 1 calc R U . . .
C7 C -0.0638(3) 0.2910(2) 0.3818(2) 0.0161(5) Uani 1 1 d . . . . .
C8 C 0.0617(3) 0.1052(2) 0.4076(2) 0.0174(5) Uani 1 1 d . . . . .
C9 C 0.2988(3) 0.1094(3) 0.2989(2) 0.0192(5) Uani 1 1 d . . . . .
C10 C 0.4562(3) 0.0805(3) 0.2396(2) 0.0225(5) Uani 1 1 d . . . . .
H10A H 0.4727 0.1476 0.1941 0.027 Uiso 1 1 calc R U . . .
H10B H 0.5672 0.0844 0.3035 0.027 Uiso 1 1 calc R U . . .
C11 C 0.5460(3) -0.1158(3) 0.1018(2) 0.0199(5) Uani 1 1 d . . . . .
C12 C 0.4949(3) -0.2503(3) 0.0245(2) 0.0223(5) Uani 1 1 d . . . . .
C13 C 0.6245(3) -0.3210(3) -0.0306(2) 0.0286(6) Uani 1 1 d . . . . .
H13 H 0.5934 -0.4112 -0.0826 0.034 Uiso 1 1 calc R U . . .
C14 C 0.7986(3) -0.2599(3) -0.0096(2) 0.0309(6) Uani 1 1 d . . . . .
H14 H 0.8839 -0.3093 -0.0464 0.037 Uiso 1 1 calc R U . . .
C15 C 0.8454(3) -0.1264(3) 0.0656(2) 0.0291(6) Uani 1 1 d . . . . .
H15 H 0.9624 -0.0852 0.0790 0.035 Uiso 1 1 calc R U . . .
C16 C 0.7189(3) -0.0516(3) 0.1222(2) 0.0230(5) Uani 1 1 d . . . . .
H16 H 0.7499 0.0393 0.1724 0.028 Uiso 1 1 calc R U . . .
C17 C 0.3052(3) -0.3143(3) 0.0014(2) 0.0306(6) Uani 1 1 d . . . . .
H17A H 0.2927 -0.4067 -0.0540 0.046 Uiso 1 1 calc R U . . .
H17B H 0.2206 -0.2599 -0.0372 0.046 Uiso 1 1 calc R U . . .
H17C H 0.2805 -0.3175 0.0805 0.046 Uiso 1 1 calc R U . . .
N1 N -0.1569(2) 0.2303(2) 0.44168(17) 0.0185(4) Uani 1 1 d . . . . .
N2 N -0.0789(2) 0.1113(2) 0.45835(18) 0.0191(4) Uani 1 1 d . . . . .
N3 N 0.0768(2) 0.2131(2) 0.35847(17) 0.0161(4) Uani 1 1 d . . . . .
N4 N 0.2124(2) 0.2181(2) 0.29520(17) 0.0185(4) Uani 1 1 d . . . . .
S1 S 0.22830(7) -0.00350(6) 0.37765(6) 0.02053(14) Uani 1 1 d . . . . .
Br1 Br -0.52215(3) 0.67326(3) 0.37552(2) 0.02884(9) Uani 1 1 d . . . . .
O1 O 0.4119(2) -0.05472(18) 0.15500(15) 0.0222(4) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C6 1.390(3) . ?
C1 C2 1.396(3) . ?
C1 C7 1.460(3) . ?
C2 C3 1.375(3) . ?
C2 H2 0.9300 . ?
C3 C4 1.380(3) . ?
C3 Br1 1.901(2) . ?
C4 C5 1.387(3) . ?
C4 H4 0.9300 . ?
C5 C6 1.384(3) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C7 N1 1.317(3) . ?
C7 N3 1.372(3) . ?
C8 N2 1.313(3) . ?
C8 N3 1.357(3) . ?
C8 S1 1.725(2) . ?
C9 N4 1.296(3) . ?
C9 C10 1.492(3) . ?
C9 S1 1.754(2) . ?
C10 O1 1.419(3) . ?
C10 H10A 0.9700 . ?
C10 H10B 0.9700 . ?
C11 O1 1.372(2) . ?
C11 C16 1.386(3) . ?
C11 C12 1.390(4) . ?
C12 C13 1.391(3) . ?
C12 C17 1.495(3) . ?
C13 C14 1.381(4) . ?
C13 H13 0.9300 . ?
