3-(2-Amino-1,3-thia­zol-4-yl)-6-chloro-2H-chromen-2-one

Chopra, D.; Choudhury, A.R.; Venugopala, K.N.; Govender, T.; Kruger, H.G.; Maguire, G.E.M.; Guru Row, T.N.

doi:10.1107/S1600536809048247

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3111

doi:10.1107/S1600536809048247

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3-(2-Amino-1,3-thiazol-4-yl)-6-chloro-2H-chromen-2-one

Deepak Chopra,^a ^* A. R. Choudhury,^b K. N. Venugopala,^c Thavendran Govender,^d Hendrik G. Kruger,^c Glenn E. M. Maguire ^c and T. N. Guru Row ^e

^aDepartment of Chemistry, Indian Institute of Science Education and Research, Bhopal 462 023, India, ^bChemistry Group, Birla Institute of Technology and science, Pilani, Pilani, 333 031, Rajasthan, India, ^cSchool of Chemistry, University of Kwazulu-Natal, Durban 4000, South Africa, ^dSchool of Pharmacy and Pharmacology, University of Kwazulu-Natal, Durban 4000, South Africa, and ^eSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India
^*Correspondence e-mail: dchopra@iiserbhopal.ac.in

(Received 4 November 2009; accepted 13 November 2009; online 18 November 2009)

The title compound, C₁₂H₇ClN₂O₂S, crystallizes with two molecules in the asymmetric unit. The molecular conformation is roughly planar for both these molecules with maximum deviations of 0.177 (3) and 0.076 (4) Å from their respective mean planes. In the crystal, strong N—H⋯N and weak but highly directional C—H⋯O hydrogen bonds provide the links between the molecules. The structure is further stabilised by aromatic π–π stacking interactions with centroid–centroid distances in the range 3.650 (3)–3.960 (3) Å.

Related literature

For applications of coumarin compounds in photochemistry, see: Vishnumurthy et al. (2001 ). For their roles as dyes, laser dyes and in probing ultrafast solvation effects see: Morris & Rusell (1971 ); Khalfan et al., (1987 ); Maroncelli & Fleming (1987 ). For graph set motifs, see: Bernstein et al. (1995 ). For the synthesis of the title compound, see: Venugopal et al. (2004 ). For related structures see: Vishnumurthy et al. (2001).

Experimental

Crystal data

C₁₂H₇ClN₂O₂S
M_r = 278.72
Monoclinic, P 2₁ /c
a = 12.494 (8) Å
b = 7.350 (5) Å
c = 25.013 (15) Å
β = 98.156 (12)°
V = 2274 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 290 K
0.20 × 0.10 × 0.02 mm

Data collection

Bruker SMART CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick (1996 ) T_min = 0.885, T_max = 0.990
16106 measured reflections
4165 independent reflections
2561 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.118
S = 1.01
4165 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N3ⁱ	0.86	2.31	3.124 (4)	158
N4—H4A⋯N1ⁱⁱ	0.86	2.27	3.116 (4)	168
C7—H7⋯O2ⁱⁱⁱ	0.93	2.54	3.387 (4)	152
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and CAMERON (Watkin et al., 1993 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048247/sj2672sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048247/sj2672Isup2.hkl

checkCIF report

Comment top

Coumarins are an important class of organic compounds and have been extensively studied.Such molecules of vast structural diversity find useful applications in several areas of synthetic chemistry, medicinal chemistry and photochemistry. The formation of [2 + 2] cycloaddition products upon irradiation (Vishnumurthy et al.,2001) of coumarin and its derivatives has contributed immensely to the area of solid-state chemistry. Several substituted coumarin derivatives find applications in the dye industry (Morris & Rusell, 1971) and in the area of LASER dyes (Khalfan et al., 1987) based on the fact that such compounds show state dependent variations in their static dipole moments. These have also been used to probe ultrafast solvation effects (Maroncelli & Fleming, 1987). The geometry and molecular packing patterns of several coumarin derivatives have been studied to evaluate the features of non-covalent interactions (Vishnumurthy et al., 2001). Against this background, and to obtain more information on such compounds the solid-state structure of the title compound is reported here.

