2-(Benzothia­zol-2-yl­sulfanyl)­acetic acid

Fang, Z.; Wang, J.

doi:10.1107/S1600536810041796

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2912

https://doi.org/10.1107/S1600536810041796

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2-(Benzothiazol-2-ylsulfanyl)acetic acid

Zhi-li Fang ^a ^* and Jun Wang ^b

^aSchool of Basic Science, East China Jiaotong University, Nanchang 330013, People's Republic of China, and ^bZhongshan Polytechnic, Zhongshan, Guangdong 528404, People's Republic of China
^*Correspondence e-mail: fhcgdfz@yahoo.cn

(Received 18 September 2010; accepted 15 October 2010; online 23 October 2010)

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

For the structure of 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

Crystal data

C₉H₇NO₂S₂
M_r = 225.28
Monoclinic, P 2₁ /c
a = 6.0374 (5) Å
b = 19.2450 (17) Å
c = 8.1250 (7) Å
β = 90.419 (1)°
V = 944.02 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 296 K
0.23 × 0.21 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.885, T_max = 0.914
4800 measured reflections
1695 independent reflections
1439 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.079
S = 1.04
1695 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.89	2.686 (2)	165
Symmetry code: (i) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810041796/ds2058sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041796/ds2058Isup2.hkl

checkCIF report

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).

Structure description 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).

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

	Fig. 1. The structure of the title compound with 50% probability displacement ellipsoids.
	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

C₉H₇NO₂S₂	F(000) = 464
M_r = 225.28	D_x = 1.585 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2101 reflections
a = 6.0374 (5) Å	θ = 2.7–27.5°
b = 19.2450 (17) Å	µ = 0.53 mm⁻¹
c = 8.1250 (7) Å	T = 296 K
β = 90.419 (1)°	Block, pink
V = 944.02 (14) Å³	0.23 × 0.21 × 0.17 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1695 independent reflections
Radiation source: fine-focus sealed tube	1439 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
φ and ω scans	θ_max = 25.2°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→7
T_min = 0.885, T_max = 0.914	k = −22→23
4800 measured reflections	l = −9→9

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0386P)² + 0.2852P] where P = (F_o² + 2F_c²)/3
1695 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₉H₇NO₂S₂	V = 944.02 (14) Å³
M_r = 225.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0374 (5) Å	µ = 0.53 mm⁻¹
b = 19.2450 (17) Å	T = 296 K
c = 8.1250 (7) Å	0.23 × 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)
T_min = 0.885, T_max = 0.914	R_int = 0.021
4800 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
1695 reflections	Δρ_min = −0.16 e Å⁻³
129 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
C1	0.5666 (3)	0.77360 (10)	0.5938 (3)	0.0446 (5)
C2	0.4631 (3)	0.70448 (10)	0.5538 (3)	0.0424 (5)
H2A	0.4289	0.6798	0.6546	0.051*
H2B	0.5654	0.6764	0.4906	0.051*
C3	0.1497 (3)	0.63490 (9)	0.3747 (2)	0.0367 (4)
C4	−0.0451 (3)	0.55193 (10)	0.2515 (2)	0.0371 (4)
C5	0.1331 (3)	0.51163 (10)	0.3081 (2)	0.0391 (4)
C6	0.1436 (4)	0.44073 (10)	0.2773 (3)	0.0509 (5)
H6	0.2624	0.4143	0.3154	0.061*
C7	−0.0259 (4)	0.41063 (11)	0.1894 (3)	0.0556 (6)
H7	−0.0223	0.3632	0.1677	0.067*
C8	−0.2024 (4)	0.45021 (12)	0.1327 (3)	0.0531 (6)
H8	−0.3154	0.4287	0.0732	0.064*
C9	−0.2144 (3)	0.52022 (11)	0.1620 (2)	0.0458 (5)
H9	−0.3337	0.5461	0.1228	0.055*
N1	−0.0309 (3)	0.62213 (8)	0.2909 (2)	0.0396 (4)
O1	0.7348 (3)	0.76603 (7)	0.6956 (2)	0.0557 (4)
H1	0.7911	0.8041	0.7140	0.084*
O2	0.5039 (3)	0.82751 (8)	0.5396 (2)	0.0736 (5)
S1	0.21328 (9)	0.71923 (3)	0.43642 (7)	0.04900 (19)
S2	0.31920 (8)	0.56396 (2)	0.41411 (7)	0.04382 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0430 (11)	0.0378 (11)	0.0528 (12)	0.0004 (9)	−0.0105 (10)	−0.0021 (9)
C2	0.0413 (11)	0.0343 (10)	0.0515 (12)	0.0031 (8)	−0.0147 (9)	0.0004 (8)
C3	0.0340 (10)	0.0336 (10)	0.0422 (11)	0.0021 (8)	−0.0077 (8)	0.0014 (8)
C4	0.0402 (10)	0.0332 (10)	0.0378 (10)	−0.0017 (8)	−0.0033 (8)	0.0011 (8)
C5	0.0420 (11)	0.0354 (10)	0.0398 (10)	0.0014 (8)	−0.0068 (9)	0.0023 (8)
C6	0.0621 (14)	0.0344 (11)	0.0560 (13)	0.0066 (9)	−0.0087 (11)	0.0005 (9)
C7	0.0772 (16)	0.0335 (11)	0.0562 (13)	−0.0083 (11)	−0.0032 (12)	−0.0042 (10)
C8	0.0589 (14)	0.0514 (13)	0.0489 (12)	−0.0166 (11)	−0.0080 (10)	−0.0046 (10)
C9	0.0410 (11)	0.0495 (12)	0.0468 (12)	−0.0027 (9)	−0.0099 (9)	0.0009 (9)
N1	0.0387 (9)	0.0344 (8)	0.0455 (9)	0.0022 (7)	−0.0121 (7)	0.0010 (7)
O1	0.0507 (9)	0.0409 (8)	0.0751 (11)	−0.0069 (7)	−0.0270 (8)	0.0023 (7)
O2	0.0777 (12)	0.0336 (9)	0.1090 (14)	−0.0015 (8)	−0.0464 (10)	0.0066 (8)
S1	0.0454 (3)	0.0309 (3)	0.0703 (4)	0.0053 (2)	−0.0231 (3)	−0.0041 (2)
S2	0.0415 (3)	0.0336 (3)	0.0560 (3)	0.00667 (19)	−0.0177 (2)	−0.0010 (2)

