6,6'-Dihydr-oxy-3,3'-dithio-dibenzoic acid.

In the title compound, C(14)H(10)O(6)S(2), the dihedral angle between the planes of the two phenyl-ene rings is 55.9 (1)°. Both hydr-oxy groups form intra-molecular hydrogen bonds; however, one of them also engages in inter-molecular hydrogen bonding. In the crystal, mol-ecules 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 = 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

Δρmax = 0.40 e Å−3

Δρmin = −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.

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

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

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

C14H10O6S2	Dx = 1.587 Mg m−3
Mr = 338.34	Melting point: 523 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2489 reflections
a = 5.3065 (6) Å	θ = 2.5–25.5°
b = 11.1657 (13) Å	µ = 0.40 mm−1
c = 23.906 (2) Å	T = 298 K
V = 1416.5 (3) Å3	Needle, yellow
Z = 4	0.24 × 0.15 × 0.14 mm
F(000) = 696

Bruker SMART area-detector diffractometer	2502 independent reflections
Radiation source: fine-focus sealed tube	2060 reflections with I > 2σ(I)
graphite	Rint = 0.043
φ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
Tmin = 0.910, Tmax = 0.946	k = −13→13
6436 measured reflections	l = −28→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103	w = 1/[σ2(Fo2) + (0.0345P)2 + 0.9484P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
2502 reflections	Δρmax = 0.40 e Å−3
211 parameters	Δρmin = −0.28 e Å−3
4 restraints	Absolute structure: Flack (1983), 1007 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.49 (13)

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.

	x	y	z	Uiso*/Ueq
O1	−0.4934 (6)	0.8216 (2)	0.21892 (11)	0.0439 (7)
O2	−0.6036 (6)	0.6399 (3)	0.18732 (11)	0.0439 (8)
H2	−0.717 (6)	0.643 (4)	0.2123 (14)	0.066*
O3	−0.1299 (6)	0.9391 (3)	0.16941 (13)	0.0519 (8)
H3	−0.254 (6)	0.934 (5)	0.1911 (17)	0.078*
O4	−0.1551 (7)	0.3528 (3)	0.20456 (12)	0.0505 (8)
H4	−0.269 (7)	0.338 (4)	0.2286 (15)	0.076*
O5	−0.0215 (6)	0.1743 (3)	0.23556 (11)	0.0438 (7)
O6	0.3765 (6)	0.0759 (3)	0.18767 (12)	0.0503 (8)
H6	0.252 (6)	0.080 (5)	0.2099 (17)	0.075*
S1	−0.0244 (2)	0.52404 (9)	0.01641 (4)	0.0370 (3)
S2	0.34345 (19)	0.46809 (9)	0.01989 (4)	0.0360 (2)
C1	−0.4622 (8)	0.7376 (4)	0.18627 (14)	0.0343 (9)
C2	−0.2645 (7)	0.7386 (3)	0.14288 (15)	0.0303 (9)
C3	−0.1095 (8)	0.8396 (3)	0.13723 (15)	0.0360 (10)
C4	0.0804 (8)	0.8402 (4)	0.09698 (16)	0.0391 (10)
H4A	0.1880	0.9057	0.0942	0.047*
C5	0.1095 (8)	0.7447 (3)	0.06154 (16)	0.0391 (10)
H5	0.2337	0.7470	0.0341	0.047*
C6	−0.0443 (8)	0.6441 (3)	0.06607 (15)	0.0324 (9)
C7	−0.2280 (8)	0.6406 (3)	0.10693 (15)	0.0339 (9)
H7	−0.3285	0.5729	0.1107	0.041*
C8	−0.0058 (8)	0.2582 (4)	0.20199 (16)	0.0367 (9)
C9	0.1795 (7)	0.2604 (3)	0.15645 (15)	0.0314 (9)
C10	0.3593 (8)	0.1685 (3)	0.15118 (15)	0.0356 (9)
C11	0.5317 (8)	0.1726 (3)	0.10729 (16)	0.0404 (10)
H11	0.6534	0.1130	0.1041	0.048*
C12	0.5236 (8)	0.2640 (3)	0.06854 (16)	0.0387 (9)
H12	0.6396	0.2651	0.0394	0.046*
C13	0.3440 (8)	0.3550 (3)	0.07246 (14)	0.0312 (9)
C14	0.1790 (8)	0.3533 (3)	0.11681 (15)	0.0350 (9)
H14	0.0637	0.4155	0.1207	0.042*