C14 C15 1.371(4) . ?
C14 H14 0.9300 . ?
C15 C16 1.397(3) . ?
C15 H15 0.9300 . ?
C16 H16 0.9300 . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
N1 N2 1.388(3) . ?
N3 N4 1.382(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
C6 C1 C2 119.9(2) . . ?
C6 C1 C7 122.41(19) . . ?
C2 C1 C7 117.70(19) . . ?
C3 C2 C1 118.9(2) . . ?
C3 C2 H2 120.6 . . ?
C1 C2 H2 120.6 . . ?
C2 C3 C4 122.3(2) . . ?
C2 C3 Br1 118.19(18) . . ?
C4 C3 Br1 119.44(17) . . ?
C3 C4 C5 118.2(2) . . ?
C3 C4 H4 120.9 . . ?
C5 C4 H4 120.9 . . ?
C6 C5 C4 121.0(2) . . ?
C6 C5 H5 119.5 . . ?
C4 C5 H5 119.5 . . ?
C5 C6 C1 119.7(2) . . ?
C5 C6 H6 120.1 . . ?
C1 C6 H6 120.1 . . ?
N1 C7 N3 107.79(18) . . ?
N1 C7 C1 125.17(18) . . ?
N3 C7 C1 127.05(19) . . ?
N2 C8 N3 111.13(18) . . ?
N2 C8 S1 139.05(18) . . ?
N3 C8 S1 109.73(15) . . ?
N4 C9 C10 121.4(2) . . ?
N4 C9 S1 118.39(16) . . ?
C10 C9 S1 120.21(17) . . ?
O1 C10 C9 105.51(19) . . ?
O1 C10 H10A 110.6 . . ?
C9 C10 H10A 110.6 . . ?
O1 C10 H10B 110.6 . . ?
C9 C10 H10B 110.6 . . ?
H10A C10 H10B 108.8 . . ?
O1 C11 C16 124.0(2) . . ?
O1 C11 C12 114.2(2) . . ?
C16 C11 C12 121.7(2) . . ?
C11 C12 C13 117.9(2) . . ?
C11 C12 C17 120.2(2) . . ?
C13 C12 C17 121.9(3) . . ?
C14 C13 C12 121.3(3) . . ?
C14 C13 H13 119.4 . . ?
C12 C13 H13 119.4 . . ?
C15 C14 C13 119.9(2) . . ?
C15 C14 H14 120.1 . . ?
C13 C14 H14 120.1 . . ?
C14 C15 C16 120.6(2) . . ?
C14 C15 H15 119.7 . . ?
C16 C15 H15 119.7 . . ?
C11 C16 C15 118.6(3) . . ?
C11 C16 H16 120.7 . . ?
C15 C16 H16 120.7 . . ?
C12 C17 H17A 109.5 . . ?
C12 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C12 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C7 N1 N2 109.60(16) . . ?
C8 N2 N1 105.43(18) . . ?
C8 N3 C7 106.05(17) . . ?
C8 N3 N4 118.49(17) . . ?
C7 N3 N4 135.37(18) . . ?
C9 N4 N3 106.38(18) . . ?
C8 S1 C9 87.01(10) . . ?
C11 O1 C10 117.53(18) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6 C1 C2 C3 0.2(3) . . . . ?
C7 C1 C2 C3 178.5(2) . . . . ?
C1 C2 C3 C4 0.0(4) . . . . ?
C1 C2 C3 Br1 -178.23(17) . . . . ?
C2 C3 C4 C5 -0.1(4) . . . . ?
Br1 C3 C4 C5 178.17(17) . . . . ?
C3 C4 C5 C6 -0.1(4) . . . . ?
C4 C5 C6 C1 0.3(4) . . . . ?
C2 C1 C6 C5 -0.3(3) . . . . ?
C7 C1 C6 C5 -178.6(2) . . . . ?
C6 C1 C7 N1 172.6(2) . . . . ?
C2 C1 C7 N1 -5.7(3) . . . . ?
C6 C1 C7 N3 -7.7(4) . . . . ?
C2 C1 C7 N3 174.0(2) . . . . ?
N4 C9 C10 O1 -125.0(2) . . . . ?
S1 C9 C10 O1 55.8(2) . . . . ?
O1 C11 C12 C13 -178.39(19) . . . . ?
C16 C11 C12 C13 1.4(3) . . . . ?
O1 C11 C12 C17 2.3(3) . . . . ?
