6-Bromo-2-methyl-sulfanyl-1,3-benzo-thia-zole.

The title mol-ecule, C(8)H(6)BrNS(2), is almost planar with a dihedral angle of 0.9 (1)° between the benzene and thia-zole rings. The values of the geometry-based index of aromaticity (HOMA) and the nucleus-independent chemical shift (NICS) for the two cyclic fragments of the title mol-ecule are 0.95 and -9.61, respectively, for the benzene ring, and 0.69 and -7.71, respectively, for the thia-zole ring. They show that the benzene ring exhibits substanti-ally higher cyclic π-electron delocalization than the thia-zole ring. Comparison with other similar benzothia-zole fragments reveals a similar trend.

Related literature

For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For related structures, see: Chen et al. (2003 ▶, 2010 ▶); Li et al. (2009 ▶); Liu et al. (2003 ▶); Loghmani-Khouzani et al. (2009 ▶); Matthews et al. (1996 ▶); Saravanan et al. (2007 ▶); Zhao et al. (2009 ▶); Zou et al. (2003 ▶). For the aromaticity of benzothia­zoles, see: Karolak-Wojciechowska et al. (2007 ▶). For the Gaussian program, see: Frisch et al. (2009 ▶). For the HOMA index, see: Kruszewski & Krygowski (1972 ▶); Krygowski & Cyrański (2001 ▶) and for the NICS index, see: Schleyer et al. (1996 ▶).

Experimental

Crystal data

C8H6BrNS2

M = 260.18

Monoclinic,

a = 9.7843 (4) Å

b = 3.9514 (2) Å

c = 11.6076 (5) Å

β = 96.353 (4)°

V = 446.01 (3) Å3

Z = 2

Mo Kα radiation

μ = 5.01 mm−1

T = 100 K

0.4 × 0.15 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur S diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T min = 0.422, T max = 0.606

3437 measured reflections

1227 independent reflections

1125 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.033

S = 0.99

1227 reflections

110 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 315 Friedel pairs

Flack parameter: 0.005 (9)

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681105015X/gk2424sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681105015X/gk2424Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681105015X/gk2424Isup3.cml

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

C8H6BrNS2	F(000) = 256
Mr = 260.18	Dx = 1.937 Mg m−3
Monoclinic, P21	Melting point = 371–374 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.7843 (4) Å	Cell parameters from 2764 reflections
b = 3.9514 (2) Å	θ = 2.9–28.5°
c = 11.6076 (5) Å	µ = 5.01 mm−1
β = 96.353 (4)°	T = 100 K
V = 446.01 (3) Å3	Needle, colourless
Z = 2	0.4 × 0.15 × 0.1 mm

Oxford Diffraction Xcalibur S diffractometer	1227 independent reflections
Radiation source: fine-focus sealed tube	1125 reflections with I > 2σ(I)
graphite	Rint = 0.024
Detector resolution: 8.6479 pixels mm-1	θmax = 25.0°, θmin = 2.9°
phi and ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −4→3
Tmin = 0.422, Tmax = 0.606	l = −13→13
3437 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.017	H-atom parameters constrained
wR(F2) = 0.033	w = 1/[σ2(Fo2) + (0.0143P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.002
1227 reflections	Δρmax = 0.36 e Å−3
110 parameters	Δρmin = −0.22 e Å−3
1 restraint	Absolute structure: Flack (1983), 315 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.005 (9)

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
C1	0.7671 (3)	0.6254 (7)	0.9919 (3)	0.0141 (7)
C2	0.8559 (3)	0.5366 (12)	0.9147 (2)	0.0123 (6)
C3	0.8181 (3)	0.6157 (7)	0.7984 (3)	0.0121 (7)
C4	0.6939 (3)	0.7815 (8)	0.7626 (3)	0.0121 (7)
C5	0.6060 (3)	0.8712 (7)	0.8439 (3)	0.0137 (7)
C6	0.6430 (3)	0.7938 (8)	0.9590 (3)	0.0135 (7)
C7	0.7722 (3)	0.7402 (8)	0.5934 (3)	0.0127 (7)
C8	0.6257 (3)	0.9551 (10)	0.3940 (3)	0.0192 (8)
N1	0.6702 (3)	0.8486 (6)	0.6440 (2)	0.0131 (6)
S1	0.90775 (7)	0.5420 (3)	0.68048 (6)	0.01509 (19)
S2	0.79094 (8)	0.7776 (2)	0.44632 (7)	0.01761 (19)
Br1	0.81246 (3)	0.50973 (9)	1.15124 (2)	0.01701 (9)
H2	0.9403	0.4254	0.9390	0.015*
H5	0.5218	0.9841	0.8205	0.016*
H6	0.5845	0.8546	1.0158	0.016*
H8A	0.6084	1.1556	0.4399	0.029*
H8B	0.5537	0.7867	0.4011	0.029*
H8C	0.6254	1.0196	0.3124	0.029*