	U11	U22	U33	U12	U13	U23
O1	0.0515 (18)	0.0345 (16)	0.0456 (15)	0.0031 (16)	0.0185 (17)	−0.0067 (13)
O2	0.047 (2)	0.0394 (16)	0.0449 (16)	−0.0082 (15)	0.0179 (15)	−0.0035 (14)
O3	0.057 (2)	0.0356 (16)	0.063 (2)	−0.0068 (15)	0.0226 (17)	−0.0158 (15)
O4	0.0540 (19)	0.0474 (18)	0.0502 (18)	0.0124 (17)	0.0237 (16)	0.0074 (15)
O5	0.0474 (18)	0.0416 (17)	0.0423 (16)	0.0038 (16)	0.0113 (16)	0.0068 (13)
O6	0.050 (2)	0.0404 (17)	0.0605 (19)	0.0127 (16)	0.0138 (17)	0.0138 (16)
S1	0.0372 (6)	0.0428 (5)	0.0311 (5)	0.0055 (5)	−0.0017 (5)	−0.0050 (5)
S2	0.0371 (5)	0.0370 (5)	0.0340 (5)	0.0005 (5)	0.0064 (5)	0.0011 (5)
C1	0.034 (2)	0.040 (2)	0.0291 (19)	0.005 (2)	0.0003 (19)	0.0052 (18)
C2	0.031 (2)	0.0292 (19)	0.031 (2)	0.0008 (18)	−0.0014 (18)	0.0029 (17)
C3	0.040 (2)	0.032 (2)	0.036 (2)	0.0092 (19)	0.002 (2)	−0.0012 (18)
C4	0.036 (3)	0.033 (2)	0.049 (2)	−0.0035 (19)	0.006 (2)	0.004 (2)
C5	0.044 (3)	0.040 (2)	0.033 (2)	0.007 (2)	0.009 (2)	0.009 (2)
C6	0.036 (2)	0.031 (2)	0.0302 (19)	0.0064 (19)	−0.0022 (19)	0.0001 (16)
C7	0.039 (2)	0.031 (2)	0.032 (2)	0.0007 (19)	−0.0032 (19)	0.0034 (17)
C8	0.032 (2)	0.038 (2)	0.040 (2)	0.003 (2)	−0.001 (2)	−0.0059 (19)
C9	0.031 (2)	0.034 (2)	0.0297 (19)	−0.0025 (18)	0.0036 (18)	−0.0039 (17)
C10	0.041 (2)	0.034 (2)	0.032 (2)	0.000 (2)	−0.002 (2)	−0.0023 (17)
C11	0.034 (2)	0.034 (2)	0.052 (2)	0.011 (2)	0.009 (2)	−0.0032 (19)
C12	0.033 (2)	0.045 (2)	0.038 (2)	0.003 (2)	0.008 (2)	−0.0022 (19)
C13	0.031 (2)	0.033 (2)	0.0293 (19)	−0.0027 (19)	0.0005 (19)	−0.0065 (17)
C14	0.035 (2)	0.035 (2)	0.035 (2)	0.0044 (19)	−0.0009 (19)	−0.0021 (18)