In the title compound, we have a chloro substituted coumarin ring crystallizing in monoclinic centrosymmetric space group with two unique molecules in the asymmetric unit [(A) and (B)]. Both the molecules are essentially planar with the dihedral angles between the least squares planes passing through the coumarin ring and thiazoyl ring being 9.1 (1) and 4.9 (1)Å in A and B respectively. The largest displacement is observed for the atom C11 being -0.020 (3)Å for molecule A and atom C13 being -0.041 (4)Å for molecule B from the weighted least squares planes through C1/O2 and C13/O3 respectively. Aromatic π···π stacking interactions are found with distances Cg2···Cg6 = 3.942 (3) Å, Cg2···Cg7 = 3.650 (3) Å, and Cg3···Cg7 = 3.960 (3)Å between the molecules A and B. Cg2, Cg3, Cg6 and Cg7 are the centroids of the six-membered rings O2/C8, C4/C9, O3/C20 and C16/C21 (Figure 1). Molecules A are linked by alternating C—H···O interactions (involving H7 and O2) forming R²2(8) ring dimers [Bernstein et al., 1995]. N—H···N hydrogen bonds form hetero-dimeric motifs linking A and B molecules. (Figure 2, Table 1). Thus the supramolecular assembly is built up by an interplay of strong N—H···N, weak C—H···O and π···π van der Waals interactions. A short Cl···S contact of distance 3.532 (2)Å ( symmetry code: x, -y+1+1/2, z-1/2) is also present in the crystal lattice

Related literature top

For applications of coumarin compounds in photochemistry, see: Vishnumurthy et al. (2001). For their roles as dyes, laser dyes and in probing ultrafast solvation effects see: Morris & Rusell (1971); Khalfan et al., (1987); Maroncelli & Fleming (1987). For graph set motifs, see: Bernstein et al. (1995). For the synthesis of the title compound, see: Venugopal et al. (2004). For related structures see: Vishnumurthy et al. (2001).

Experimental top

The compounds were synthesized in accordance with the procedure reported in the literature (Venugopal et al., 2004). Single crystals of the compound were grown from chloroform:methanol (1:1) by slow evaporation at 275–277 K.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. : The structure of the title compound drawn with 50% ellipsoidal probability showing the two molecules in the asymmetric unit (Molecules A and B). The dotted lines indicate inter-molecular centroid···centroid interactions. Cg2, Cg3, Cg6 and Cg7 are the centroids of the pyranone ring O2/C9 and the phenyl ring C4/C9 in Molecule A, and the pyranone ring O3/C15 and phenyl ring C16/C21 in Molecule B.

Fig. 2. : Packing of the title compound highlighting the C—H···O dimers and N—H···N heterodimeric units. Only participating H atoms have been shown, others have been omitted for clarity.

3-(2-amino-1,3-thiazol-4-yl)-6-chloro-2H-chromen-2-one top

Crystal data top

C₁₂H₇ClN₂O₂S	F(000) = 1136
M_r = 278.72	D_x = 1.628 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 845 reflections
a = 12.494 (8) Å	θ = 1.6–25.8°
b = 7.350 (5) Å	µ = 0.51 mm⁻¹
c = 25.013 (15) Å	T = 290 K
β = 98.156 (12)°	Plate, yellow
V = 2274 (3) Å³	0.20 × 0.10 × 0.02 mm
Z = 8

Data collection top

Bruker SMART CCD area detector diffractometer	4165 independent reflections
Radiation source: fine-focus sealed tube	2561 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 25.4°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick (1996)	h = −15→15
T_min = 0.885, T_max = 0.990	k = −8→8
16106 measured reflections	l = −29→30

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0493P)²] where P = (F_o² + 2F_c²)/3
4165 reflections	(Δ/σ)_max < 0.001
325 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₂H₇ClN₂O₂S	V = 2274 (3) Å³
M_r = 278.72	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.494 (8) Å	µ = 0.51 mm⁻¹
b = 7.350 (5) Å	T = 290 K
c = 25.013 (15) Å	0.20 × 0.10 × 0.02 mm
β = 98.156 (12)°

