# 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_TQ4
_database_code_depnum_ccdc_archive 'CCDC 991643'
_audit_update_record             
;
2014-03-13 deposited with the CCDC.
2015-03-19 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 '2-(4-bromophenyl)-3-nitro-2H-thiopyrano[2,3-b]quinoline'
;
_chemical_name_common            
2-(4-bromophenyl)-3-nitro-2H-thiopyrano[2,3-b]quinoline
_chemical_melting_point          471.15
_chemical_formula_moiety         'C18 H11 Br N2 O2 S'
_chemical_formula_sum            'C18 H11 Br N2 O2 S'
_chemical_formula_weight         399.26

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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

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

_cell_length_a                   6.57240(10)
_cell_length_b                   12.7939(3)
_cell_length_c                   19.4514(5)
_cell_angle_alpha                90
_cell_angle_beta                 97.7056(14)
_cell_angle_gamma                90
_cell_volume                     1620.83(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       Block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.636
_exptl_crystal_F_000             800
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    2.678
_shelx_estimated_absorpt_T_min   0.501
_shelx_estimated_absorpt_T_max   0.739
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.501
_exptl_absorpt_correction_T_max  0.739
_exptl_absorpt_process_details   'SADABS (Bruker,2004)'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEXII CCD Area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            13135
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.646
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.974
_reflns_number_total             2850
_reflns_number_gt                2343
_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       'APEXII (Bruker, 2004)'
_computing_cell_refinement       'APEXII/SAINT (Bruker, 2004)'
_computing_data_reduction        'SAINT/XPREP (Bruker, 2004)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2013)'
_computing_molecular_graphics    'ORTEP3 (Farrugia, 1997) '
_computing_publication_material  'SHELXL-97 (Sheldrick, 2013)'


_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)+(0.0431P)²+0.8627P] 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         2850
_refine_ls_number_parameters     217
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0294
_refine_ls_wR_factor_ref         0.0813
_refine_ls_wR_factor_gt          0.0749
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_restrained_S_all      1.018
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.07823(5) 0.37216(2) 0.43224(2) 0.06325(14) Uani 1 1 d . . . . .
C1 C 0.5544(4) -0.0209(2) 0.84243(15) 0.0624(8) Uani 1 1 d . . . . .
H1 H 0.5599 0.0379 0.8707 0.075 Uiso 1 1 calc R U . . .