C16 C11 C12 C17 -177.9(2) . . . . ?
C11 C12 C13 C14 -0.1(3) . . . . ?
C17 C12 C13 C14 179.2(2) . . . . ?
C12 C13 C14 C15 -0.8(3) . . . . ?
C13 C14 C15 C16 0.5(3) . . . . ?
O1 C11 C16 C15 178.08(19) . . . . ?
C12 C11 C16 C15 -1.7(3) . . . . ?
C14 C15 C16 C11 0.7(3) . . . . ?
N3 C7 N1 N2 -0.1(2) . . . . ?
C1 C7 N1 N2 179.6(2) . . . . ?
N3 C8 N2 N1 -0.5(3) . . . . ?
S1 C8 N2 N1 -176.5(2) . . . . ?
C7 N1 N2 C8 0.4(3) . . . . ?
N2 C8 N3 C7 0.5(3) . . . . ?
S1 C8 N3 C7 177.69(16) . . . . ?
N2 C8 N3 N4 -176.5(2) . . . . ?
S1 C8 N3 N4 0.7(3) . . . . ?
N1 C7 N3 C8 -0.2(2) . . . . ?
C1 C7 N3 C8 -180.0(2) . . . . ?
N1 C7 N3 N4 176.0(2) . . . . ?
C1 C7 N3 N4 -3.7(4) . . . . ?
C10 C9 N4 N3 -179.9(2) . . . . ?
S1 C9 N4 N3 -0.6(2) . . . . ?
C8 N3 N4 C9 -0.1(3) . . . . ?
C7 N3 N4 C9 -176.0(2) . . . . ?
N2 C8 S1 C9 175.2(3) . . . . ?
N3 C8 S1 C9 -0.79(17) . . . . ?
N4 C9 S1 C8 0.9(2) . . . . ?
C10 C9 S1 C8 -179.9(2) . . . . ?
C16 C11 O1 C10 -2.4(3) . . . . ?
C12 C11 O1 C10 177.35(18) . . . . ?
C9 C10 O1 C11 -170.23(17) . . . . ?

_refine_diff_density_max         0.472
_refine_diff_density_min         -0.512
_refine_diff_density_rms         0.084

# start Validation Reply Form
_vrf_PLAT430_shelx               
;
PROBLEM: Short Inter D...A Contact S1 .. N2 .. 2.80 Ang. 
RESPONSE: This is a chemically valid short contact which is an example of a
sigma-hole interaction between the nitrogen and the sulphur
;
# end Validation Reply Form


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Ethanol'
####################################################################### 
# 
# 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 1033197'
_audit_update_record             
;
2014-11-08 deposited with the CCDC.
2015-02-12 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          481-482
_chemical_formula_moiety         ?
_chemical_formula_sum            'C23 H18 N4 O S'
_chemical_formula_weight         398.47
_chemical_oxdiff_usercomment     'Imtiaz Khan RXN-5'


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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   13.0300(3)
_cell_length_b                   17.3539(4)
_cell_length_c                   8.6142(2)
_cell_angle_alpha                90
_cell_angle_beta                 98.990(2)
_cell_angle_gamma                90
_cell_volume                     1923.93(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    130.0(1)
_cell_measurement_reflns_used    1923
_cell_measurement_theta_min      2.8971
_cell_measurement_theta_max      28.9998

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_F_000             832
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_exptl_absorpt_coefficient_mu    0.191
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_T_min  0.86346
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      130.0(21)
_diffrn_radiation_wavelength     0.7107
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_source         'SuperNova (Mo) X-ray Source'
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_reflns_number            11392
_diffrn_reflns_av_unetI/netI     0.0496
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.903
_diffrn_reflns_theta_max         29.188
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.881
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.881
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.881
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4578
_reflns_number_gt                3421
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0560P)²+0.6953P] 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         4578
_refine_ls_number_parameters     263
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0736
_refine_ls_R_factor_gt           0.0505
_refine_ls_wR_factor_ref         0.1343
_refine_ls_wR_factor_gt          0.1156
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_restrained_S_all      1.053
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.67825(14) -0.33750(11) 0.2952(2) 0.0268(4) Uani 1 1 d . . . . .
C2 C 0.68767(14) -0.41651(12) 0.3217(2) 0.0287(4) Uani 1 1 d . . . . .
