# 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_ay23m
_database_code_depnum_ccdc_archive 'CCDC 1410087'
_audit_update_record             
;
2015-07-02 deposited with the CCDC.
2015-09-29 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT431_ay23m               
;
PROBLEM:
PLAT431_ALERT_2_B This test reports on short intermolecular 
Halogen .. Donor/Acceptor atom-type distances.
RESPONSE:
An intermolecular interaction of sulfur atom with the bromide anion is 
seen in the crystal structure (J. Am. Chem. Soc.1977,99,pp 4860-4862). 
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
'(2Z)-N,3-dibutyl-4-(2-oxo-2H-chromen-3-yl)-2,3-dihydro-1,3-thiazol-2-iminium bromide'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C20 H25 N2 O2 S, Br'
_chemical_formula_sum            'C20 H25 Br N2 O2 S'
_chemical_formula_weight         437.39

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'
Br Br -0.2901 2.4595 '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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'P 21/c  '
_symmetry_space_group_name_Hall  '-P 2ybc '

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

_cell_length_a                   11.7828(8)
_cell_length_b                   11.0859(7)
_cell_length_c                   16.1335(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.1990(10)
_cell_angle_gamma                90.00
_cell_volume                     2104.1(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    5202
_cell_measurement_theta_min      2.23
_cell_measurement_theta_max      27.07

_exptl_crystal_description       plate
_exptl_crystal_colour            brown
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             904
_exptl_absorpt_coefficient_mu    2.069
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5313
_exptl_absorpt_correction_T_max  0.8198
_exptl_absorpt_process_details   'Bruker AXS SADABS program'

_exptl_special_details           
; 
 Sheldrick,G.M.,(2003),University of gottingen,Germany 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            19639
_diffrn_reflns_av_R_equivalents  0.0202
_diffrn_reflns_av_sigmaI/netI    0.0148
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.73
_diffrn_reflns_theta_max         25.00
_reflns_number_total             3696
_reflns_number_gt                3291
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0513P)²+0.7023P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3696
_refine_ls_number_parameters     241
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0293
_refine_ls_wR_factor_ref         0.0827
_refine_ls_wR_factor_gt          0.0797
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_restrained_S_all      1.041
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.315808(18) 0.04841(2) 0.517802(13) 0.04817(10) Uani 1 1 d . . .
C1 C 0.69164(19) 0.05554(19) 0.85683(15) 0.0465(5) Uani 1 1 d . . .
C2 C 0.66052(17) 0.18349(19) 0.85590(12) 0.0401(4) Uani 1 1 d . . .
C3 C 0.73741(18) 0.26743(19) 0.88092(13) 0.0438(5) Uani 1 1 d . . .
H3 H 0.7154 0.3479 0.8831 0.053 Uiso 1 1 calc R . .
C4 C 0.85225(17) 0.2355(2) 0.90419(13) 0.0442(5) Uani 1 1 d . . .
C5 C 0.88369(18) 0.1156(2) 0.89829(14) 0.0463(5) Uani 1 1 d . . .
C6 C 0.9950(2) 0.0785(2) 0.91401(17) 0.0594(6) Uani 1 1 d . . .
H6 H 1.0149 -0.0022 0.9087 0.071 Uiso 1 1 calc R . .
C7 C 1.0755(2) 0.1632(3) 0.93761(17) 0.0656(7) Uani 1 1 d . . .
H7 H 1.1506 0.1394 0.9483 0.079 Uiso 1 1 calc R . .
C8 C 1.0470(2) 0.2820(3) 0.94570(17) 0.0670(7) Uani 1 1 d . . .
H8 H 1.1024 0.3380 0.9624 0.080 Uiso 1 1 calc R . .
C9 C 0.9365(2) 0.3190(2) 0.92928(16) 0.0584(6) Uani 1 1 d . . .
H9 H 0.9176 0.3999 0.9349 0.070 Uiso 1 1 calc R . .
C10 C 0.54083(16) 0.21534(18) 0.83555(13) 0.0399(4) Uani 1 1 d . . .
C11 C 0.47572(18) 0.2781(2) 0.88478(13) 0.0459(5) Uani 1 1 d . . .
