3-(2-Amino-1,3-thia-zol-4-yl)-6-chloro-2H-chromen-2-one.

The title compound, C(12)H(7)ClN(2)O(2)S, crystallizes with two mol-ecules in the asymmetric unit. The mol-ecular conformation is roughly planar for both these mol-ecules 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 mol-ecules. The structure is further stabilised by aromatic π-π stacking inter-actions 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 = 278.72

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.118

S = 1.01

4165 reflections

325 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.27 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H7ClN2O2S	F(000) = 1136
Mr = 278.72	Dx = 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

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

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(Fo2) + (0.0493P)2] where P = (Fo2 + 2Fc2)/3
4165 reflections	(Δ/σ)max < 0.001
325 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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

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) ; (ii) ; (iii) .