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Acta Cryst. (2010). E66, o2912    [ doi:10.1107/S1600536810041796 ]

2-(Benzothiazol-2-ylsulfanyl)acetic acid

Z. Fang and J. Wang

Abstract top

In the title compound, C9H7NO2S2, the benzine ring is essentially co-planar with the thiazole ring, making a dihedral angle of 0.36 (7)°. In the crystal structure, molecules are linked by intermolecular O-H...N hydrogen bonds between the carboxy group and the thiazole N atom into chains along [10\overline1]. The chains are assembled into a supermolecular layer structure by thiazole ring S...S contacts [3.5679 (7) Å].

Related literature top

For a related structure, tris(2-hydroxyethyl)ammonium 3-benzothiazole-2-thiolate, see: Zhu et al. (2009). For S···S contacts in similar compounds, see: Dai et al. (1997).

Experimental top

A solution of benzothiazole-2-thiol (167.2 mg, 1.00 mmol) and K2CO3 (207.0 mg, 1.50 mmol) in CH3OH (15 ml) was slowly added to a solution of 2-chloroacetic acid (113.4 mg, 1.20 mmol) in CH3OH (10 ml). The resultant solution was stirred and refluxed for 20 h and then filtered. Colorless crystals suitable for X-ray diffraction were obtained in about a week by slow diffusion of diethyl ether into a dilute solution of the title compound in methanol. yield: ca 82.3% (based on benzothiazole-2-thiol).