H2 H 0.6481 -0.4397 0.3896 0.034 Uiso 1 1 calc R U . . .
C3 C 0.75430(14) -0.46147(12) 0.2499(2) 0.0303(4) Uani 1 1 d . . . . .
H3 H 0.7586 -0.5143 0.2681 0.036 Uiso 1 1 calc R U . . .
C4 C 0.81489(14) -0.42674(12) 0.1501(2) 0.0280(4) Uani 1 1 d . . . . .
C5 C 0.80623(15) -0.34804(12) 0.1226(2) 0.0303(4) Uani 1 1 d . . . . .
H5 H 0.8461 -0.3250 0.0550 0.036 Uiso 1 1 calc R U . . .
C6 C 0.73960(14) -0.30369(12) 0.1937(2) 0.0287(4) Uani 1 1 d . . . . .
H6 H 0.7352 -0.2510 0.1745 0.034 Uiso 1 1 calc R U . . .
C7 C 0.60215(14) -0.29531(11) 0.3705(2) 0.0267(4) Uani 1 1 d . . . . .
C8 C 0.50276(14) -0.20655(12) 0.4468(2) 0.0283(4) Uani 1 1 d . . . . .
C9 C 0.49318(14) -0.07868(12) 0.2901(2) 0.0292(4) Uani 1 1 d . . . . .
H9A H 0.4504 -0.1024 0.2005 0.035 Uiso 1 1 calc R U . . .
H9B H 0.4815 -0.0235 0.2836 0.035 Uiso 1 1 calc R U . . .
C10 C 0.60568(14) -0.09514(11) 0.2832(2) 0.0250(4) Uani 1 1 d . . . . .
C11 C 0.67281(14) -0.03587(11) 0.2293(2) 0.0250(4) Uani 1 1 d . . . . .
C12 C 0.77705(14) -0.05214(11) 0.2214(2) 0.0266(4) Uani 1 1 d . . . . .
H12 H 0.8056 -0.0988 0.2601 0.032 Uiso 1 1 calc R U . . .
C13 C 0.83787(14) 0.00006(11) 0.1569(2) 0.0271(4) Uani 1 1 d . . . . .
H13 H 0.9069 -0.0121 0.1525 0.032 Uiso 1 1 calc R U . . .
C14 C 0.79828(14) 0.07084(11) 0.0979(2) 0.0245(4) Uani 1 1 d . . . . .
C15 C 0.69589(14) 0.08788(11) 0.1124(2) 0.0277(4) Uani 1 1 d . . . . .
H15 H 0.6684 0.1356 0.0788 0.033 Uiso 1 1 calc R U . . .
C16 C 0.63406(14) 0.03545(11) 0.1759(2) 0.0273(4) Uani 1 1 d . . . . .
H16 H 0.5656 0.0482 0.1828 0.033 Uiso 1 1 calc R U . . .
C17 C 0.86004(14) 0.12389(11) 0.0144(2) 0.0258(4) Uani 1 1 d . . . . .
C18 C 0.96797(15) 0.12361(11) 0.0430(2) 0.0297(4) Uani 1 1 d . . . . .
H18 H 1.0025 0.0908 0.1193 0.036 Uiso 1 1 calc R U . . .
C19 C 1.02491(16) 0.17136(12) -0.0402(3) 0.0353(5) Uani 1 1 d . . . . .
H19 H 1.0971 0.1705 -0.0194 0.042 Uiso 1 1 calc R U . . .
C20 C 0.97502(17) 0.22019(13) -0.1539(3) 0.0402(5) Uani 1 1 d . . . . .
H20 H 1.0133 0.2516 -0.2110 0.048 Uiso 1 1 calc R U . . .
C21 C 0.86767(18) 0.22219(13) -0.1822(3) 0.0410(5) Uani 1 1 d . . . . .
H21 H 0.8336 0.2556 -0.2576 0.049 Uiso 1 1 calc R U . . .
C22 C 0.81085(16) 0.17472(12) -0.0990(3) 0.0336(5) Uani 1 1 d . . . . .
H22 H 0.7387 0.1766 -0.1188 0.040 Uiso 1 1 calc R U . . .
C23 C 0.88557(18) -0.54677(13) 0.0827(3) 0.0422(6) Uani 1 1 d . . . . .
H23A H 0.9046 -0.5635 0.1896 0.063 Uiso 1 1 calc R U . . .
