2-[(2-Carboxy­phen­yl)sulfan­yl]acetic acid

Zhan, C.-H.; Chen, L.-X.; Feng, Y.-L.

doi:10.1107/S1600536809034126

organic compounds

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Volume 65| Part 10| October 2009| Page o2315

doi:10.1107/S1600536809034126

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2-[(2-Carboxyphenyl)sulfanyl]acetic acid

Cai-Hong Zhan,^a Ling-Xian Chen ^a and Yun-Long Feng ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: sky37@zjnu.edu.cn

(Received 9 August 2009; accepted 26 August 2009; online 5 September 2009)

The title compound, C₉H₈O₄S, affords a zigzig chain in the crystal structure by intermolecular O—H⋯O hydrogen bonds. The molecular geometry suggests that extensive but not uniform π-electron delocalization is present in the benzene ring and extends over the exocyclic C—S and C—C bonds.

Related literature

For background to the coordination chemistry of rigid carboxylate system, see: Sagatys et al. (2003 ); Sokolov et al. (2001 ).

Experimental

Crystal data

C₉H₈O₄S
M_r = 212.22
Triclinic, $[P \overline 1]$
a = 5.1786 (5) Å
b = 9.2973 (9) Å
c = 10.4776 (11) Å
α = 69.980 (4)°
β = 81.959 (6)°
γ = 79.732 (6)°
V = 464.69 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.33 × 0.24 × 0.15 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.910, T_max = 0.952
6609 measured reflections
2110 independent reflections
1941 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.222
S = 1.19
2110 reflections
133 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.86 (7)	1.92 (5)	2.687 (6)	149 (8)
O3—H3⋯O4ⁱⁱ	0.85 (2)	1.80 (5)	2.634 (4)	167 (6)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x, -y, -z.

Data collection: APEX2 (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); 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: 10.1107/S1600536809034126/at2858sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034126/at2858Isup2.hkl

checkCIF report

Comment top

Thioacetatebenzoic acid (I) is an interesting ligand from a structural point of view since it can display a wide range of coordination patterns with metal ions. The ligand (I) belongs to dicarboxylic acids. The characteristic coordination chemistry of the rigid carboxylate system may facilitate the formation of inorganic-organic materials with high thermal stability and form large channels, while the peculiar coordination chemistry of the flexible carboxylate system employed in the self-assembly reaction has versatile coordination behavior and may be favorable for the formation of the helical structure (Sagatys et al., 2003; Sokolov et al., 2001). As shown in Fig.1, the bond lengths within the benzene ring exhibit the expected pattern with C—C bonds (1.368 (8)–1.399 (6) Å) between the single and double bonds. And the bond distance of C1—C7 (1.476 (5) Å) and S1—C6 (1.768 (4) Å) also fall between the double and single bonds. All these interatomic distances suggest that extensive but not uniform π electron delocalization is present in the benzene ring and extends over the exocyclic C—S and C—C bonds. The torsion angle of C6—S1—C8—C9 is -71.7 (4)°. O—H···O hydrogen bonds link independent molecules to form a zigzig chain.

Related literature top

For background to the coordination chemistry of rigid carboxylate system, see: Sagatys et al. (2003); Sokolov et al. (2001).

Experimental top

To an aqueous solution of 2-thiobenzoic acid (1.54 g, 10.0 mmol) and NaOH (0.80 g, 20.0 mmol) were sequentially added the aqueous solution of chloroactic acid (2.835 g, 30.0 mmol) and NaOH (1.400 g, 35.0 mmol). After stirring for 4 h at 353 K under nitrogen atmosphere, the mixture was cooled to room temperature slowly. Adjusted the pH to 2 by adding 1.0 mol/L HCl, the pink deposit appeared rapidly. The solids were filtered and washed with water. The single crystals suitable for X-ray diffraction were obtained by the recrystallization of sieved solid in the ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 molecular structure of the title compound, showing 30% probability displacement ellipsoids

2-[(2-Carboxyphenyl)sulfanyl]acetic acid top

Crystal data top

C₉H₈O₄S	Z = 2
M_r = 212.22	F(000) = 220
Triclinic, P1	D_x = 1.517 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1786 (5) Å	Cell parameters from 5343 reflections
b = 9.2973 (9) Å	θ = 2.1–27.7°
c = 10.4776 (11) Å	µ = 0.33 mm⁻¹
α = 69.980 (4)°	T = 296 K
β = 81.959 (6)°	Block, colourless
γ = 79.732 (6)°	0.33 × 0.24 × 0.15 mm
V = 464.69 (8) Å³

