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

The mol-ecule of the title compound, C(12)H(7)BrN(2)O(2)S, is essentially planar with a maximum deviation of 0.234 (3) Å from the mean plane through all non-H atoms. The dihedral angle between the coumarin ring plane and that of the five-membered thia-zole ring is 12.9 (1)°. In the crystal, strong N-H⋯O, N-H⋯N and weak but highly directional C-H⋯O hydrogen bonds provide the links between the mol-ecules. In addition, C-H⋯π and π-π inter-actions [centroid-centroid distances = 3.950 (3)-4.024 (3) Å] provide additional stability to the inter-layer regions in the lattice.

Related literature

For applications of coumarin compounds in photochemistry, see: Vishnumurthy et al. (2001 ▶). For their roles as dyes or laser dyes, see: Hooper et al. (1982 ▶); Nemkovich et al. (1997 ▶). For graph-set motifs, see: Bernstein et al. (1995 ▶). For the synthesis of the title compound, see: Venugopala et al. (2004 ▶). For related structures see: Vishnumurthy et al. (2001 ▶).

Experimental

Crystal data

C12H7BrN2O2S

M = 323.17

Monoclinic,

a = 7.031 (4) Å

b = 13.804 (8) Å

c = 12.453 (7) Å

β = 90.047 (9)°

V = 1208.6 (12) Å3

Z = 4

Mo Kα radiation

μ = 3.57 mm−1

T = 290 K

0.32 × 0.12 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick,1996 ▶) T min = 0.641, T max = 0.675

9232 measured reflections

2431 independent reflections

2017 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.090

S = 1.03

2431 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.56 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/S1600536809046674/sj2669sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046674/sj2669Isup2.hkl

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

C12H7BrN2O2S	F(000) = 640
Mr = 323.17	Dx = 1.776 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 895 reflections
a = 7.031 (4) Å	θ = 1.5–25.8°
b = 13.804 (8) Å	µ = 3.57 mm−1
c = 12.453 (7) Å	T = 290 K
β = 90.047 (9)°	Needle, yellow
V = 1208.6 (12) Å3	0.32 × 0.12 × 0.11 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2431 independent reflections
Radiation source: fine-focus sealed tube	2017 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	h = −8→8
Tmin = 0.641, Tmax = 0.675	k = −17→17
9232 measured reflections	l = −14→15

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0453P)2 + 0.6906P] where P = (Fo2 + 2Fc2)/3
2431 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.56 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
Br1	0.15344 (4)	0.88591 (3)	1.08569 (3)	0.06615 (15)
S1	1.40939 (9)	0.60168 (5)	0.82189 (6)	0.04711 (19)
N1	1.0835 (3)	0.61538 (14)	0.91596 (17)	0.0384 (5)
N2	1.2684 (4)	0.48369 (18)	0.9743 (2)	0.0507 (6)
O1	1.0382 (3)	0.84207 (14)	0.68021 (15)	0.0525 (5)
O2	0.7679 (3)	0.88987 (13)	0.74985 (15)	0.0489 (5)
C1	0.9241 (4)	0.83052 (17)	0.7517 (2)	0.0407 (6)
C2	0.9369 (3)	0.75986 (16)	0.83941 (19)	0.0368 (5)
C3	0.8015 (4)	0.75970 (18)	0.9159 (2)	0.0405 (6)
C4	0.4977 (4)	0.82387 (19)	0.9903 (2)	0.0445 (6)
C5	0.3471 (4)	0.88597 (19)	0.9794 (2)	0.0463 (6)
C6	0.3340 (4)	0.9488 (2)	0.8935 (3)	0.0552 (7)
C7	0.4756 (4)	0.9503 (2)	0.8172 (3)	0.0560 (7)
C8	0.6280 (4)	0.88711 (17)	0.8272 (2)	0.0412 (6)
C9	0.6421 (3)	0.82394 (17)	0.91312 (19)	0.0383 (5)
C10	1.0974 (3)	0.69189 (17)	0.84259 (19)	0.0373 (5)
C11	1.2368 (3)	0.56253 (17)	0.9130 (2)	0.0382 (5)
C12	1.2599 (4)	0.6948 (2)	0.7847 (2)	0.0445 (6)
H2A	1.1820	0.4644	1.0183	0.060*
H2B	1.3722	0.4518	0.9676	0.060*
H3	0.8123	0.7161	0.9728	0.048*
H4	0.5037	0.7819	1.0485	0.053*
H6	0.2303	0.9902	0.8875	0.066*
H7	0.4694	0.9929	0.7595	0.068*
H12	1.2876	0.7407	0.7324	0.053*