H23B H 0.9347 -0.5664 0.0204 0.063 Uiso 1 1 calc R U . . .
H23C H 0.8175 -0.5657 0.0419 0.063 Uiso 1 1 calc R U . . .
N1 N 0.53661(12) -0.32879(10) 0.4505(2) 0.0305(4) Uani 1 1 d . . . . .
N2 N 0.47310(13) -0.27192(10) 0.5002(2) 0.0322(4) Uani 1 1 d . . . . .
N3 N 0.58311(11) -0.21737(9) 0.36466(19) 0.0246(3) Uani 1 1 d . . . . .
N4 N 0.64663(11) -0.16188(9) 0.31366(18) 0.0254(3) Uani 1 1 d . . . . .
O1 O 0.88542(11) -0.46463(8) 0.07710(17) 0.0350(4) Uani 1 1 d . . . . .
S1 S 0.45485(4) -0.11504(3) 0.46989(6) 0.03185(16) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C2 1.392(3) . ?
C1 C6 1.402(3) . ?
C1 C7 1.463(3) . ?
C2 C3 1.383(3) . ?
C3 C4 1.392(3) . ?
C4 O1 1.361(2) . ?
C4 C5 1.388(3) . ?
C5 C6 1.374(3) . ?
C7 N1 1.314(2) . ?
C7 N3 1.375(2) . ?
C8 N2 1.305(3) . ?
C8 N3 1.365(2) . ?
C8 S1 1.729(2) . ?
C9 C10 1.504(3) . ?
C9 S1 1.813(2) . ?
C10 N4 1.285(2) . ?
C10 C11 1.472(3) . ?
C11 C16 1.388(3) . ?
C11 C12 1.399(3) . ?
C12 C13 1.377(3) . ?
C13 C14 1.397(3) . ?
C14 C15 1.391(3) . ?
C14 C17 1.481(3) . ?
C15 C16 1.383(3) . ?
C17 C18 1.389(3) . ?
C17 C22 1.396(3) . ?
C18 C19 1.385(3) . ?
C19 C20 1.378(3) . ?
C20 C21 1.382(3) . ?
C21 C22 1.381(3) . ?
C23 O1 1.426(3) . ?
N1 N2 1.397(2) . ?
N3 N4 1.385(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
C2 C1 C6 118.06(18) . . ?
C2 C1 C7 117.93(17) . . ?
C6 C1 C7 123.98(18) . . ?
C3 C2 C1 121.84(18) . . ?
C2 C3 C4 119.21(18) . . ?
O1 C4 C5 116.05(17) . . ?
O1 C4 C3 124.41(18) . . ?
C5 C4 C3 119.53(18) . . ?
C6 C5 C4 121.01(18) . . ?
C5 C6 C1 120.35(18) . . ?
N1 C7 N3 109.00(17) . . ?
N1 C7 C1 123.54(18) . . ?
N3 C7 C1 127.39(17) . . ?
N2 C8 N3 110.89(18) . . ?
N2 C8 S1 128.71(15) . . ?
N3 C8 S1 120.39(15) . . ?
C10 C9 S1 111.57(14) . . ?
N4 C10 C11 116.49(16) . . ?
N4 C10 C9 122.65(17) . . ?
C11 C10 C9 120.71(16) . . ?
C16 C11 C12 117.98(17) . . ?
C16 C11 C10 121.65(17) . . ?
C12 C11 C10 120.24(17) . . ?
C13 C12 C11 120.75(17) . . ?
C12 C13 C14 121.49(17) . . ?
C15 C14 C13 117.33(17) . . ?
C15 C14 C17 120.86(17) . . ?
C13 C14 C17 121.70(16) . . ?
C16 C15 C14 121.45(18) . . ?
C15 C16 C11 120.90(17) . . ?
C18 C17 C22 117.89(18) . . ?
C18 C17 C14 121.57(17) . . ?
C22 C17 C14 120.52(17) . . ?
C19 C18 C17 121.03(19) . . ?
C20 C19 C18 120.28(19) . . ?
C19 C20 C21 119.5(2) . . ?
C22 C21 C20 120.2(2) . . ?
C21 C22 C17 121.05(19) . . ?
C7 N1 N2 108.25(16) . . ?
C8 N2 N1 106.47(15) . . ?
C8 N3 C7 105.38(16) . . ?
C8 N3 N4 127.84(16) . . ?
C7 N3 N4 125.60(15) . . ?