H11 H 0.5011 0.3083 0.9363 0.055 Uiso 1 1 calc R . .
C12 C 0.37462(16) 0.21684(18) 0.75535(13) 0.0401(4) Uani 1 1 d . . .
C13 C 0.54055(17) 0.13619(19) 0.68678(13) 0.0431(5) Uani 1 1 d . . .
H13A H 0.4930 0.0751 0.6593 0.052 Uiso 1 1 calc R . .
H13B H 0.6118 0.0984 0.7051 0.052 Uiso 1 1 calc R . .
C14 C 0.56399(19) 0.2347(2) 0.62515(14) 0.0508(5) Uani 1 1 d . . .
H14A H 0.4920 0.2669 0.6030 0.061 Uiso 1 1 calc R . .
H14B H 0.6022 0.1994 0.5793 0.061 Uiso 1 1 calc R . .
C15 C 0.6359(2) 0.3382(2) 0.66052(16) 0.0610(6) Uani 1 1 d . . .
H15A H 0.7058 0.3060 0.6864 0.073 Uiso 1 1 calc R . .
H15B H 0.5951 0.3784 0.7032 0.073 Uiso 1 1 calc R . .
C16 C 0.6651(4) 0.4300(3) 0.5951(3) 0.1000(12) Uani 1 1 d . . .
H16A H 0.7098 0.3920 0.5546 0.150 Uiso 1 1 calc R . .
H16B H 0.7077 0.4950 0.6210 0.150 Uiso 1 1 calc R . .
H16C H 0.5964 0.4610 0.5684 0.150 Uiso 1 1 calc R . .
C17 C 0.18533(18) 0.2388(2) 0.68655(18) 0.0578(6) Uani 1 1 d . . .
H17A H 0.1731 0.2842 0.6354 0.069 Uiso 1 1 calc R . .
H17B H 0.1746 0.2935 0.7324 0.069 Uiso 1 1 calc R . .
C18 C 0.09947(19) 0.1408(2) 0.68815(17) 0.0584(6) Uani 1 1 d . . .
H18A H 0.1109 0.0965 0.7398 0.070 Uiso 1 1 calc R . .
H18B H 0.1114 0.0853 0.6430 0.070 Uiso 1 1 calc R . .
C19 C -0.0224(2) 0.1861(3) 0.68036(19) 0.0714(8) Uani 1 1 d . . .
H19A H -0.0372 0.2338 0.7290 0.086 Uiso 1 1 calc R . .
H19B H -0.0314 0.2384 0.6322 0.086 Uiso 1 1 calc R . .
C20 C -0.1084(3) 0.0858(4) 0.6719(3) 0.1032(13) Uani 1 1 d . . .
H20A H -0.1072 0.0513 0.6174 0.155 Uiso 1 1 calc R . .
H20B H -0.1828 0.1174 0.6802 0.155 Uiso 1 1 calc R . .
H20C H -0.0901 0.0248 0.7127 0.155 Uiso 1 1 calc R . .
H1N H 0.3227(19) 0.157(2) 0.6502(12) 0.046(6) Uiso 1 1 d D . .
N1 N 0.48364(13) 0.18161(15) 0.76005(10) 0.0380(4) Uani 1 1 d . . .
N2 N 0.30179(15) 0.19430(17) 0.69242(13) 0.0477(4) Uani 1 1 d D . .
O1 O 0.62877(15) -0.02720(15) 0.84172(13) 0.0648(5) Uani 1 1 d . . .
O2 O 0.80414(13) 0.02874(13) 0.87654(11) 0.0533(4) Uani 1 1 d . . .
S1 S 0.33903(4) 0.29712(5) 0.84251(3) 0.04605(15) 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 O1 1.196(3) . ?
C1 O2 1.378(3) . ?
C1 C2 1.465(3) . ?
C2 C3 1.345(3) . ?
C2 C10 1.473(3) . ?
C3 C4 1.428(3) . ?
C3 H3 0.9300 . ?
C4 C5 1.385(3) . ?
C4 C9 1.400(3) . ?
C5 O2 1.375(3) . ?
C5 C6 1.384(3) . ?
C6 C7 1.374(4) . ?
C6 H6 0.9300 . ?
C7 C8 1.367(4) . ?
