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ISSN: 2056-9890

2,2′-(p-Phenyl­enedi­thio)di­acetic acid

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.cn

(Received 24 April 2009; accepted 28 April 2009; online 7 May 2009)

The complete molecule of the title compound, C10H10O4S2, is generated by a crystallographic inversion centre. In the crystal, mol­ecules are linked into a one-dimensional chain by inter­molecular O—H⋯O hydrogen bonds.

Related literature

For rigid aromatic carboxylic acids, see: Hu et al. (2006[Hu, T. L., Li, J. R., Liu, C. S., Shi, X. S., Zhou, J. N., Bu, X. H. & Ribas, J. (2006). Inorg. Chem. 45, 162-173.]). The title compound, a new flexible aromatic multicarboxyl­ate acid, was designed and synthesized on the basis of the 1,4-benzene­bisoxyacetate (Li et al., 2006[Li, X. F., Han, Z. B., Cheng, X. N. & Chen, X. M. (2006). Inorg. Chem. Commun. 9, 1091-1095.]) and phenyl­thio­acetate (Sandhu et al., 1991[Sandhu, G. K., Sharma, N. & Tiekink, E. R. T. (1991). J. Organomet. Chem. 403, 119-131.]) analogues.

[Scheme 1]

Experimental

Crystal data
  • C10H10O4S2

  • Mr = 258.30

  • Triclinic, [P \overline 1]

  • a = 5.5633 (4) Å

  • b = 6.9311 (5) Å

  • c = 7.6173 (6) Å

  • α = 79.809 (5)°

  • β = 70.738 (4)°

  • γ = 76.112 (4)°

  • V = 267.64 (3) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 0.49 mm−1

  • T = 296 K

  • 0.47 × 0.30 × 0.20 mm

Data collection
  • Bruker APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.839, Tmax = 0.908

  • 3837 measured reflections

  • 1209 independent reflections

  • 1136 reflections with I > 2σ(I)

  • Rint = 0.016

Refinement
  • R[F2 > 2σ(F2)] = 0.027

  • wR(F2) = 0.073

  • S = 1.09

  • 1209 reflections

  • 77 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O2i 0.82 (2) 1.82 (2) 2.6440 (14) 177 (2)
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Researches on the aromatic carboxylic acids mainly focused on the rigid acids (Hu et al., 2006). Compared with the rigid acids, the flexible aromatic carboxylate acids contain more coordination sites and may lead to the versatile and novel metal-organic complexes. We successfully designed and synthesized a new flexible aromatic multicarboxylate acid,1,4-benzenebis(thioacetic acid) (I), on the basis of the 1,4-benzenebisoxyacetate (Li et al., 2006) and phenylthioacetate (Sandhu et al., 1991).

The compound (I) possesses two flexible carboxyl groups (Fig. 1). The centroid of the benzene ring of the molecule is an inversion centre and the asymmetric unit contains an half-molecule. The bond lengths and angles are as expected. In the crystal structure, intermolecular O—H···O hydrogen bonds link the molecules into a one-dimensional chain (Fig. 2).

Related literature top

For rigid aromatic carboxylic acids, see: Hu et al. (2006). The title compound, a new flexible aromatic multicarboxylate acid, was designed and synthesized on the basis of the 1,4-benzenebisoxyacetate (Li et al., 2006) and phenylthioacetate (Sandhu et al., 1991).

Experimental top

The solution of 1,4-benzenebisthiol (7.11 g, 0.05 mol) in water (10 ml) neutralized with NaOH (4.00 g, 0.10 mol) was added to a 1:1 mixture of chloroacetic acid (18.90 g, 0.20 mol) and NaOH (8.00 g, 0.20 mol) with stirring to adjust the pH value of the mixture to ca 11 and refluxed at 363 K for 3 h. Then adjust the pH value to 2–3 with concentrated hydrochloric acid as soon as the reaction finished. The sample was filtrated, washed by water, then dried, the compound (I) was obtained with a yield of 80%.

Refinement top

The H atoms bonded to C atoms were positioned geometrically [aliphatic C—H = 0.97 Å and aromatic C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C)]. The H atoms bonded to O atoms were located in a difference Fourier maps and refined with Uiso(H) = 1.5Ueq(O).