Data collection top

Bruker SMART CCD area detector diffractometer	4165 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick (1996)	2561 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.990	R_int = 0.054
16106 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.01	Δρ_max = 0.28 e Å⁻³
4165 reflections	Δρ_min = −0.27 e Å⁻³
325 parameters

Special details top

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

Refinement. 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.23200 (7)	0.90698 (12)	0.22923 (3)	0.0415 (2)
S2	0.28374 (8)	0.49152 (15)	0.13304 (4)	0.0563 (3)
Cl1	0.07808 (7)	0.52598 (14)	0.60106 (3)	0.0559 (3)
Cl2	0.12399 (7)	0.11642 (12)	0.50115 (3)	0.0533 (3)
O1	0.44938 (19)	0.7077 (4)	0.37710 (10)	0.0724 (8)
O2	0.39831 (17)	0.6431 (3)	0.45510 (9)	0.0475 (6)
O3	0.45453 (17)	0.2376 (3)	0.36083 (9)	0.0485 (6)
O4	0.50908 (19)	0.3322 (4)	0.28593 (10)	0.0684 (8)
N1	0.12697 (19)	0.8694 (3)	0.31039 (10)	0.0338 (6)
N2	0.0231 (3)	0.9983 (5)	0.23312 (13)	0.0502 (9)
N3	0.1780 (2)	0.4062 (3)	0.21072 (10)	0.0365 (6)
N4	0.0660 (3)	0.4837 (5)	0.13067 (14)	0.0530 (9)
C1	0.3740 (3)	0.6983 (5)	0.40182 (14)	0.0436 (9)
C2	0.2602 (2)	0.7400 (4)	0.38192 (12)	0.0308 (7)
C3	0.1857 (3)	0.7177 (4)	0.41557 (13)	0.0332 (8)
C4	0.1379 (3)	0.6270 (4)	0.50590 (13)	0.0366 (8)
C5	0.1731 (3)	0.5640 (4)	0.55710 (13)	0.0370 (8)
C6	0.2809 (3)	0.5279 (5)	0.57507 (15)	0.0444 (9)
C7	0.3557 (3)	0.5552 (5)	0.54048 (14)	0.0436 (9)
C8	0.3206 (2)	0.6182 (4)	0.48857 (13)	0.0353 (8)
C9	0.2130 (2)	0.6547 (4)	0.47006 (12)	0.0319 (7)
C10	0.2323 (2)	0.8062 (4)	0.32644 (12)	0.0317 (7)
C11	0.1171 (3)	0.9292 (4)	0.26057 (13)	0.0352 (8)
C12	0.2989 (3)	0.8191 (4)	0.28810 (13)	0.0388 (8)
C13	0.4323 (3)	0.3045 (5)	0.30836 (14)	0.0443 (9)
C14	0.3174 (2)	0.3330 (4)	0.28654 (12)	0.0340 (8)
C15	0.2416 (3)	0.3064 (4)	0.31904 (13)	0.0346 (8)
C16	0.1909 (3)	0.2176 (4)	0.40798 (13)	0.0354 (8)
C17	0.2229 (3)	0.1554 (4)	0.45952 (13)	0.0378 (8)
C18	0.3301 (3)	0.1209 (5)	0.47895 (14)	0.0441 (9)
C19	0.4068 (3)	0.1491 (5)	0.44523 (15)	0.0484 (10)
C20	0.3756 (3)	0.2112 (4)	0.39311 (13)	0.0384 (8)
C21	0.2678 (2)	0.2457 (4)	0.37355 (12)	0.0315 (7)
C22	0.2884 (2)	0.3895 (4)	0.23001 (13)	0.0357 (8)
C23	0.1654 (3)	0.4575 (4)	0.16061 (13)	0.0375 (8)
C24	0.3552 (3)	0.4296 (5)	0.19410 (14)	0.0487 (10)
H2A	−0.0333	1.0075	0.2492	0.062*
H2B	0.0214	1.0376	0.2008	0.062*
H3	0.1138	0.7442	0.4028	0.039*
H4	0.0648	0.6505	0.4950	0.044*
H4A	0.0083	0.4664	0.1450	0.063*
H4B	0.0614	0.5185	0.0976	0.063*
H6	0.3028	0.4849	0.6099	0.053*
H7	0.4289	0.5323	0.5515	0.052*
H12	0.3712	0.7846	0.2928	0.047*
H15	0.1694	0.3273	0.3053	0.041*
H16	0.1181	0.2406	0.3960	0.042*
H18	0.3502	0.0795	0.5140	0.053*
H19	0.4799	0.1262	0.4575	0.057*