	U11	U22	U33	U12	U13	U23
C1	0.0180 (18)	0.0130 (17)	0.0109 (16)	−0.0034 (13)	−0.0003 (14)	0.0000 (13)
C2	0.0133 (13)	0.0076 (16)	0.0157 (14)	−0.0013 (16)	0.0000 (10)	0.0028 (16)
C3	0.0103 (16)	0.0095 (15)	0.0169 (16)	−0.0012 (12)	0.0029 (13)	−0.0044 (12)
C4	0.0120 (17)	0.0099 (16)	0.0144 (17)	−0.0050 (14)	0.0012 (13)	−0.0032 (14)
C5	0.0122 (17)	0.0110 (15)	0.0178 (18)	0.0005 (12)	0.0013 (13)	−0.0010 (13)
C6	0.0134 (17)	0.0123 (16)	0.0157 (18)	−0.0017 (14)	0.0051 (13)	−0.0050 (14)
C7	0.0137 (17)	0.0090 (15)	0.0150 (17)	−0.0048 (14)	−0.0001 (14)	−0.0006 (14)
C8	0.0213 (17)	0.019 (2)	0.0171 (16)	−0.0014 (17)	−0.0006 (13)	0.0025 (17)
N1	0.0132 (15)	0.0136 (13)	0.0122 (14)	−0.0018 (11)	0.0011 (11)	0.0012 (11)
S1	0.0140 (4)	0.0166 (5)	0.0149 (4)	0.0027 (5)	0.0027 (3)	−0.0012 (5)
S2	0.0190 (5)	0.0197 (4)	0.0149 (4)	0.0020 (4)	0.0049 (3)	0.0010 (4)
Br1	0.02064 (16)	0.01663 (14)	0.01365 (15)	0.0003 (2)	0.00146 (11)	0.0021 (2)

S1—C3	1.730 (3)	C6—H6	0.9500
S1—C7	1.760 (3)	C3—C4	1.402 (4)
N1—C7	1.286 (4)	C4—C5	1.391 (4)
N1—C4	1.396 (4)	C5—H5	0.9500
C2—C1	1.362 (4)	C7—S2	1.744 (3)
C2—C3	1.395 (4)	S2—C8	1.805 (3)
C2—H2	0.9500	C8—H8A	0.9800
C1—C6	1.400 (4)	C8—H8B	0.9800
C1—Br1	1.909 (3)	C8—H8C	0.9800
C6—C5	1.379 (4)
C3—S1—C7	87.90 (14)	C5—C4—C3	119.9 (3)
C7—N1—C4	109.5 (3)	N1—C4—C3	115.2 (3)
C1—C2—C3	117.3 (3)	C6—C5—C4	119.0 (3)
C1—C2—H2	121.3	C6—C5—H5	120.5
C3—C2—H2	121.3	C4—C5—H5	120.5
C2—C1—C6	122.7 (3)	N1—C7—S2	126.2 (2)
C2—C1—Br1	118.6 (2)	N1—C7—S1	117.4 (2)
C6—C1—Br1	118.7 (2)	S2—C7—S1	116.46 (18)
C5—C6—C1	119.8 (3)	C7—S2—C8	100.09 (15)
C5—C6—H6	120.1	S2—C8—H8A	109.5
C1—C6—H6	120.1	S2—C8—H8B	109.5
C2—C3—C4	121.3 (3)	H8A—C8—H8B	109.5
C2—C3—S1	128.6 (2)	S2—C8—H8C	109.5
C4—C3—S1	110.0 (2)	H8A—C8—H8C	109.5
C5—C4—N1	124.9 (3)	H8B—C8—H8C	109.5
C3—C2—C1—C6	−0.9 (5)	C2—C3—C4—N1	179.2 (3)
C3—C2—C1—Br1	178.1 (3)	S1—C3—C4—N1	0.1 (3)
C2—C1—C6—C5	1.0 (5)	C1—C6—C5—C4	−0.4 (4)
Br1—C1—C6—C5	−178.1 (2)	N1—C4—C5—C6	−179.0 (3)
C1—C2—C3—C4	0.3 (5)	C3—C4—C5—C6	−0.1 (4)
C1—C2—C3—S1	179.3 (3)	C4—N1—C7—S2	−178.1 (2)
C7—S1—C3—C2	−178.8 (4)	C4—N1—C7—S1	0.6 (3)
C7—S1—C3—C4	0.2 (2)	C3—S1—C7—N1	−0.5 (3)
C7—N1—C4—C5	178.5 (3)	C3—S1—C7—S2	178.36 (19)
C7—N1—C4—C3	−0.4 (4)	N1—C7—S2—C8	−6.0 (3)
C2—C3—C4—C5	0.2 (5)	S1—C7—S2—C8	175.2 (2)
S1—C3—C4—C5	−178.9 (2)