Data collection top

Bruker APEXII diffractometer	2110 independent reflections
Radiation source: fine-focus sealed tube	1941 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 27.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.910, T_max = 0.952	k = −12→11
6609 measured reflections	l = −13→12

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.222	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ²(F_o²) + (0.0736P)² + 1.2589P] where P = (F_o² + 2F_c²)/3
2110 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.65 e Å⁻³
2 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₉H₈O₄S	γ = 79.732 (6)°
M_r = 212.22	V = 464.69 (8) Å³
Triclinic, P1	Z = 2
a = 5.1786 (5) Å	Mo Kα radiation
b = 9.2973 (9) Å	µ = 0.33 mm⁻¹
c = 10.4776 (11) Å	T = 296 K
α = 69.980 (4)°	0.33 × 0.24 × 0.15 mm
β = 81.959 (6)°

Data collection top

Bruker APEXII diffractometer	2110 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1941 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.952	R_int = 0.024
6609 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	2 restraints
wR(F²) = 0.222	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	Δρ_max = 0.65 e Å⁻³
2110 reflections	Δρ_min = −0.34 e Å⁻³
133 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
S1	0.2028 (2)	0.36823 (12)	0.11601 (11)	0.0417 (3)
O1	−0.0678 (11)	0.4660 (9)	0.3612 (6)	0.116 (2)
O2	0.2828 (9)	0.5474 (7)	0.3870 (5)	0.0891 (16)
H2	0.173 (12)	0.569 (10)	0.449 (6)	0.107*
O3	0.2508 (7)	−0.1074 (4)	0.1122 (4)	0.0549 (9)
H3	0.127 (8)	−0.107 (7)	0.067 (5)	0.066*
O4	0.0891 (7)	0.1410 (4)	0.0369 (3)	0.0506 (8)
C1	0.4065 (8)	0.0579 (5)	0.2004 (4)	0.0383 (9)
C2	0.5712 (9)	−0.0691 (6)	0.2747 (5)	0.0482 (10)
H2A	0.5667	−0.1659	0.2682	0.058*
C3	0.7421 (10)	−0.0540 (7)	0.3583 (5)	0.0571 (12)
H3A	0.8511	−0.1398	0.4081	0.068*
C4	0.7485 (10)	0.0890 (7)	0.3665 (5)	0.0571 (13)
H4A	0.8638	0.1000	0.4221	0.068*
C5	0.5879 (9)	0.2166 (6)	0.2942 (5)	0.0465 (10)
H5A	0.5959	0.3124	0.3018	0.056*
C6	0.4120 (8)	0.2051 (5)	0.2093 (4)	0.0365 (8)
C7	0.2342 (8)	0.0364 (5)	0.1093 (4)	0.0402 (9)
C8	0.2613 (11)	0.5208 (5)	0.1742 (5)	0.0488 (11)
H8A	0.4498	0.5209	0.1687	0.059*
H8B	0.1864	0.6192	0.1130	0.059*
C9	0.1482 (10)	0.5076 (6)	0.3179 (5)	0.0504 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0549 (7)	0.0366 (5)	0.0400 (6)	−0.0082 (4)	−0.0092 (4)	−0.0178 (4)
O1	0.093 (3)	0.210 (7)	0.109 (4)	−0.084 (4)	0.041 (3)	−0.121 (5)
O2	0.076 (3)	0.149 (5)	0.077 (3)	−0.034 (3)	0.002 (2)	−0.075 (3)
O3	0.064 (2)	0.0412 (17)	0.073 (2)	0.0014 (15)	−0.0322 (18)	−0.0301 (16)
O4	0.063 (2)	0.0398 (16)	0.060 (2)	−0.0022 (14)	−0.0285 (16)	−0.0241 (15)
C1	0.040 (2)	0.043 (2)	0.038 (2)	−0.0067 (17)	−0.0030 (16)	−0.0202 (17)
C2	0.052 (3)	0.046 (2)	0.050 (3)	−0.004 (2)	−0.012 (2)	−0.020 (2)
C3	0.056 (3)	0.062 (3)	0.055 (3)	0.000 (2)	−0.021 (2)	−0.020 (2)
C4	0.046 (3)	0.077 (3)	0.060 (3)	−0.005 (2)	−0.020 (2)	−0.033 (3)
C5	0.042 (2)	0.058 (3)	0.054 (3)	−0.012 (2)	−0.0053 (19)	−0.033 (2)
C6	0.0368 (19)	0.044 (2)	0.0344 (19)	−0.0082 (16)	−0.0008 (15)	−0.0194 (16)
C7	0.043 (2)	0.041 (2)	0.045 (2)	−0.0066 (17)	−0.0047 (17)	−0.0241 (18)
C8	0.067 (3)	0.038 (2)	0.050 (2)	−0.016 (2)	−0.008 (2)	−0.0189 (19)
C9	0.058 (3)	0.047 (2)	0.060 (3)	−0.010 (2)	−0.009 (2)	−0.032 (2)