C2 C 0.7100(4) -0.0921(3) 0.85060(18) 0.0697(9) Uani 1 1 d . . . . .
H2 H 0.8206 -0.0816 0.8851 0.084 Uiso 1 1 calc R U . . .
C3 C 0.7068(4) -0.1803(3) 0.80834(18) 0.0674(9) Uani 1 1 d . . . . .
H3 H 0.8158 -0.2272 0.8147 0.081 Uiso 1 1 calc R U . . .
C4 C 0.5454(4) -0.1986(2) 0.75774(15) 0.0515(7) Uani 1 1 d . . . . .
H4 H 0.5446 -0.2575 0.7296 0.062 Uiso 1 1 calc R U . . .
C5 C 0.3788(3) -0.12687(18) 0.74845(13) 0.0397(6) Uani 1 1 d . . . . .
C6 C 0.2028(3) -0.14242(17) 0.69983(12) 0.0351(5) Uani 1 1 d . . . . .
H6 H 0.1933 -0.2014 0.6716 0.042 Uiso 1 1 calc R U . . .
C7 C 0.0450(3) -0.07135(17) 0.69365(11) 0.0314(5) Uani 1 1 d . . . . .
C8 C -0.1454(3) -0.09104(18) 0.64920(11) 0.0335(5) Uani 1 1 d . . . . .
H8 H -0.1697 -0.1582 0.6317 0.040 Uiso 1 1 calc R U . . .
C9 C -0.2878(3) -0.01828(18) 0.63184(11) 0.0345(5) Uani 1 1 d . . . . .
C10 C -0.2722(3) 0.09550(18) 0.64902(12) 0.0377(5) Uani 1 1 d . . . . .
H10 H -0.4118 0.1199 0.6524 0.045 Uiso 1 1 calc R U . . .
C11 C 0.0720(3) 0.01963(17) 0.73673(11) 0.0347(5) Uani 1 1 d . . . . .
C12 C 0.3844(4) -0.0371(2) 0.79073(13) 0.0432(6) Uani 1 1 d . . . . .
C13 C -0.1912(3) 0.16190(18) 0.59403(11) 0.0339(5) Uani 1 1 d . . . . .
C14 C -0.0198(4) 0.13111(18) 0.56481(12) 0.0408(6) Uani 1 1 d . . . . .
H14 H 0.0412 0.0670 0.5771 0.049 Uiso 1 1 calc R U . . .
C15 C 0.0621(4) 0.19427(19) 0.51764(12) 0.0424(6) Uani 1 1 d . . . . .
H15 H 0.1787 0.1738 0.4988 0.051 Uiso 1 1 calc R U . . .
C16 C -0.0325(4) 0.28796(18) 0.49913(12) 0.0414(6) Uani 1 1 d . . . . .
C17 C -0.2029(4) 0.31961(19) 0.52649(13) 0.0484(6) Uani 1 1 d . . . . .
H17 H -0.2655 0.3829 0.5130 0.058 Uiso 1 1 calc R U . . .
C18 C -0.2817(4) 0.25684(19) 0.57439(13) 0.0442(6) Uani 1 1 d . . . . .
H18 H -0.3967 0.2787 0.5936 0.053 Uiso 1 1 calc R U . . .
N1 N 0.2314(3) 0.03694(16) 0.78321(10) 0.0433(5) Uani 1 1 d . . . . .
N2 N -0.4766(3) -0.0509(2) 0.58792(11) 0.0472(5) Uani 1 1 d . . . . .
O1 O -0.5024(3) -0.14272(17) 0.57352(11) 0.0642(6) Uani 1 1 d . . . . .
O2 O -0.6003(3) 0.01796(19) 0.56831(12) 0.0724(6) Uani 1 1 d . . . . .
S1 S -0.12291(10) 0.11429(5) 0.73453(3) 0.04444(17) 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
Br1 C16 1.907(2) . ?
C1 C2 1.362(5) . ?
C1 C12 1.415(4) . ?
C1 H1 0.9300 . ?
C2 C3 1.395(5) . ?
C2 H2 0.9300 . ?
C3 C4 1.367(4) . ?
C3 H3 0.9300 . ?
C4 C5 1.422(3) . ?
C4 H4 0.9300 . ?
C5 C6 1.407(3) . ?
C5 C12 1.410(4) . ?
C6 C7 1.372(3) . ?
C6 H6 0.9300 . ?
C7 C11 1.431(3) . ?
C7 C8 1.445(3) . ?
C8 C9 1.331(3) . ?
C8 H8 0.9300 . ?
C9 N2 1.470(3) . ?
C9 C10 1.494(3) . ?
C10 C13 1.517(3) . ?
C10 S1 1.830(2) . ?
C10 H10 0.9800 . ?
C11 N1 1.308(3) . ?
C11 S1 1.759(2) . ?
C12 N1 1.374(3) . ?
C13 C18 1.384(3) . ?
C13 C14 1.385(3) . ?
C14 C15 1.385(3) . ?
C14 H14 0.9300 . ?
C15 C16 1.376(3) . ?
C15 H15 0.9300 . ?
C16 C17 1.364(4) . ?
C17 C18 1.382(4) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
N2 O1 1.214(3) . ?
N2 O2 1.225(3) . ?