refcode	R =	HOMA (total)	HOMA (thiazole)	HOMA (benzene)
This work	H	0.82	0.69	0.95
DIDBAUa	-C(Ph)=N-NH-C(O)-NH2	0.85	0.73	0.99
HUFSILb	-CH2-O-CH2-CH2-S-BT	0.83	0.69	0.98
HUYYIJc	-CH2-CH2-CH2-S-BT	0.84	0.70	0.98
MACMOTd	-CH2-S-BT	0.85	0.72	0.97
	-CH2-S-BT	0.85	0.71	0.98
MACMOT01e	-CH2-S-BT	0.85	0.70	0.98
	-CH2-S-BT	0.85	0.71	0.97
MOKJIGf	-C(O)-C(COOCH3)=N-O-CH3	0.83	0.70	0.96
PUFGEDg	-C(O)-Ph	0.84	0.70	0.96
QOTQASh	-C(O)-NH-2-MePyr	0.85	0.71	0.98
ZUQQEHi	-CH2-O-CH2-CH2-O- CH2-CH2-S-BT	0.83	0.67	0.98
Mean		0.84	0.70	0.97
E.s.d.		0.01	0.01	0.01

Table 1

HOMA indices for compounds containing benzothia­zole moieties.

BT = benzothia­zole; MePyr = methyl­pyridine.

refcode	R =	HOMA (total)	HOMA (thia­zole)	HOMA (benzene)
This work	H	0.82	0.69	0.95
DIDBAUa	-C(Ph)=N—NH—C(O)—NH2	0.85	0.73	0.99
HUFSILb	-CH2—O—CH2—CH2—S—BT	0.83	0.69	0.98
HUYYIJc	-CH2—CH2—CH2—S—BT	0.84	0.70	0.98
MACMOTd	-CH2—S—BT	0.85	0.72	0.97
	-CH2—S—BT	0.85	0.71	0.98
MACMOT01e	-CH2—S—BT	0.85	0.70	0.98
	-CH2—S—BT	0.85	0.71	0.97
MOKJIGf	-C(O)—C(COOCH3)=N—O—CH3	0.83	0.70	0.96
PUFGEDg	-C(O)—Ph	0.84	0.70	0.96
QOTQASh	-C(O)—NH-2-MePyr	0.85	0.71	0.98
ZUQQEHi	-CH2—O—CH2—CH2—O– CH2—CH2—S—BT	0.83	0.67	0.98
Mean		0.84	0.70	0.97
E.s.d.		0.01	0.01	0.01

Notes: (a) Saravanan et al. (2007 ▶); (b) Chen et al. (2010 ▶); (c) Chen et al. (2003 ▶); (d) Liu et al. (2003 ▶); (e) Zou et al. (2003 ▶); (f) Li et al. (2009 ▶); (g) Loghmani-Khouzani et al. (2009 ▶); (h) Matthews et al. (1996 ▶); (i) Zhao et al. (2009 ▶).