H24	0.4303	0.4239	0.2010	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0423 (5)	0.0528 (6)	0.0305 (5)	−0.0011 (4)	0.0088 (4)	0.0006 (4)
S2	0.0480 (6)	0.0865 (8)	0.0360 (5)	−0.0034 (5)	0.0115 (4)	0.0097 (5)
Cl1	0.0482 (6)	0.0858 (8)	0.0339 (5)	−0.0029 (5)	0.0069 (4)	0.0074 (5)
Cl2	0.0571 (6)	0.0611 (6)	0.0452 (6)	0.0043 (5)	0.0192 (5)	0.0086 (5)
N1	0.0300 (14)	0.0429 (17)	0.0278 (15)	−0.0001 (12)	0.0019 (12)	0.0017 (12)
N2	0.039 (2)	0.076 (3)	0.0348 (19)	0.0068 (18)	0.0018 (15)	0.0118 (18)
N3	0.0352 (16)	0.0448 (17)	0.0299 (16)	0.0003 (13)	0.0055 (12)	0.0012 (13)
N4	0.045 (2)	0.076 (3)	0.037 (2)	0.0023 (18)	0.0042 (17)	0.0137 (18)
O1	0.0354 (15)	0.132 (3)	0.0524 (17)	0.0247 (16)	0.0163 (13)	0.0260 (17)
O2	0.0306 (12)	0.0713 (17)	0.0400 (14)	0.0133 (12)	0.0030 (11)	0.0089 (13)
O3	0.0298 (13)	0.0725 (17)	0.0423 (15)	0.0043 (12)	0.0021 (11)	0.0100 (12)
O4	0.0332 (14)	0.118 (2)	0.0566 (17)	0.0055 (15)	0.0144 (13)	0.0211 (16)
C1	0.039 (2)	0.052 (2)	0.041 (2)	0.0098 (17)	0.0071 (17)	0.0030 (18)
C2	0.0300 (17)	0.0317 (19)	0.0310 (18)	0.0053 (14)	0.0054 (14)	−0.0028 (14)
C3	0.0269 (19)	0.0353 (19)	0.035 (2)	0.0018 (15)	−0.0019 (16)	−0.0002 (15)
C4	0.0264 (19)	0.040 (2)	0.040 (2)	0.0022 (15)	−0.0052 (16)	0.0005 (16)
C5	0.039 (2)	0.038 (2)	0.0329 (19)	−0.0025 (16)	0.0025 (15)	−0.0023 (15)
C6	0.047 (2)	0.051 (2)	0.032 (2)	0.0050 (18)	−0.0068 (17)	0.0015 (18)
C7	0.032 (2)	0.055 (2)	0.041 (2)	0.0079 (18)	−0.0040 (17)	0.0004 (18)
C8	0.0329 (18)	0.0380 (19)	0.0345 (19)	0.0044 (15)	0.0032 (15)	−0.0041 (16)
C9	0.0303 (18)	0.0296 (18)	0.0350 (19)	0.0034 (14)	0.0024 (15)	−0.0001 (14)
C10	0.0322 (18)	0.0339 (19)	0.0285 (18)	0.0001 (15)	0.0027 (14)	−0.0030 (15)
C11	0.0360 (19)	0.0357 (19)	0.0333 (19)	−0.0048 (15)	0.0025 (15)	−0.0029 (15)
C12	0.035 (2)	0.045 (2)	0.038 (2)	0.0007 (17)	0.0097 (16)	−0.0035 (16)
C13	0.035 (2)	0.058 (2)	0.039 (2)	0.0054 (17)	0.0053 (17)	0.0029 (18)
C14	0.0294 (18)	0.0353 (19)	0.0372 (19)	−0.0003 (14)	0.0044 (15)	−0.0022 (15)
C15	0.0269 (19)	0.039 (2)	0.036 (2)	−0.0015 (16)	−0.0037 (15)	0.0005 (16)
C16	0.034 (2)	0.034 (2)	0.038 (2)	0.0010 (16)	0.0022 (17)	0.0013 (16)
C17	0.046 (2)	0.0333 (19)	0.036 (2)	−0.0013 (16)	0.0108 (16)	−0.0002 (15)
C18	0.048 (2)	0.050 (2)	0.033 (2)	0.0004 (18)	−0.0014 (18)	0.0029 (18)
C19	0.030 (2)	0.064 (3)	0.048 (2)	0.0042 (18)	−0.0097 (18)	0.0080 (19)
C20	0.0322 (19)	0.043 (2)	0.038 (2)	−0.0008 (16)	0.0008 (15)	0.0002 (16)
C21	0.0293 (17)	0.0329 (19)	0.0313 (19)	0.0010 (14)	0.0006 (14)	−0.0019 (14)
C22	0.0324 (18)	0.038 (2)	0.037 (2)	−0.0023 (15)	0.0052 (15)	−0.0010 (16)
C23	0.037 (2)	0.040 (2)	0.034 (2)	−0.0023 (15)	0.0020 (16)	−0.0031 (16)
C24	0.040 (2)	0.065 (3)	0.042 (2)	−0.0030 (19)	0.0088 (18)	0.0055 (19)