Refinement top

The structure was solved using direct methods followed by Fourier synthesis. Non-H atoms were refined anisotropically. All of H atoms were placed in idealized positions (C—H = 0.93 or 0.97 Å, O—H = 0.82 Å), forced to ride on the atom to which they are bonded, and were included in the refinement in the riding-model approximation. Uiso values were set equal to 1.5Ueq(parent atom) for carboxylic H atom and to 1.2Ueq(parent atom)for all other H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Two-dimensional supramolecular layer which is connected by O—H···N [O···N 2.686 (2) Å, H···N 1.89 Å, O—H···N 165.3°, symmetry code: x + 1, -y + 3/2,z + 1/2] hydrogen bonds and S···S [S···S 3.568 Å, symmetry code: 1-x, 1-y, 1-z] contacts.
2-(Benzothiazol-2-ylsulfanyl)acetic acid top
Crystal data top
C9H7NO2S2F(000) = 464
Mr = 225.28Dx = 1.585 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2101 reflections
a = 6.0374 (5) Åθ = 2.7–27.5°
b = 19.2450 (17) ŵ = 0.53 mm−1
c = 8.1250 (7) ÅT = 296 K
β = 90.419 (1)°Block, pink
V = 944.02 (14) Å30.23 × 0.21 × 0.17 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		1695 independent reflections
Radiation source: fine-focus sealed tube1439 reflections with I > 2σ(I)
graphiteRint = 0.021
φ and ω scansθmax = 25.2°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −4→7
Tmin = 0.885, Tmax = 0.914k = −22→23
4800 measured reflectionsl = −9→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0386P)2 + 0.2852P]
where P = (Fo2 + 2Fc2)/3
1695 reflections(Δ/σ)max = 0.001
129 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.16 e Å−3
Crystal data top
C9H7NO2S2V = 944.02 (14) Å3
Mr = 225.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.0374 (5) ŵ = 0.53 mm−1
b = 19.2450 (17) ÅT = 296 K
c = 8.1250 (7) Å0.23 × 0.21 × 0.17 mm
β = 90.419 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		1695 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1439 reflections with I > 2σ(I)
Tmin = 0.885, Tmax = 0.914Rint = 0.021
4800 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.079Δρmax = 0.25 e Å−3
S = 1.04Δρmin = −0.16 e Å−3
1695 reflectionsAbsolute structure: ?
129 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.5666 (3)0.77360 (10)0.5938 (3)0.0446 (5)
C20.4631 (3)0.70448 (10)0.5538 (3)0.0424 (5)
H2A0.42890.67980.65460.051*
H2B0.56540.67640.49060.051*
C30.1497 (3)0.63490 (9)0.3747 (2)0.0367 (4)
C4−0.0451 (3)0.55193 (10)0.2515 (2)0.0371 (4)
C50.1331 (3)0.51163 (10)0.3081 (2)0.0391 (4)
C60.1436 (4)0.44073 (10)0.2773 (3)0.0509 (5)
H60.26240.41430.31540.061*
C7−0.0259 (4)0.41063 (11)0.1894 (3)0.0556 (6)
H7−0.02230.36320.16770.067*
C8−0.2024 (4)0.45021 (12)0.1327 (3)0.0531 (6)
H8−0.31540.42870.07320.064*
C9−0.2144 (3)0.52022 (11)0.1620 (2)0.0458 (5)
H9−0.33370.54610.12280.055*
N1−0.0309 (3)0.62213 (8)0.2909 (2)0.0396 (4)
O10.7348 (3)0.76603 (7)0.6956 (2)0.0557 (4)
H10.79110.80410.71400.084*
O20.5039 (3)0.82751 (8)0.5396 (2)0.0736 (5)
S10.21328 (9)0.71923 (3)0.43642 (7)0.04900 (19)
S20.31920 (8)0.56396 (2)0.41411 (7)0.04382 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0430 (11)0.0378 (11)0.0528 (12)0.0004 (9)−0.0105 (10)−0.0021 (9)
C20.0413 (11)0.0343 (10)0.0515 (12)0.0031 (8)−0.0147 (9)0.0004 (8)
C30.0340 (10)0.0336 (10)0.0422 (11)0.0021 (8)−0.0077 (8)0.0014 (8)
C40.0402 (10)0.0332 (10)0.0378 (10)−0.0017 (8)−0.0033 (8)0.0011 (8)
C50.0420 (11)0.0354 (10)0.0398 (10)0.0014 (8)−0.0068 (9)0.0023 (8)
C60.0621 (14)0.0344 (11)0.0560 (13)0.0066 (9)−0.0087 (11)0.0005 (9)
C70.0772 (16)0.0335 (11)0.0562 (13)−0.0083 (11)−0.0032 (12)−0.0042 (10)
C80.0589 (14)0.0514 (13)0.0489 (12)−0.0166 (11)−0.0080 (10)−0.0046 (10)
C90.0410 (11)0.0495 (12)0.0468 (12)−0.0027 (9)−0.0099 (9)0.0009 (9)
N10.0387 (9)0.0344 (8)0.0455 (9)0.0022 (7)−0.0121 (7)0.0010 (7)
O10.0507 (9)0.0409 (8)0.0751 (11)−0.0069 (7)−0.0270 (8)0.0023 (7)
O20.0777 (12)0.0336 (9)0.1090 (14)−0.0015 (8)−0.0464 (10)0.0066 (8)
S10.0454 (3)0.0309 (3)0.0703 (4)0.0053 (2)−0.0231 (3)−0.0041 (2)
S20.0415 (3)0.0336 (3)0.0560 (3)0.00667 (19)−0.0177 (2)−0.0010 (2)
Geometric parameters (Å, °) top
C1—O21.188 (2)C4—C51.401 (3)
C1—O11.313 (2)C5—C61.389 (3)
C1—C21.504 (3)C5—S21.7332 (19)
C2—S11.8012 (19)C6—C71.372 (3)
C2—H2A0.9700C6—H60.9300
C2—H2B0.9700C7—C81.386 (3)
C3—N11.304 (2)C7—H70.9300
C3—S21.7345 (18)C8—C91.370 (3)
C3—S11.7407 (18)C8—H80.9300
C4—N11.391 (2)C9—H90.9300
C4—C91.391 (3)O1—H10.8200
O2—C1—O1124.99 (19)C4—C5—S2109.55 (14)
O2—C1—C2124.15 (19)C7—C6—C5118.3 (2)
O1—C1—C2110.86 (17)C7—C6—H6120.9
C1—C2—S1108.66 (14)C5—C6—H6120.9
C1—C2—H2A110.0C6—C7—C8120.7 (2)
S1—C2—H2A110.0C6—C7—H7119.7
C1—C2—H2B110.0C8—C7—H7119.7
S1—C2—H2B110.0C9—C8—C7121.6 (2)
H2A—C2—H2B108.3C9—C8—H8119.2
N1—C3—S2115.97 (14)C7—C8—H8119.2
N1—C3—S1120.51 (14)C8—C9—C4118.9 (2)
S2—C3—S1123.51 (11)C8—C9—H9120.6
N1—C4—C9126.16 (18)C4—C9—H9120.6
N1—C4—C5114.61 (16)C3—N1—C4110.65 (15)
C9—C4—C5119.22 (18)C1—O1—H1109.5
C6—C5—C4121.37 (18)C3—S1—C2100.82 (9)
C6—C5—S2129.08 (16)C5—S2—C389.21 (9)
O2—C1—C2—S1−7.7 (3)C5—C4—C9—C80.4 (3)
O1—C1—C2—S1172.54 (15)S2—C3—N1—C40.0 (2)
N1—C4—C5—C6−179.50 (19)S1—C3—N1—C4178.49 (14)
C9—C4—C5—C6−0.3 (3)C9—C4—N1—C3−179.45 (19)
N1—C4—C5—S20.5 (2)C5—C4—N1—C3−0.3 (2)
C9—C4—C5—S2179.69 (15)N1—C3—S1—C2176.73 (16)
C4—C5—C6—C70.0 (3)S2—C3—S1—C2−4.87 (16)
S2—C5—C6—C7−179.96 (17)C1—C2—S1—C3170.23 (15)
C5—C6—C7—C80.2 (3)C6—C5—S2—C3179.6 (2)
C6—C7—C8—C9−0.1 (4)C4—C5—S2—C3−0.40 (15)
C7—C8—C9—C4−0.2 (3)N1—C3—S2—C50.25 (16)
N1—C4—C9—C8179.49 (19)S1—C3—S2—C5−178.21 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.821.892.686 (2)165
Symmetry codes: (i) x+1, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.821.892.686 (2)165
Symmetry codes: (i) x+1, −y+3/2, z+1/2.
Acknowledgements top

The authors acknowledge South China Normal University for supporting this work.

references
References top

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Dai, J., Munakata, M., Kuroda-Sowa, T., Suenaga, Y., Wu, L. P. & Yamamoto, M. (1997). Inorg. Chim. Acta, 258, 65–69.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhu, J.-Q., Fang, H.-C., Chen, B.-Y., Feng, M.-S. & Li, J.-N. (2009). Acta Cryst. E65, o1640.