	U11	U22	U33	U12	U13	U23
Br1	0.0496 (2)	0.0818 (3)	0.0671 (2)	0.01305 (15)	0.01552 (15)	−0.00836 (16)
S1	0.0350 (3)	0.0504 (4)	0.0559 (4)	0.0006 (3)	0.0136 (3)	−0.0006 (3)
N1	0.0351 (10)	0.0393 (11)	0.0408 (11)	0.0034 (8)	0.0086 (9)	−0.0015 (9)
N2	0.0430 (13)	0.0463 (13)	0.0628 (16)	0.0119 (11)	0.0172 (12)	0.0071 (12)
O1	0.0600 (12)	0.0502 (11)	0.0474 (11)	−0.0031 (9)	0.0160 (9)	0.0069 (9)
O2	0.0570 (11)	0.0453 (10)	0.0445 (10)	0.0075 (8)	0.0061 (9)	0.0110 (8)
C1	0.0488 (14)	0.0358 (12)	0.0374 (13)	−0.0036 (11)	0.0051 (11)	−0.0033 (10)
C2	0.0408 (13)	0.0321 (11)	0.0374 (12)	−0.0021 (10)	0.0029 (10)	−0.0008 (10)
C3	0.0445 (14)	0.0371 (13)	0.0399 (14)	0.0044 (10)	0.0036 (11)	0.0048 (11)
C4	0.0452 (14)	0.0455 (14)	0.0429 (14)	0.0055 (11)	0.0039 (11)	0.0011 (12)
C5	0.0425 (14)	0.0498 (15)	0.0466 (15)	0.0068 (11)	0.0029 (12)	−0.0077 (12)
C6	0.0507 (16)	0.0538 (17)	0.0610 (18)	0.0174 (14)	−0.0025 (14)	0.0001 (14)
C7	0.0622 (18)	0.0512 (17)	0.0547 (17)	0.0134 (14)	−0.0053 (14)	0.0085 (14)
C8	0.0441 (14)	0.0401 (13)	0.0396 (14)	0.0026 (11)	0.0024 (11)	0.0013 (10)
C9	0.0409 (13)	0.0354 (12)	0.0386 (13)	0.0031 (10)	0.0011 (10)	−0.0009 (10)
C10	0.0396 (12)	0.0347 (12)	0.0376 (12)	−0.0029 (10)	0.0045 (10)	−0.0026 (10)
C11	0.0344 (12)	0.0380 (12)	0.0423 (13)	0.0000 (10)	0.0064 (10)	−0.0054 (10)
C12	0.0402 (14)	0.0444 (14)	0.0489 (15)	−0.0025 (11)	0.0083 (12)	0.0036 (12)

Br1—C5	1.900 (3)	C3—C9	1.431 (4)
S1—C12	1.722 (3)	C3—H3	0.9300
S1—C11	1.748 (3)	C11—N2	1.344 (3)
N1—C11	1.303 (3)	C5—C6	1.379 (4)
N1—C10	1.399 (3)	C2—C1	1.469 (3)
O2—C1	1.370 (3)	C8—C7	1.383 (4)
O2—C8	1.379 (3)	C8—C9	1.384 (4)
C4—C5	1.369 (4)	C6—C7	1.380 (4)
C4—C9	1.399 (4)	C6—H6	0.9300
C4—H4	0.9300	C7—H7	0.9300
O1—C1	1.209 (3)	N2—H2A	0.8600
C10—C12	1.353 (4)	N2—H2B	0.8600
C10—C2	1.468 (3)	C12—H12	0.9300
C3—C2	1.348 (3)
C12—S1—C11	88.97 (13)	O2—C8—C7	118.2 (2)
C11—N1—C10	110.3 (2)	O2—C8—C9	120.4 (2)
C1—O2—C8	123.0 (2)	C7—C8—C9	121.4 (3)
C5—C4—C9	119.6 (3)	O1—C1—O2	116.3 (2)
C5—C4—H4	120.2	O1—C1—C2	126.5 (2)
C9—C4—H4	120.2	O2—C1—C2	117.3 (2)
C12—C10—N1	115.4 (2)	C5—C6—C7	119.7 (3)
C12—C10—C2	128.1 (2)	C5—C6—H6	120.2
N1—C10—C2	116.5 (2)	C7—C6—H6	120.2
C2—C3—C9	122.3 (2)	C6—C7—C8	119.2 (3)
C2—C3—H3	118.8	C6—C7—H7	120.4
C9—C3—H3	118.8	C8—C7—H7	120.4
N1—C11—N2	124.9 (2)	C8—C9—C4	118.6 (2)
N1—C11—S1	114.80 (19)	C8—C9—C3	117.8 (2)
N2—C11—S1	120.32 (19)	C4—C9—C3	123.5 (2)
C4—C5—C6	121.4 (3)	C11—N2—H2A	120.0
C4—C5—Br1	119.0 (2)	C11—N2—H2B	120.0
C6—C5—Br1	119.5 (2)	H2A—N2—H2B	120.0
C3—C2—C10	121.5 (2)	C10—C12—S1	110.5 (2)
C3—C2—C1	119.1 (2)	C10—C12—H12	124.7
C10—C2—C1	119.4 (2)	S1—C12—H12	124.7

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.32	3.141 (4)	160
N2—H2B···O1ii	0.86	2.47	3.058 (3)	127
C4—H4···O1iii	0.93	2.38	3.304 (4)	172
C7—H7···Cg1iv	0.93	2.74	3.587 (4)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.32	3.141 (4)	160
N2—H2B⋯O1ii	0.86	2.47	3.058 (3)	127
C4—H4⋯O1iii	0.93	2.38	3.304 (4)	172
C7—H7⋯Cg1iv	0.93	2.74	3.587 (4)	151

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg1 is the centroid of the thiazoyl ring.