C10 N4 N3 116.21(15) . . ?
C4 O1 C23 117.68(15) . . ?
C8 S1 C9 93.93(9) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6 C1 C2 C3 -0.7(3) . . . . ?
C7 C1 C2 C3 177.15(18) . . . . ?
C1 C2 C3 C4 1.0(3) . . . . ?
C2 C3 C4 O1 177.81(18) . . . . ?
C2 C3 C4 C5 -1.0(3) . . . . ?
O1 C4 C5 C6 -178.16(17) . . . . ?
C3 C4 C5 C6 0.7(3) . . . . ?
C4 C5 C6 C1 -0.5(3) . . . . ?
C2 C1 C6 C5 0.4(3) . . . . ?
C7 C1 C6 C5 -177.28(18) . . . . ?
C2 C1 C7 N1 -5.9(3) . . . . ?
C6 C1 C7 N1 171.82(18) . . . . ?
C2 C1 C7 N3 177.44(18) . . . . ?
C6 C1 C7 N3 -4.9(3) . . . . ?
S1 C9 C10 N4 47.9(2) . . . . ?
S1 C9 C10 C11 -136.67(15) . . . . ?
N4 C10 C11 C16 172.49(18) . . . . ?
C9 C10 C11 C16 -3.2(3) . . . . ?
N4 C10 C11 C12 -3.4(3) . . . . ?
C9 C10 C11 C12 -179.13(18) . . . . ?
C16 C11 C12 C13 -2.4(3) . . . . ?
C10 C11 C12 C13 173.63(18) . . . . ?
C11 C12 C13 C14 0.3(3) . . . . ?
C12 C13 C14 C15 2.4(3) . . . . ?
C12 C13 C14 C17 -173.89(18) . . . . ?
C13 C14 C15 C16 -3.0(3) . . . . ?
C17 C14 C15 C16 173.36(18) . . . . ?
C14 C15 C16 C11 0.9(3) . . . . ?
C12 C11 C16 C15 1.9(3) . . . . ?
C10 C11 C16 C15 -174.13(18) . . . . ?
C15 C14 C17 C18 157.29(19) . . . . ?
C13 C14 C17 C18 -26.5(3) . . . . ?
C15 C14 C17 C22 -24.3(3) . . . . ?
C13 C14 C17 C22 151.9(2) . . . . ?
C22 C17 C18 C19 -1.0(3) . . . . ?
C14 C17 C18 C19 177.42(19) . . . . ?
C17 C18 C19 C20 -0.1(3) . . . . ?
C18 C19 C20 C21 1.2(3) . . . . ?
C19 C20 C21 C22 -1.0(4) . . . . ?
C20 C21 C22 C17 -0.2(3) . . . . ?
C18 C17 C22 C21 1.2(3) . . . . ?
C14 C17 C22 C21 -177.3(2) . . . . ?
N3 C7 N1 N2 -0.5(2) . . . . ?
C1 C7 N1 N2 -177.68(17) . . . . ?
N3 C8 N2 N1 -0.3(2) . . . . ?
S1 C8 N2 N1 -179.55(15) . . . . ?
C7 N1 N2 C8 0.5(2) . . . . ?
N2 C8 N3 C7 0.0(2) . . . . ?
S1 C8 N3 C7 179.34(14) . . . . ?
N2 C8 N3 N4 -168.01(17) . . . . ?
S1 C8 N3 N4 11.4(3) . . . . ?
N1 C7 N3 C8 0.3(2) . . . . ?
C1 C7 N3 C8 177.38(18) . . . . ?
N1 C7 N3 N4 168.65(16) . . . . ?
C1 C7 N3 N4 -14.3(3) . . . . ?
C11 C10 N4 N3 179.87(15) . . . . ?
C9 C10 N4 N3 -4.5(3) . . . . ?
C8 N3 N4 C10 -29.5(3) . . . . ?
C7 N3 N4 C10 164.82(18) . . . . ?
C5 C4 O1 C23 -170.65(19) . . . . ?
C3 C4 O1 C23 10.5(3) . . . . ?
N2 C8 S1 C9 -153.6(2) . . . . ?
N3 C8 S1 C9 27.21(17) . . . . ?
C10 C9 S1 C8 -51.63(16) . . . . ?

_refine_diff_density_max         0.316
_refine_diff_density_min         -0.400
_refine_diff_density_rms         0.059


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Ethanol'