Geometric parameters (Å, º) top

S1—C12	1.713 (4)	C13—C14	1.475 (4)
S1—C11	1.738 (3)	C7—C6	1.376 (5)
Cl2—C17	1.749 (3)	C7—H7	0.9300
Cl1—C5	1.750 (3)	C2—C10	1.464 (4)
S2—C24	1.714 (4)	C2—C1	1.470 (5)
S2—C23	1.736 (3)	C15—C14	1.347 (4)
C3—C2	1.349 (4)	C15—H15	0.9300
C3—C9	1.436 (4)	C22—C24	1.347 (4)
C3—H3	0.9300	C22—C14	1.467 (4)
O3—C20	1.371 (4)	C23—N4	1.369 (4)
O3—C13	1.392 (4)	C10—C12	1.364 (4)
O2—C8	1.381 (4)	C5—C4	1.375 (4)
O2—C1	1.385 (4)	C5—C6	1.388 (5)
N3—C23	1.298 (4)	C1—O1	1.200 (4)
N3—C22	1.402 (4)	C18—C19	1.381 (5)
C8—C9	1.385 (4)	C18—C17	1.385 (5)
C8—C7	1.387 (4)	C18—H18	0.9300
C16—C17	1.372 (4)	C11—N2	1.369 (4)
C16—C21	1.395 (4)	C6—H6	0.9300
C16—H16	0.9300	C4—H4	0.9300
C21—C20	1.392 (4)	C24—H24	0.9300
C21—C15	1.429 (4)	C19—H19	0.9300
C9—C4	1.402 (4)	C12—H12	0.9300
C20—C19	1.385 (4)	N4—H4A	0.8600
N1—C11	1.311 (4)	N4—H4B	0.8600
N1—C10	1.401 (4)	N2—H2A	0.8600
C13—O4	1.196 (4)	N2—H2B	0.8600

