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

Yin, J.-L.; Feng, Y.-L.

doi:10.1107/S1600536809015967

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1206

doi:10.1107/S1600536809015967

Open

access

2,2′-(p-Phenylenedithio)diacetic acid

Jian-Ling Yin ^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.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 ). 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 ) analogues.

Experimental

Crystal data

C₁₀H₁₀O₄S₂
M_r = 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 ) T_min = 0.839, T_max = 0.908
3837 measured reflections
1209 independent reflections
1136 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015967/at2772sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015967/at2772Isup2.hkl

checkCIF report

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%.

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

	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.
	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

C₁₀H₁₀O₄S₂	Z = 1
M_r = 258.30	F(000) = 134
Triclinic, P1	D_x = 1.603 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5633 (4) Å	Cell parameters from 2874 reflections
b = 6.9311 (5) Å	θ = 2.9–27.6°
c = 7.6173 (6) Å	µ = 0.49 mm⁻¹
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 tube	1136 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 27.6°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.839, T_max = 0.908	k = −8→9
3837 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0362P)² + 0.0845P] where P = (F_o² + 2F_c²)/3
1209 reflections	(Δ/σ)_max < 0.001
77 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₀H₁₀O₄S₂	γ = 76.112 (4)°
M_r = 258.30	V = 267.64 (3) Å³
Triclinic, P1	Z = 1
a = 5.5633 (4) Å	Mo Kα radiation
b = 6.9311 (5) Å	µ = 0.49 mm⁻¹
c = 7.6173 (6) Å	T = 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)
T_min = 0.839, T_max = 0.908	R_int = 0.016
3837 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.19 e Å⁻³
1209 reflections	Δρ_min = −0.26 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	0.66238 (6)	0.55947 (5)	0.67832 (5)	0.03597 (14)
O2	0.6441 (2)	0.17946 (15)	0.87948 (16)	0.0469 (3)
O1	0.2166 (2)	0.19194 (15)	0.97977 (16)	0.0425 (3)
H1	0.263 (4)	0.075 (4)	1.019 (3)	0.069 (7)*
C1	0.5592 (3)	0.80504 (18)	0.58268 (18)	0.0294 (3)
C2	0.3044 (3)	0.9090 (2)	0.6244 (2)	0.0396 (3)
H2A	0.1718	0.8488	0.7077	0.048*
C3	0.2472 (3)	1.1024 (2)	0.5422 (2)	0.0390 (3)
H3A	0.0759	1.1712	0.5713	0.047*
C4	0.3615 (3)	0.47918 (19)	0.80700 (19)	0.0327 (3)
H4A	0.2621	0.5652	0.9046	0.039*
H4B	0.2589	0.4866	0.7240	0.039*
C5	0.4234 (3)	0.26763 (19)	0.89175 (19)	0.0327 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0319 (2)	0.02282 (19)	0.0434 (2)	−0.00331 (13)	−0.00692 (15)	0.01037 (13)
O2	0.0351 (6)	0.0282 (5)	0.0625 (7)	−0.0045 (4)	−0.0070 (5)	0.0159 (5)
O1	0.0346 (5)	0.0263 (5)	0.0558 (7)	−0.0073 (4)	−0.0062 (5)	0.0111 (5)
C1	0.0329 (6)	0.0197 (6)	0.0314 (6)	−0.0045 (5)	−0.0078 (5)	0.0035 (5)
C2	0.0305 (7)	0.0276 (7)	0.0469 (8)	−0.0061 (5)	−0.0006 (6)	0.0106 (6)
C3	0.0278 (6)	0.0274 (7)	0.0494 (8)	−0.0018 (5)	−0.0038 (6)	0.0075 (6)
C4	0.0327 (7)	0.0227 (6)	0.0361 (7)	−0.0042 (5)	−0.0071 (5)	0.0060 (5)
C5	0.0351 (7)	0.0241 (6)	0.0337 (7)	−0.0061 (5)	−0.0065 (5)	0.0031 (5)

Geometric parameters (Å, º) top

S1—C1	1.7679 (12)	C2—C3	1.3860 (19)
S1—C4	1.8010 (14)	C2—H2A	0.9300
O2—C5	1.2139 (18)	C3—C1ⁱ	1.3843 (19)
O1—C5	1.3058 (17)	C3—H3A	0.9300
O1—H1	0.82 (2)	C4—C5	1.5015 (17)
C1—C3ⁱ	1.3843 (19)	C4—H4A	0.9700
C1—C2	1.3866 (19)	C4—H4B	0.9700

C1—S1—C4	103.14 (6)	C2—C3—H3A	119.4
C5—O1—H1	108.3 (16)	C5—C4—S1	108.38 (9)
C3ⁱ—C1—C2	118.87 (12)	C5—C4—H4A	110.0
C3ⁱ—C1—S1	115.93 (10)	S1—C4—H4A	110.0
C2—C1—S1	125.20 (10)	C5—C4—H4B	110.0
C3—C2—C1	120.01 (13)	S1—C4—H4B	110.0
C3—C2—H2A	120.0	H4A—C4—H4B	108.4
C1—C2—H2A	120.0	O2—C5—O1	124.48 (12)
C1ⁱ—C3—C2	121.12 (13)	O2—C5—C4	122.57 (12)
C1ⁱ—C3—H3A	119.4	O1—C5—C4	112.95 (12)

C4—S1—C1—C3ⁱ	−173.10 (11)	C1—C2—C3—C1ⁱ	0.2 (3)
C4—S1—C1—C2	7.47 (15)	C1—S1—C4—C5	178.43 (9)
C3ⁱ—C1—C2—C3	−0.2 (3)	S1—C4—C5—O2	4.17 (19)
S1—C1—C2—C3	179.18 (12)	S1—C4—C5—O1	−176.44 (10)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱⁱ	0.82 (2)	1.82 (2)	2.6440 (14)	177 (2)

Symmetry code: (ii) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀O₄S₂
M_r	258.30
Crystal system, space group	Triclinic, 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)
V (Å³)	267.64 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.47 × 0.30 × 0.20

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.839, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	3837, 1209, 1136
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.09
No. of reflections	1209
No. of parameters	77
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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.

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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. Web of Science CSD CrossRef PubMed CAS Google Scholar
Li, X. F., Han, Z. B., Cheng, X. N. & Chen, X. M. (2006). Inorg. Chem. Commun. 9, 1091–1095. Web of Science CSD CrossRef CAS Google Scholar
Sandhu, G. K., Sharma, N. & Tiekink, E. R. T. (1991). J. Organomet. Chem. 403, 119–131. CSD CrossRef CAS Web of Science 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1206

doi:10.1107/S1600536809015967

Open

access