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 C12 119.6(3) . . ?
C2 C1 H1 120.2 . . ?
C12 C1 H1 120.2 . . ?
C1 C2 C3 121.3(3) . . ?
C1 C2 H2 119.3 . . ?
C3 C2 H2 119.3 . . ?
C4 C3 C2 120.8(3) . . ?
C4 C3 H3 119.6 . . ?
C2 C3 H3 119.6 . . ?
C3 C4 C5 119.4(3) . . ?
C3 C4 H4 120.3 . . ?
C5 C4 H4 120.3 . . ?
C6 C5 C12 117.5(2) . . ?
C6 C5 C4 123.0(2) . . ?
C12 C5 C4 119.5(2) . . ?
C7 C6 C5 120.6(2) . . ?
C7 C6 H6 119.7 . . ?
C5 C6 H6 119.7 . . ?
C6 C7 C11 117.0(2) . . ?
C6 C7 C8 121.4(2) . . ?
C11 C7 C8 121.44(19) . . ?
C9 C8 C7 123.6(2) . . ?
C9 C8 H8 118.2 . . ?
C7 C8 H8 118.2 . . ?
C8 C9 N2 117.3(2) . . ?
C8 C9 C10 126.8(2) . . ?
N2 C9 C10 115.74(19) . . ?
C9 C10 C13 114.07(19) . . ?
C9 C10 S1 110.10(16) . . ?
C13 C10 S1 111.80(16) . . ?
C9 C10 H10 106.8 . . ?
C13 C10 H10 106.8 . . ?
S1 C10 H10 106.8 . . ?
N1 C11 C7 124.6(2) . . ?
N1 C11 S1 114.42(17) . . ?
C7 C11 S1 120.86(17) . . ?
N1 C12 C5 122.5(2) . . ?
N1 C12 C1 118.1(3) . . ?
C5 C12 C1 119.3(2) . . ?
C18 C13 C14 118.7(2) . . ?
C18 C13 C10 120.5(2) . . ?
C14 C13 C10 120.8(2) . . ?
C13 C14 C15 121.0(2) . . ?
C13 C14 H14 119.5 . . ?
C15 C14 H14 119.5 . . ?
C16 C15 C14 118.7(2) . . ?
C16 C15 H15 120.7 . . ?
C14 C15 H15 120.7 . . ?
C17 C16 C15 121.5(2) . . ?
C17 C16 Br1 120.45(18) . . ?
C15 C16 Br1 118.04(18) . . ?
C16 C17 C18 119.5(2) . . ?
C16 C17 H17 120.3 . . ?
C18 C17 H17 120.3 . . ?
C17 C18 C13 120.7(2) . . ?
C17 C18 H18 119.7 . . ?
C13 C18 H18 119.7 . . ?
C11 N1 C12 117.6(2) . . ?
O1 N2 O2 123.9(2) . . ?
O1 N2 C9 119.3(2) . . ?
O2 N2 C9 116.7(2) . . ?
C11 S1 C10 103.39(10) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C12 C1 C2 C3 0.9(4) . . . . ?
C1 C2 C3 C4 -0.8(5) . . . . ?
C2 C3 C4 C5 -0.2(4) . . . . ?
C3 C4 C5 C6 -177.0(2) . . . . ?
C3 C4 C5 C12 1.1(3) . . . . ?
C12 C5 C6 C7 0.9(3) . . . . ?
C4 C5 C6 C7 179.1(2) . . . . ?
C5 C6 C7 C11 2.2(3) . . . . ?
C5 C6 C7 C8 -173.6(2) . . . . ?
C6 C7 C8 C9 -167.7(2) . . . . ?
C11 C7 C8 C9 16.6(3) . . . . ?
C7 C8 C9 N2 -178.10(19) . . . . ?
C7 C8 C9 C10 5.5(4) . . . . ?
C8 C9 C10 C13 91.9(3) . . . . ?
N2 C9 C10 C13 -84.5(2) . . . . ?
C8 C9 C10 S1 -34.7(3) . . . . ?
N2 C9 C10 S1 148.89(16) . . . . ?
C6 C7 C11 N1 -3.2(3) . . . . ?
C8 C7 C11 N1 172.7(2) . . . . ?
C6 C7 C11 S1 -178.49(16) . . . . ?
C8 C7 C11 S1 -2.7(3) . . . . ?
C6 C5 C12 N1 -3.7(3) . . . . ?
C4 C5 C12 N1 178.1(2) . . . . ?
C6 C5 C12 C1 177.2(2) . . . . ?
C4 C5 C12 C1 -1.0(3) . . . . ?
C2 C1 C12 N1 -179.1(2) . . . . ?
C2 C1 C12 C5 0.0(4) . . . . ?
C9 C10 C13 C18 136.7(2) . . . . ?
S1 C10 C13 C18 -97.6(2) . . . . ?
C9 C10 C13 C14 -46.3(3) . . . . ?
S1 C10 C13 C14 79.5(3) . . . . ?
C18 C13 C14 C15 0.9(4) . . . . ?
C10 C13 C14 C15 -176.1(2) . . . . ?
C13 C14 C15 C16 -1.2(4) . . . . ?
C14 C15 C16 C17 0.4(4) . . . . ?
C14 C15 C16 Br1 -178.36(19) . . . . ?
C15 C16 C17 C18 0.6(4) . . . . ?
Br1 C16 C17 C18 179.36(19) . . . . ?
C16 C17 C18 C13 -0.9(4) . . . . ?
C14 C13 C18 C17 0.1(4) . . . . ?
C10 C13 C18 C17 177.2(2) . . . . ?
C7 C11 N1 C12 0.6(3) . . . . ?
S1 C11 N1 C12 176.19(16) . . . . ?
C5 C12 N1 C11 2.9(3) . . . . ?
C1 C12 N1 C11 -177.9(2) . . . . ?
C8 C9 N2 O1 5.3(3) . . . . ?
C10 C9 N2 O1 -177.9(2) . . . . ?
C8 C9 N2 O2 -175.1(2) . . . . ?
C10 C9 N2 O2 1.7(3) . . . . ?
N1 C11 S1 C10 160.91(17) . . . . ?
C7 C11 S1 C10 -23.3(2) . . . . ?
C9 C10 S1 C11 38.30(17) . . . . ?
C13 C10 S1 C11 -89.58(17) . . . . ?

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
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556
C8 H8 Br1 0.93 3.10 3.978(2) 158.4 3_556

_refine_diff_density_max         0.427
_refine_diff_density_min         -0.704
_refine_diff_density_rms         0.062

_shelxl_version_number           2013-4