Geometric parameters (Å, º) top

S1—C6	1.768 (4)	C2—C3	1.385 (6)
S1—C8	1.809 (4)	C2—H2A	0.9300
O1—C9	1.224 (7)	C3—C4	1.368 (8)
O2—C9	1.251 (6)	C3—H3A	0.9300
O2—H2	0.86 (7)	C4—C5	1.372 (7)
O3—C7	1.315 (5)	C4—H4A	0.9300
O3—H3	0.85 (2)	C5—C6	1.399 (6)
O4—C7	1.216 (5)	C5—H5A	0.9300
C1—C2	1.388 (6)	C8—C9	1.509 (7)
C1—C6	1.409 (6)	C8—H8A	0.9700
C1—C7	1.476 (5)	C8—H8B	0.9700

C6—S1—C8	103.4 (2)	C6—C5—H5A	119.4
C9—O2—H2	105 (6)	C5—C6—C1	117.6 (4)
C7—O3—H3	105 (4)	C5—C6—S1	121.8 (3)
C2—C1—C6	120.0 (4)	C1—C6—S1	120.6 (3)
C2—C1—C7	118.8 (4)	O4—C7—O3	122.1 (4)
C6—C1—C7	121.2 (4)	O4—C7—C1	123.9 (4)
C3—C2—C1	121.0 (4)	O3—C7—C1	114.1 (4)
C3—C2—H2A	119.5	C9—C8—S1	114.5 (3)
C1—C2—H2A	119.5	C9—C8—H8A	108.6
C4—C3—C2	119.1 (5)	S1—C8—H8A	108.6
C4—C3—H3A	120.5	C9—C8—H8B	108.6
C2—C3—H3A	120.5	S1—C8—H8B	108.6
C3—C4—C5	121.1 (4)	H8A—C8—H8B	107.6
C3—C4—H4A	119.4	O1—C9—O2	122.5 (5)
C5—C4—H4A	119.4	O1—C9—C8	121.3 (4)
C4—C5—C6	121.2 (4)	O2—C9—C8	116.1 (5)
C4—C5—H5A	119.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.86 (7)	1.92 (5)	2.687 (6)	149 (8)
O3—H3···O4ⁱⁱ	0.85 (2)	1.80 (5)	2.634 (4)	167 (6)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₉H₈O₄S
M_r	212.22
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.1786 (5), 9.2973 (9), 10.4776 (11)
α, β, γ (°)	69.980 (4), 81.959 (6), 79.732 (6)
V (Å³)	464.69 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.33 × 0.24 × 0.15

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.910, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	6609, 2110, 1941
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.222, 1.19
No. of reflections	2110
No. of parameters	133
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.34

Computer programs: APEX2 (Bruker, 2002), SAINT (Bruker, 2002), 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
O2—H2···O1ⁱ	0.86 (7)	1.92 (5)	2.687 (6)	149 (8)
O3—H3···O4ⁱⁱ	0.85 (2)	1.80 (5)	2.634 (4)	167 (6)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z.

References

Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sagatys, D. S., Smith, G., Bott, R. C. & Healy, P. C. (2003). Aust. J. Chem. 56, 941–943. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sokolov, M., Fyodorova, N., Pervukhina, N. & Fedorov, V. (2001). Inorg. Chem. Commun. 4, 261–263. Web of Science CSD CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2315

doi:10.1107/S1600536809034126

Open

access