C12—S1—C11	89.03 (16)	C12—C10—N1	114.5 (3)
C24—S2—C23	88.61 (17)	C12—C10—C2	127.5 (3)
C2—C3—C9	122.6 (3)	N1—C10—C2	118.0 (3)
C2—C3—H3	118.7	C15—C14—C22	121.5 (3)
C9—C3—H3	118.7	C15—C14—C13	119.1 (3)
C20—O3—C13	122.8 (3)	C22—C14—C13	119.3 (3)
C8—O2—C1	123.1 (3)	C4—C5—C6	122.3 (3)
C23—N3—C22	109.8 (3)	C4—C5—Cl1	118.9 (3)
O2—C8—C9	120.2 (3)	C6—C5—Cl1	118.8 (3)
O2—C8—C7	117.0 (3)	O1—C1—O2	115.5 (3)
C9—C8—C7	122.8 (3)	O1—C1—C2	127.3 (3)
C17—C16—C21	119.6 (3)	O2—C1—C2	117.1 (3)
C17—C16—H16	120.2	C19—C18—C17	119.0 (3)
C21—C16—H16	120.2	C19—C18—H18	120.5
C20—C21—C16	118.3 (3)	C17—C18—H18	120.5
C20—C21—C15	118.2 (3)	N1—C11—N2	123.8 (3)
C16—C21—C15	123.4 (3)	N1—C11—S1	115.1 (2)
C8—C9—C4	117.7 (3)	N2—C11—S1	121.0 (3)
C8—C9—C3	118.0 (3)	C16—C17—C18	122.0 (3)
C4—C9—C3	124.2 (3)	C16—C17—Cl2	118.5 (3)
O3—C20—C19	118.0 (3)	C18—C17—Cl2	119.5 (3)
O3—C20—C21	120.4 (3)	C7—C6—C5	119.0 (3)
C19—C20—C21	121.6 (3)	C7—C6—H6	120.5
C11—N1—C10	110.0 (3)	C5—C6—H6	120.5
O4—C13—O3	115.8 (3)	C5—C4—C9	119.3 (3)
O4—C13—C14	127.3 (3)	C5—C4—H4	120.4
O3—C13—C14	116.9 (3)	C9—C4—H4	120.4
C6—C7—C8	118.9 (3)	C22—C24—S2	111.1 (3)
C6—C7—H7	120.5	C22—C24—H24	124.4
C8—C7—H7	120.5	S2—C24—H24	124.4
C3—C2—C10	122.6 (3)	C18—C19—C20	119.9 (3)
C3—C2—C1	118.9 (3)	C18—C19—H19	120.2
C10—C2—C1	118.5 (3)	C20—C19—H19	120.2
C14—C15—C21	122.3 (3)	C10—C12—S1	111.2 (2)
C14—C15—H15	118.8	C10—C12—H12	124.4
C21—C15—H15	118.8	S1—C12—H12	124.4
C24—C22—N3	114.9 (3)	C23—N4—H4A	120.0
C24—C22—C14	128.1 (3)	C23—N4—H4B	120.0
N3—C22—C14	117.0 (3)	H4A—N4—H4B	120.0
N3—C23—N4	123.2 (3)	C11—N2—H2A	120.0
N3—C23—S2	115.5 (3)	C11—N2—H2B	120.0
N4—C23—S2	121.3 (3)	H2A—N2—H2B	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱ	0.86	2.31	3.124 (4)	158
N4—H4A···N1ⁱⁱ	0.86	2.27	3.116 (4)	168
C7—H7···O2ⁱⁱⁱ	0.93	2.54	3.387 (4)	152

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₇ClN₂O₂S
M_r	278.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	12.494 (8), 7.350 (5), 25.013 (15)
β (°)	98.156 (12)
V (Å³)	2274 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.20 × 0.10 × 0.02

Data collection
Diffractometer	Bruker SMART CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick (1996)
T_min, T_max	0.885, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	16106, 4165, 2561
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.118, 1.01
No. of reflections	4165
No. of parameters	325
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.27

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱ	0.86	2.31	3.124 (4)	158
N4—H4A···N1ⁱⁱ	0.86	2.27	3.116 (4)	168
C7—H7···O2ⁱⁱⁱ	0.93	2.54	3.387 (4)	152

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Acknowledgements

We thank the Department of Science and Technology, India, for the data collection at the CCD facility set up under the IRHPA–DST program.

References

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