Geometric parameters (Å, º) top

C1—O2	1.188 (2)	C4—C5	1.401 (3)
C1—O1	1.313 (2)	C5—C6	1.389 (3)
C1—C2	1.504 (3)	C5—S2	1.7332 (19)
C2—S1	1.8012 (19)	C6—C7	1.372 (3)
C2—H2A	0.9700	C6—H6	0.9300
C2—H2B	0.9700	C7—C8	1.386 (3)
C3—N1	1.304 (2)	C7—H7	0.9300
C3—S2	1.7345 (18)	C8—C9	1.370 (3)
C3—S1	1.7407 (18)	C8—H8	0.9300
C4—N1	1.391 (2)	C9—H9	0.9300
C4—C9	1.391 (3)	O1—H1	0.8200

O2—C1—O1	124.99 (19)	C4—C5—S2	109.55 (14)
O2—C1—C2	124.15 (19)	C7—C6—C5	118.3 (2)
O1—C1—C2	110.86 (17)	C7—C6—H6	120.9
C1—C2—S1	108.66 (14)	C5—C6—H6	120.9
C1—C2—H2A	110.0	C6—C7—C8	120.7 (2)
S1—C2—H2A	110.0	C6—C7—H7	119.7
C1—C2—H2B	110.0	C8—C7—H7	119.7
S1—C2—H2B	110.0	C9—C8—C7	121.6 (2)
H2A—C2—H2B	108.3	C9—C8—H8	119.2
N1—C3—S2	115.97 (14)	C7—C8—H8	119.2
N1—C3—S1	120.51 (14)	C8—C9—C4	118.9 (2)
S2—C3—S1	123.51 (11)	C8—C9—H9	120.6
N1—C4—C9	126.16 (18)	C4—C9—H9	120.6
N1—C4—C5	114.61 (16)	C3—N1—C4	110.65 (15)
C9—C4—C5	119.22 (18)	C1—O1—H1	109.5
C6—C5—C4	121.37 (18)	C3—S1—C2	100.82 (9)
C6—C5—S2	129.08 (16)	C5—S2—C3	89.21 (9)

O2—C1—C2—S1	−7.7 (3)	C5—C4—C9—C8	0.4 (3)
O1—C1—C2—S1	172.54 (15)	S2—C3—N1—C4	0.0 (2)
N1—C4—C5—C6	−179.50 (19)	S1—C3—N1—C4	178.49 (14)
C9—C4—C5—C6	−0.3 (3)	C9—C4—N1—C3	−179.45 (19)
N1—C4—C5—S2	0.5 (2)	C5—C4—N1—C3	−0.3 (2)
C9—C4—C5—S2	179.69 (15)	N1—C3—S1—C2	176.73 (16)
C4—C5—C6—C7	0.0 (3)	S2—C3—S1—C2	−4.87 (16)
S2—C5—C6—C7	−179.96 (17)	C1—C2—S1—C3	170.23 (15)
C5—C6—C7—C8	0.2 (3)	C6—C5—S2—C3	179.6 (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—C5	0.25 (16)
N1—C4—C9—C8	179.49 (19)	S1—C3—S2—C5	−178.21 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.89	2.686 (2)	165

Symmetry code: (i) x+1, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₇NO₂S₂
M_r	225.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	6.0374 (5), 19.2450 (17), 8.1250 (7)
β (°)	90.419 (1)
V (Å³)	944.02 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.23 × 0.21 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.885, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	4800, 1695, 1439
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.04
No. of reflections	1695
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.89	2.686 (2)	165.3

Symmetry code: (i) x+1, −y+3/2, z+1/2.

Acknowledgements

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

References

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