C7 H7 0.9300 . ?
C8 C9 1.377(3) . ?
C8 H8 0.9300 . ?
C9 H9 0.9300 . ?
C10 C11 1.331(3) . ?
C10 N1 1.409(3) . ?
C11 S1 1.727(2) . ?
C11 H11 0.9300 . ?
C12 N2 1.316(3) . ?
C12 N1 1.341(2) . ?
C12 S1 1.735(2) . ?
C13 N1 1.480(3) . ?
C13 C14 1.513(3) . ?
C13 H13A 0.9700 . ?
C13 H13B 0.9700 . ?
C14 C15 1.519(3) . ?
C14 H14A 0.9700 . ?
C14 H14B 0.9700 . ?
C15 C16 1.519(4) . ?
C15 H15A 0.9700 . ?
C15 H15B 0.9700 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C17 N2 1.456(3) . ?
C17 C18 1.486(3) . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?
C18 C19 1.519(3) . ?
C18 H18A 0.9700 . ?
C18 H18B 0.9700 . ?
C19 C20 1.506(4) . ?
C19 H19A 0.9700 . ?
C19 H19B 0.9700 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
N2 H1N 0.846(16) . ?

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 O2 117.30(19) . . ?
O1 C1 C2 126.1(2) . . ?
O2 C1 C2 116.62(18) . . ?
C3 C2 C1 120.19(19) . . ?
C3 C2 C10 121.43(19) . . ?
C1 C2 C10 118.06(18) . . ?
C2 C3 C4 121.3(2) . . ?
C2 C3 H3 119.3 . . ?
C4 C3 H3 119.3 . . ?
C5 C4 C9 117.8(2) . . ?
C5 C4 C3 118.22(19) . . ?
C9 C4 C3 123.9(2) . . ?
O2 C5 C6 117.6(2) . . ?
O2 C5 C4 120.56(19) . . ?
C6 C5 C4 121.8(2) . . ?
C7 C6 C5 118.7(2) . . ?
C7 C6 H6 120.7 . . ?
C5 C6 H6 120.7 . . ?
C8 C7 C6 121.1(2) . . ?
C8 C7 H7 119.5 . . ?
C6 C7 H7 119.5 . . ?
C7 C8 C9 120.2(2) . . ?
C7 C8 H8 119.9 . . ?
C9 C8 H8 119.9 . . ?
C8 C9 C4 120.4(2) . . ?
C8 C9 H9 119.8 . . ?
C4 C9 H9 119.8 . . ?
C11 C10 N1 113.00(18) . . ?
C11 C10 C2 124.67(19) . . ?
N1 C10 C2 122.32(17) . . ?
C10 C11 S1 112.59(16) . . ?
C10 C11 H11 123.7 . . ?
S1 C11 H11 123.7 . . ?
N2 C12 N1 124.73(19) . . ?
N2 C12 S1 123.08(16) . . ?
N1 C12 S1 112.18(14) . . ?
N1 C13 C14 112.76(17) . . ?
N1 C13 H13A 109.0 . . ?
C14 C13 H13A 109.0 . . ?
N1 C13 H13B 109.0 . . ?
C14 C13 H13B 109.0 . . ?
H13A C13 H13B 107.8 . . ?
C13 C14 C15 114.66(19) . . ?
C13 C14 H14A 108.6 . . ?
C15 C14 H14A 108.6 . . ?
C13 C14 H14B 108.6 . . ?
C15 C14 H14B 108.6 . . ?
H14A C14 H14B 107.6 . . ?
C14 C15 C16 112.9(3) . . ?
C14 C15 H15A 109.0 . . ?
C16 C15 H15A 109.0 . . ?
C14 C15 H15B 109.0 . . ?
C16 C15 H15B 109.0 . . ?
H15A C15 H15B 107.8 . . ?
C15 C16 H16A 109.5 . . ?
C15 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C15 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
N2 C17 C18 113.0(2) . . ?
N2 C17 H17A 109.0 . . ?
C18 C17 H17A 109.0 . . ?
N2 C17 H17B 109.0 . . ?
C18 C17 H17B 109.0 . . ?
H17A C17 H17B 107.8 . . ?
