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

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

doi:10.1107/S1600536809046674

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o3047-o3048

doi:10.1107/S1600536809046674

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3-(2-Amino-1,3-thiazol-4-yl)-6-bromo-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, 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 2 November 2009; accepted 5 November 2009; online 11 November 2009)

The molecule of the title compound, C₁₂H₇BrN₂O₂S, 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 thiazole 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 molecules. In addition, C—H⋯π and π–π interactions [centroid–centroid distances = 3.950 (3)–4.024 (3) Å] provide additional stability to the interlayer 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_r = 323.17
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.03
2431 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.56 e Å⁻³

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⋯Cg1^iv	0.93	2.74	3.587 (4)	151
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of the thiazoyl ring.

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/S1600536809046674/sj2669sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046674/sj2669Isup2.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 (Hooper et al., 1982 )and in the area of laser dyes (Nemkovich et al., 1997) based on the fact that such compounds show state dependent variations in their static dipole moments. The geometry and molecular packing patterns of several coumarins 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.

The molecular structure consists of a bromo substituted coumarin ring attached to an amino thiazoyl moiety (Figure 1). This compound crystallizes in a monoclinic centrosymmetric space group with Z'=1. The molecule is approximately planar, with a dihedral angle between the two rings being 12.9 (1) °. An analysis of the weighted least-squares plane through the coumarin ring C1/O2 and the thiazoyl ring shows that it is planar with the largest displacement of -0.019 (2)Å for C9. A characteristic Br···S short contact with distance 3.411 (2)Å is observed in the crystal lattice. Strong N—H···N and N—H···O hydrogen bonds (involving both H2A and H2B of the amino group with the ring nitrogen N1 and keto oxygen O1) form R²2(8) [Bernstein et al., 1995] molecular dimers. These are linked by C(8) molecular chains along the crystallographic b axis forming a characteristic "chain of dimers". Furthermore, C—H···π interactions (involving H7 and the aromatic thiazoyl ring) provide additional stability forming chains along 'b' axis. Two such one-dimensional chains are linked by intermolecular C—H···O hydrogen bonds (involving H4 and O1) forming C(7) molecular chains along 'n' glide leading to the formation of a two dimensional sheet-like structure (Figure 2). π–π Stacking interactions involving the C4/C9 aromatic ring, Cg···Cg distance 3.950 (3)Å [Symmetry code: -x + 1, -y, -z] and between the thiazoyl ring and the C4/C9 ring [Cg···Cg distance = 4.024 (3) Å] [Symmetry code: x - 1, y, z] provide additional stability linking the layers of molecules.

Related literature top

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). Cg1 is the centroid of the thiazoyl ring.

Experimental top

The compounds were synthesized in accordance with the procedure reported in the literature (Venugopala et al., 2004). Single crystals of the compound were grown both 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: SHELXL97 (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% probability displacement ellipsoids.
	Fig. 2. Packing diagram highlighting N—H···N/O hydrogen bonds and C—H···O intermolecular interactions. Only participating H atoms have been shown, others have been omitted for clarity.

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

Crystal data top

C₁₂H₇BrN₂O₂S	F(000) = 640
M_r = 323.17	D_x = 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

Data collection top

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

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0453P)² + 0.6906P] where P = (F_o² + 2F_c²)/3
2431 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₁₂H₇BrN₂O₂S	V = 1208.6 (12) Å³
M_r = 323.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.031 (4) Å	µ = 3.57 mm⁻¹
b = 13.804 (8) Å	T = 290 K
c = 12.453 (7) Å	0.32 × 0.12 × 0.11 mm
β = 90.047 (9)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2431 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	2017 reflections with I > 2σ(I)
T_min = 0.641, T_max = 0.675	R_int = 0.019
9232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.03	Δρ_max = 0.54 e Å⁻³
2431 reflections	Δρ_min = −0.56 e Å⁻³
163 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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···Cg1^iv	0.93	2.74	3.587 (4)	151

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+5/2, y−1/2, −z+3/2; (iii) x−1/2, −y+3/2, z+1/2; (iv) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₇BrN₂O₂S
M_r	323.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	290
a, b, c (Å)	7.031 (4), 13.804 (8), 12.453 (7)
β (°)	90.047 (9)
V (Å³)	1208.6 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.57
Crystal size (mm)	0.32 × 0.12 × 0.11

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick,1996)
T_min, T_max	0.641, 0.675
No. of measured, independent and observed [I > 2σ(I)] reflections	9232, 2431, 2017
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.03
No. of reflections	2431
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.56

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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···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···Cg1^iv	0.93	2.74	3.587 (4)	151

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+5/2, y−1/2, −z+3/2; (iii) x−1/2, −y+3/2, z+1/2; (iv) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

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

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