O1—C1	1.231 (4)	C4—C5	1.371 (5)
O2—C1	1.324 (5)	C4—H4A	0.9300
O2—H2	0.848 (10)	C5—C6	1.393 (5)
O3—C3	1.356 (5)	C5—H5	0.9300
O3—H3	0.842 (10)	C6—C7	1.380 (5)
O4—C8	1.322 (5)	C7—H7	0.9300
O4—H4	0.848 (10)	C8—C9	1.467 (5)
O5—C8	1.236 (5)	C9—C14	1.405 (5)
O6—C10	1.356 (4)	C9—C10	1.407 (6)
O6—H6	0.849 (10)	C10—C11	1.393 (5)
S1—C6	1.793 (4)	C11—C12	1.380 (5)
S1—S2	2.0511 (15)	C11—H11	0.9300
S2—C13	1.781 (4)	C12—C13	1.396 (5)
C1—C2	1.476 (5)	C12—H12	0.9300
C2—C3	1.402 (5)	C13—C14	1.375 (5)
C2—C7	1.404 (5)	C14—H14	0.9300
C3—C4	1.394 (5)
C1—O2—H2	113 (3)	C6—C7—C2	120.6 (4)
C3—O3—H3	111 (4)	C6—C7—H7	119.7
C8—O4—H4	108 (4)	C2—C7—H7	119.7
C10—O6—H6	108 (4)	O5—C8—O4	122.4 (4)
C6—S1—S2	104.89 (14)	O5—C8—C9	122.7 (4)
C13—S2—S1	104.24 (14)	O4—C8—C9	115.0 (4)
O1—C1—O2	122.6 (4)	C14—C9—C10	118.6 (3)
O1—C1—C2	122.4 (4)	C14—C9—C8	120.8 (4)
O2—C1—C2	115.0 (3)	C10—C9—C8	120.6 (3)
C3—C2—C7	119.1 (3)	O6—C10—C11	117.7 (4)
C3—C2—C1	119.4 (3)	O6—C10—C9	123.0 (3)
C7—C2—C1	121.5 (3)	C11—C10—C9	119.3 (4)
O3—C3—C4	116.4 (4)	C12—C11—C10	120.6 (4)
O3—C3—C2	123.9 (4)	C12—C11—H11	119.7
C4—C3—C2	119.6 (4)	C10—C11—H11	119.7
C5—C4—C3	120.3 (4)	C11—C12—C13	121.0 (4)
C5—C4—H4A	119.9	C11—C12—H12	119.5
C3—C4—H4A	119.9	C13—C12—H12	119.5
C4—C5—C6	120.9 (4)	C14—C13—C12	118.4 (4)
C4—C5—H5	119.6	C14—C13—S2	123.6 (3)
C6—C5—H5	119.6	C12—C13—S2	118.0 (3)
C7—C6—C5	119.4 (3)	C13—C14—C9	121.9 (4)
C7—C6—S1	119.3 (3)	C13—C14—H14	119.0
C5—C6—S1	121.1 (3)	C9—C14—H14	119.0
C6—S1—S2—C13	89.96 (17)	O5—C8—C9—C14	175.4 (4)
O1—C1—C2—C3	−1.7 (5)	O4—C8—C9—C14	−4.7 (5)
O2—C1—C2—C3	178.1 (3)	O5—C8—C9—C10	−3.8 (6)
O1—C1—C2—C7	178.4 (4)	O4—C8—C9—C10	176.1 (4)
O2—C1—C2—C7	−1.7 (5)	C14—C9—C10—O6	179.2 (4)
C7—C2—C3—O3	179.5 (3)	C8—C9—C10—O6	−1.6 (6)
C1—C2—C3—O3	−0.3 (6)	C14—C9—C10—C11	0.4 (6)
C7—C2—C3—C4	−1.3 (6)	C8—C9—C10—C11	179.5 (4)
C1—C2—C3—C4	178.9 (3)	O6—C10—C11—C12	179.7 (4)
O3—C3—C4—C5	−178.1 (4)	C9—C10—C11—C12	−1.4 (6)
C2—C3—C4—C5	2.7 (6)	C10—C11—C12—C13	0.4 (6)
C3—C4—C5—C6	−1.9 (6)	C11—C12—C13—C14	1.8 (6)
C4—C5—C6—C7	−0.2 (6)	C11—C12—C13—S2	−178.8 (3)
C4—C5—C6—S1	174.9 (3)	S1—S2—C13—C14	−29.0 (3)
S2—S1—C6—C7	−127.2 (3)	S1—S2—C13—C12	151.6 (3)
S2—S1—C6—C5	57.7 (3)	C12—C13—C14—C9	−2.9 (6)
C5—C6—C7—C2	1.5 (6)	S2—C13—C14—C9	177.8 (3)
S1—C6—C7—C2	−173.7 (3)	C10—C9—C14—C13	1.8 (6)
C3—C2—C7—C6	−0.8 (6)	C8—C9—C14—C13	−177.4 (4)
C1—C2—C7—C6	179.0 (3)

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)

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)

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