C17 C18 C19 113.5(2) . . ?
C17 C18 H18A 108.9 . . ?
C19 C18 H18A 108.9 . . ?
C17 C18 H18B 108.9 . . ?
C19 C18 H18B 108.9 . . ?
H18A C18 H18B 107.7 . . ?
C20 C19 C18 113.1(3) . . ?
C20 C19 H19A 109.0 . . ?
C18 C19 H19A 109.0 . . ?
C20 C19 H19B 109.0 . . ?
C18 C19 H19B 109.0 . . ?
H19A C19 H19B 107.8 . . ?
C19 C20 H20A 109.5 . . ?
C19 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C19 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C12 N1 C10 112.46(16) . . ?
C12 N1 C13 121.96(16) . . ?
C10 N1 C13 124.39(16) . . ?
C12 N2 C17 123.9(2) . . ?
C12 N2 H1N 120.5(16) . . ?
C17 N2 H1N 115.5(16) . . ?
C5 O2 C1 122.75(17) . . ?
C11 S1 C12 89.72(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
O1 C1 C2 C3 174.4(2) . . . . ?
O2 C1 C2 C3 -6.0(3) . . . . ?
O1 C1 C2 C10 0.8(4) . . . . ?
O2 C1 C2 C10 -179.66(18) . . . . ?
C1 C2 C3 C4 3.7(3) . . . . ?
C10 C2 C3 C4 177.15(19) . . . . ?
C2 C3 C4 C5 1.7(3) . . . . ?
C2 C3 C4 C9 178.8(2) . . . . ?
C9 C4 C5 O2 177.9(2) . . . . ?
C3 C4 C5 O2 -4.8(3) . . . . ?
C9 C4 C5 C6 -1.9(3) . . . . ?
C3 C4 C5 C6 175.4(2) . . . . ?
O2 C5 C6 C7 -178.6(2) . . . . ?
C4 C5 C6 C7 1.3(4) . . . . ?
C5 C6 C7 C8 0.1(4) . . . . ?
C6 C7 C8 C9 -0.7(4) . . . . ?
C7 C8 C9 C4 0.0(4) . . . . ?
C5 C4 C9 C8 1.3(4) . . . . ?
C3 C4 C9 C8 -175.9(2) . . . . ?
C3 C2 C10 C11 -51.6(3) . . . . ?
C1 C2 C10 C11 122.0(2) . . . . ?
C3 C2 C10 N1 128.2(2) . . . . ?
C1 C2 C10 N1 -58.3(3) . . . . ?
N1 C10 C11 S1 1.3(3) . . . . ?
C2 C10 C11 S1 -178.98(17) . . . . ?
N1 C13 C14 C15 57.5(3) . . . . ?
C13 C14 C15 C16 175.5(3) . . . . ?
N2 C17 C18 C19 -178.9(2) . . . . ?
C17 C18 C19 C20 173.2(3) . . . . ?
N2 C12 N1 C10 -178.3(2) . . . . ?
S1 C12 N1 C10 1.8(2) . . . . ?
N2 C12 N1 C13 13.7(3) . . . . ?
S1 C12 N1 C13 -166.21(15) . . . . ?
C11 C10 N1 C12 -2.0(3) . . . . ?
C2 C10 N1 C12 178.22(19) . . . . ?
C11 C10 N1 C13 165.68(19) . . . . ?
C2 C10 N1 C13 -14.1(3) . . . . ?
C14 C13 N1 C12 71.9(2) . . . . ?
C14 C13 N1 C10 -94.7(2) . . . . ?
N1 C12 N2 C17 -176.6(2) . . . . ?
S1 C12 N2 C17 3.2(3) . . . . ?
C18 C17 N2 C12 -115.0(3) . . . . ?
C6 C5 O2 C1 -177.8(2) . . . . ?
C4 C5 O2 C1 2.3(3) . . . . ?
O1 C1 O2 C5 -177.4(2) . . . . ?
C2 C1 O2 C5 3.0(3) . . . . ?
C10 C11 S1 C12 -0.19(18) . . . . ?
N2 C12 S1 C11 179.2(2) . . . . ?
N1 C12 S1 C11 -0.96(16) . . . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.187
_refine_diff_density_rms         0.058