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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecule of the compound (I), showing the atom-labelling scheme. displacement ellipsoids are shown at the 30% probability level.
[Figure 2] Fig. 2. A view of the one-dimentional chain formed via O—H···O bydrogen bonds.
2,2'-(p-Phenylenedithio)diacetic acid top
Crystal data top
C10H10O4S2Z = 1
Mr = 258.30F(000) = 134
Triclinic, P1Dx = 1.603 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.5633 (4) ÅCell parameters from 2874 reflections
b = 6.9311 (5) Åθ = 2.9–27.6°
c = 7.6173 (6) ŵ = 0.49 mm1
α = 79.809 (5)°T = 296 K
β = 70.738 (4)°Block, colourless
γ = 76.112 (4)°0.47 × 0.30 × 0.20 mm
V = 267.64 (3) Å3
Data collection top
Bruker APEXII
diffractometer
1209 independent reflections
Radiation source: fine-focus sealed tube1136 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω scansθmax = 27.6°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.839, Tmax = 0.908k = 89
3837 measured reflectionsl = 99
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0362P)2 + 0.0845P]
where P = (Fo2 + 2Fc2)/3
1209 reflections(Δ/σ)max < 0.001
77 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C10H10O4S2γ = 76.112 (4)°
Mr = 258.30V = 267.64 (3) Å3
Triclinic, P1Z = 1
a = 5.5633 (4) ÅMo Kα radiation
b = 6.9311 (5) ŵ = 0.49 mm1
c = 7.6173 (6) ÅT = 296 K
α = 79.809 (5)°0.47 × 0.30 × 0.20 mm
β = 70.738 (4)°
Data collection top
Bruker APEXII
diffractometer
1209 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1136 reflections with I > 2σ(I)
Tmin = 0.839, Tmax = 0.908Rint = 0.016
3837 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.19 e Å3
1209 reflectionsΔρmin = 0.26 e Å3
77 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
xyzUiso*/Ueq
S10.66238 (6)0.55947 (5)0.67832 (5)0.03597 (14)
O20.6441 (2)0.17946 (15)0.87948 (16)0.0469 (3)
O10.2166 (2)0.19194 (15)0.97977 (16)0.0425 (3)
H10.263 (4)0.075 (4)1.019 (3)0.069 (7)*
C10.5592 (3)0.80504 (18)0.58268 (18)0.0294 (3)
C20.3044 (3)0.9090 (2)0.6244 (2)0.0396 (3)
H2A0.17180.84880.70770.048*
C30.2472 (3)1.1024 (2)0.5422 (2)0.0390 (3)
H3A0.07591.17120.57130.047*
C40.3615 (3)0.47918 (19)0.80700 (19)0.0327 (3)
H4A0.26210.56520.90460.039*
H4B0.25890.48660.72400.039*
C50.4234 (3)0.26763 (19)0.89175 (19)0.0327 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0319 (2)0.02282 (19)0.0434 (2)0.00331 (13)0.00692 (15)0.01037 (13)
O20.0351 (6)0.0282 (5)0.0625 (7)0.0045 (4)0.0070 (5)0.0159 (5)
O10.0346 (5)0.0263 (5)0.0558 (7)0.0073 (4)0.0062 (5)0.0111 (5)
C10.0329 (6)0.0197 (6)0.0314 (6)0.0045 (5)0.0078 (5)0.0035 (5)
C20.0305 (7)0.0276 (7)0.0469 (8)0.0061 (5)0.0006 (6)0.0106 (6)
C30.0278 (6)0.0274 (7)0.0494 (8)0.0018 (5)0.0038 (6)0.0075 (6)
C40.0327 (7)0.0227 (6)0.0361 (7)0.0042 (5)0.0071 (5)0.0060 (5)
C50.0351 (7)0.0241 (6)0.0337 (7)0.0061 (5)0.0065 (5)0.0031 (5)
Geometric parameters (Å, º) top
S1—C11.7679 (12)C2—C31.3860 (19)
S1—C41.8010 (14)C2—H2A0.9300
O2—C51.2139 (18)C3—C1i1.3843 (19)
O1—C51.3058 (17)C3—H3A0.9300
O1—H10.82 (2)C4—C51.5015 (17)
C1—C3i1.3843 (19)C4—H4A0.9700
C1—C21.3866 (19)C4—H4B0.9700
C1—S1—C4103.14 (6)C2—C3—H3A119.4
C5—O1—H1108.3 (16)C5—C4—S1108.38 (9)
C3i—C1—C2118.87 (12)C5—C4—H4A110.0
C3i—C1—S1115.93 (10)S1—C4—H4A110.0
C2—C1—S1125.20 (10)C5—C4—H4B110.0
C3—C2—C1120.01 (13)S1—C4—H4B110.0
C3—C2—H2A120.0H4A—C4—H4B108.4
C1—C2—H2A120.0O2—C5—O1124.48 (12)
C1i—C3—C2121.12 (13)O2—C5—C4122.57 (12)
C1i—C3—H3A119.4O1—C5—C4112.95 (12)
C4—S1—C1—C3i173.10 (11)C1—C2—C3—C1i0.2 (3)
C4—S1—C1—C27.47 (15)C1—S1—C4—C5178.43 (9)
C3i—C1—C2—C30.2 (3)S1—C4—C5—O24.17 (19)
S1—C1—C2—C3179.18 (12)S1—C4—C5—O1176.44 (10)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2ii0.82 (2)1.82 (2)2.6440 (14)177 (2)
Symmetry code: (ii) x+1, y, z+2.

Experimental details

Crystal data
Chemical formulaC10H10O4S2
Mr258.30
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)5.5633 (4), 6.9311 (5), 7.6173 (6)
α, β, γ (°)79.809 (5), 70.738 (4), 76.112 (4)
V3)267.64 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.47 × 0.30 × 0.20
Data collection
DiffractometerBruker APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.839, 0.908
No. of measured, independent and
observed [I > 2σ(I)] reflections
3837, 1209, 1136
Rint0.016
(sin θ/λ)max1)0.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.073, 1.09
No. of reflections1209
No. of parameters77
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.26

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···AD—HH···AD···AD—H···A
O1—H1···O2i0.82 (2)1.82 (2)2.6440 (14)177 (2)
Symmetry code: (i) x+1, y, z+2.
 

References

First citationBruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationHu, T. L., Li, J. R., Liu, C. S., Shi, X. S., Zhou, J. N., Bu, X. H. & Ribas, J. (2006). Inorg. Chem. 45, 162–173.  Web of Science CSD CrossRef PubMed CAS
First citationLi, X. F., Han, Z. B., Cheng, X. N. & Chen, X. M. (2006). Inorg. Chem. Commun. 9, 1091–1095.  Web of Science CSD CrossRef CAS
First citationSandhu, G. K., Sharma, N. & Tiekink, E. R. T. (1991). J. Organomet. Chem. 403, 119–131.  CSD CrossRef CAS Web of Science
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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