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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2315.
Published online 2009 September 5. doi:  10.1107/S1600536809034126
PMCID: PMC2970427

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

Abstract

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 [triangle]); Sokolov et al. (2001 [triangle]).

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Object name is e-65-o2315-scheme1.jpg

Experimental

Crystal data

  • C9H8O4S
  • M r = 212.22
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2315-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.074
  • wR(F 2) = 0.222
  • S = 1.19
  • 2110 reflections
  • 133 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.65 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034126/at2858sup1.cif

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

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The H atoms bonded to C atoms were positioned geometrically [aromatic C—H = 0.93 Å and aliphatic C—H = 0.97 Å, Uiso(H) = 1.2Ueq(C)]. The H atoms bonded to O atoms were located in a difference Fourier map and refined freely.

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids

Crystal data

C9H8O4SZ = 2
Mr = 212.22F(000) = 220
Triclinic, P1Dx = 1.517 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.1786 (5) ÅCell parameters from 5343 reflections
b = 9.2973 (9) Åθ = 2.1–27.7°
c = 10.4776 (11) ŵ = 0.33 mm1
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

Bruker APEXII diffractometer2110 independent reflections
Radiation source: fine-focus sealed tube1941 reflections with I > 2σ(I)
graphiteRint = 0.024
ω scansθmax = 27.7°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −6→6
Tmin = 0.910, Tmax = 0.952k = −12→11
6609 measured reflectionsl = −13→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.074Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.222H atoms treated by a mixture of independent and constrained refinement
S = 1.19w = 1/[σ2(Fo2) + (0.0736P)2 + 1.2589P] where P = (Fo2 + 2Fc2)/3
2110 reflections(Δ/σ)max < 0.001
133 parametersΔρmax = 0.65 e Å3
2 restraintsΔρmin = −0.34 e Å3

Special details

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)

xyzUiso*/Ueq
S10.2028 (2)0.36823 (12)0.11601 (11)0.0417 (3)
O1−0.0678 (11)0.4660 (9)0.3612 (6)0.116 (2)
O20.2828 (9)0.5474 (7)0.3870 (5)0.0891 (16)
H20.173 (12)0.569 (10)0.449 (6)0.107*
O30.2508 (7)−0.1074 (4)0.1122 (4)0.0549 (9)
H30.127 (8)−0.107 (7)0.067 (5)0.066*
O40.0891 (7)0.1410 (4)0.0369 (3)0.0506 (8)
C10.4065 (8)0.0579 (5)0.2004 (4)0.0383 (9)
C20.5712 (9)−0.0691 (6)0.2747 (5)0.0482 (10)
H2A0.5667−0.16590.26820.058*
C30.7421 (10)−0.0540 (7)0.3583 (5)0.0571 (12)
H3A0.8511−0.13980.40810.068*
C40.7485 (10)0.0890 (7)0.3665 (5)0.0571 (13)
H4A0.86380.10000.42210.068*
C50.5879 (9)0.2166 (6)0.2942 (5)0.0465 (10)
H5A0.59590.31240.30180.056*
C60.4120 (8)0.2051 (5)0.2093 (4)0.0365 (8)
C70.2342 (8)0.0364 (5)0.1093 (4)0.0402 (9)
C80.2613 (11)0.5208 (5)0.1742 (5)0.0488 (11)
H8A0.44980.52090.16870.059*
H8B0.18640.61920.11300.059*
C90.1482 (10)0.5076 (6)0.3179 (5)0.0504 (11)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0549 (7)0.0366 (5)0.0400 (6)−0.0082 (4)−0.0092 (4)−0.0178 (4)
O10.093 (3)0.210 (7)0.109 (4)−0.084 (4)0.041 (3)−0.121 (5)
O20.076 (3)0.149 (5)0.077 (3)−0.034 (3)0.002 (2)−0.075 (3)
O30.064 (2)0.0412 (17)0.073 (2)0.0014 (15)−0.0322 (18)−0.0301 (16)
O40.063 (2)0.0398 (16)0.060 (2)−0.0022 (14)−0.0285 (16)−0.0241 (15)
C10.040 (2)0.043 (2)0.038 (2)−0.0067 (17)−0.0030 (16)−0.0202 (17)
C20.052 (3)0.046 (2)0.050 (3)−0.004 (2)−0.012 (2)−0.020 (2)
C30.056 (3)0.062 (3)0.055 (3)0.000 (2)−0.021 (2)−0.020 (2)
C40.046 (3)0.077 (3)0.060 (3)−0.005 (2)−0.020 (2)−0.033 (3)
C50.042 (2)0.058 (3)0.054 (3)−0.012 (2)−0.0053 (19)−0.033 (2)
C60.0368 (19)0.044 (2)0.0344 (19)−0.0082 (16)−0.0008 (15)−0.0194 (16)
C70.043 (2)0.041 (2)0.045 (2)−0.0066 (17)−0.0047 (17)−0.0241 (18)
C80.067 (3)0.038 (2)0.050 (2)−0.016 (2)−0.008 (2)−0.0189 (19)
C90.058 (3)0.047 (2)0.060 (3)−0.010 (2)−0.009 (2)−0.032 (2)

Geometric parameters (Å, °)

S1—C61.768 (4)C2—C31.385 (6)
S1—C81.809 (4)C2—H2A0.9300
O1—C91.224 (7)C3—C41.368 (8)
O2—C91.251 (6)C3—H3A0.9300
O2—H20.86 (7)C4—C51.372 (7)
O3—C71.315 (5)C4—H4A0.9300
O3—H30.85 (2)C5—C61.399 (6)
O4—C71.216 (5)C5—H5A0.9300
C1—C21.388 (6)C8—C91.509 (7)
C1—C61.409 (6)C8—H8A0.9700
C1—C71.476 (5)C8—H8B0.9700
C6—S1—C8103.4 (2)C6—C5—H5A119.4
C9—O2—H2105 (6)C5—C6—C1117.6 (4)
C7—O3—H3105 (4)C5—C6—S1121.8 (3)
C2—C1—C6120.0 (4)C1—C6—S1120.6 (3)
C2—C1—C7118.8 (4)O4—C7—O3122.1 (4)
C6—C1—C7121.2 (4)O4—C7—C1123.9 (4)
C3—C2—C1121.0 (4)O3—C7—C1114.1 (4)
C3—C2—H2A119.5C9—C8—S1114.5 (3)
C1—C2—H2A119.5C9—C8—H8A108.6
C4—C3—C2119.1 (5)S1—C8—H8A108.6
C4—C3—H3A120.5C9—C8—H8B108.6
C2—C3—H3A120.5S1—C8—H8B108.6
C3—C4—C5121.1 (4)H8A—C8—H8B107.6
C3—C4—H4A119.4O1—C9—O2122.5 (5)
C5—C4—H4A119.4O1—C9—C8121.3 (4)
C4—C5—C6121.2 (4)O2—C9—C8116.1 (5)
C4—C5—H5A119.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.86 (7)1.92 (5)2.687 (6)149 (8)
O3—H3···O4ii0.85 (2)1.80 (5)2.634 (4)167 (6)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2858).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography