6,6′-Dihydr­oxy-3,3′-dithio­dibenzoic acid

Shu-Wen Sun; Fu-Lin Zhou; Gao-Feng Wang; Gui-Hua Cui

doi:10.1107/S1600536809023757

. 2009 Jun 27;65(Pt 7):o1701. doi: 10.1107/S1600536809023757

6,6′-Dihydroxy-3,3′-dithiodibenzoic acid

Shu-Wen Sun ^a,^*, Fu-Lin Zhou ^b, Gao-Feng Wang ^a, Gui-Hua Cui ^a

PMCID: PMC2969348 PMID: 21582954

Abstract

In the title compound, C₁₄H₁₀O₆S₂, the dihedral angle between the planes of the two phenylene rings is 55.9 (1)°. Both hydroxy groups form intramolecular hydrogen bonds; however, one of them also engages in intermolecular hydrogen bonding. In the crystal, molecules are connected into helical chains by O—H⋯O hydrogen bonds. The crystal studied was an inversion twin with a domain ratio of 0.51 (13):0.49 (13).

Related literature

For hydrogen bonds and π–π stacking interactions in aromatic compounds, see: Janiak (2000 ▶); Hunter & Sanders (1990 ▶); Orr et al. (1999 ▶); Kaafarani et al. (2001 ▶). For a comparison of bond dimensions for disulfide compounds, see: Kaitner & Pavlovic (1997 ▶); Korp & Bernal (1984 ▶); Ni et al. (2004 ▶); Sacerdoti et al. (1975 ▶).

Experimental

Crystal data

C₁₄H₁₀O₆S₂
M _r = 338.34
Orthorhombic,
a = 5.3065 (6) Å
b = 11.1657 (13) Å
c = 23.906 (2) Å
V = 1416.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 298 K
0.24 × 0.15 × 0.14 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.910, T _max = 0.946
6436 measured reflections
2502 independent reflections
2060 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.103
S = 1.09
2502 reflections
211 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ▶), 1007 Friedel pairs
Flack parameter: 0.49 (13)

Data collection: SMART (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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023757/ng2599sup1.cif

e-65-o1701-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023757/ng2599Isup2.hkl

e-65-o1701-Isup2.hkl^{(122.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O5ⁱ	0.85 (3)	1.90 (3)	2.739 (4)	171 (4)
O3—H3⋯O1	0.84 (4)	1.91 (5)	2.616 (4)	142 (5)
O3—H3⋯O6ⁱⁱ	0.84 (4)	2.52 (4)	3.063 (5)	123 (4)
O4—H4⋯O1ⁱⁱⁱ	0.85 (4)	1.79 (4)	2.636 (4)	175 (4)
O6—H6⋯O5	0.85 (4)	1.90 (4)	2.642 (4)	146 (5)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We are grateful to Professor Da-QI Wang, Liaocheng University, for the X-ray structure determination.

supplementary crystallographic information

Comment

Hydrogen bonds and π–π stacking interactions play an important role in the self-assembly and recognition of aromatic compounds((Janiak, 2000; Hunter & Sanders, 1990) as an auxiliary stabilizing short contact (Orr et al., 1999; Kaafarani et al., 2001).

The two phenyl rings of the title compound are bonded with two S atoms at a distance of 1.781 (4)Å (S2—C13) and 1.793 (4) Å (S1—C6), and the C—C distances of two phenyl groups range from 1.371 (5) to 1.407 (6) Å (Figure. 1 and Table 1). Interestingly, there are intermolecular S···S interactions in the crystal structures, which are not common in diphenyl disulfide derivaties (Korp & Bernal, 1984; Kaitner & Pavlovic 1997; Ni et al., 2004; Sacerdoti et al., 1975). The intermolecular S···S interactions distance is 3.414 (2) Å, whereas the shorter intramolecular S—S distance is 2.051 (2) Å. The dihedral angle of these two phenyl rings is 55.9 (1)°, which is different from other molecules such as 4, 4'-dithiodiphenol (48.1 (2)°) (Ni et al., 2004) and diphenyl disulfide (76.7 (3)°) (Sacerdoti et al., 1975).

The crystal structure of 5, 5'-dithiodisalicylic acid demonstrates the self-assembly of molecules into three dimensional networks via hydrogen bonds(Table 2) and intermolecular S···S interactions.

Experimental

The title compound (I) was prepared as follows: To a solution of 5-(chlorosulfonyl)-2-hydroxybenzoic acid(19 mmol, 4.5 g) in conc. HCl (30 ml) cooled to 0 °C in an ice bath, Sn(118 mmol, 14.0 g) was added. The reaction mixture was stirred for 12 h and then refluxed for 6 h. The precipitate was separated and dissolved in Et₂O. After filtration the organic layer was concentrated under reduced pressure to afford a solid that was subsequently purified by recrystallization using a mixture of EtOH and H₂O. Yellow needle crystals of (I) were obtained by slow evaporation from EtOH/acetone/DMSO/DMF(5:1:3:3) after five months. Analysis calculated for C₁₄H₁₀O₆S₂: C 49.70, H 2.98%; found: C 49.18, H 2.75%.