4-Thioxo-3,5-dithia-1,7-hepta­nedioic acid

Zeng, G.-S.; Zou, J.-P.; Peng, Q.; Wen, Z.-H.; Zhang, A.-Q.

doi:10.1107/S1600536808030997

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o2047

doi:10.1107/S1600536808030997

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4-Thioxo-3,5-dithia-1,7-heptanedioic acid

Gui-Sheng Zeng,^a Jian-Ping Zou,^a ^* Qiang Peng,^a Zhen-Hai Wen ^a and Ai-Qing Zhang ^a

^aSchool of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang, Jiangxi 330063, People's Republic of China
^*Correspondence e-mail: zjp_112@126.com

(Received 18 September 2008; accepted 25 September 2008; online 30 September 2008)

The complete molecule of the title compound, C₅H₆O₄S₃, is generated by crystallographic twofold symmetry with the C=S group lying on the rotation axis. The molecules are linked through weak hydrogen-bond contacts by glide-plane operations to form R₂²(20) rings and ladder-like C(4) chains along the c axis.

Related literature

For related literature, see: Bernstein et al. (1995 ); El-Bindary et al. (1994 ); Ng (1995 ); Reid (1962 ); Strube (1963 ).

Experimental

Crystal data

C₅H₆O₄S₃
M_r = 226.28
Monoclinic, C 2/c
a = 18.899 (14) Å
b = 5.965 (4) Å
c = 7.565 (6) Å
β = 92.992 (2)°
V = 851.7 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 293 (2) K
0.15 × 0.12 × 0.08 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002 ) T_min = 0.912, T_max = 1.000 (expected range = 0.853–0.935)
2955 measured reflections
967 independent reflections
868 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.120
S = 1.00
967 reflections
56 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2ⁱ	0.82	1.82	2.631 (3)	168
Symmetry code: (i) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030997/si2112sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030997/si2112Isup2.hkl

checkCIF report

Comment top

Although the synthesis and the molecular structure of the title compound, also named as trithiocarbodiglycolic acid (TTCD), have been reported, to our knowledge, there is no report on the unit-cell parameters and the crystal structure of TTCD in the literature (Reid, 1962; Strube, 1963; El-Bindary et al., 1994). The crystal structure of a 1:1:1 cocrystal of TTCD and trithiocarbodiglycolate and bis(dicyclohexylammonium) (Ng, 1995) have been reported.

The molecule of the title compound occupies a crystallographic twofold rotation axis with one half-molecule in the asymmetric unit, the C₂ axis running through the C═S group (Fig. 1). The same molecular symmetry can be observed for the trithiocarbodiglycolate^2- and the neutral TTCD molecules in the structure reported by Ng (1995), which crystallises in space group P2/a. Bond distances and angles (Table 1) are close to those in the complexes composed of TTCD reported in the literature (Ng, 1995).

The molecules are linked through weak hydrogen-bond contacts (Table 2) by glide-plane operations to form R₂²(20) rings and C(4) chains along the c axis (Fig. 2).

Related literature top

For related literature, see: Bernstein et al. (1995); El-Bindary et al. (1994); Ng (1995); Reid (1962); Strube (1963).

Experimental top

A mixture of trithiocarbodiglycolic acid (0.25 mmol), CoCl₂.6H₂O (0.25 mmol) was dissolved in a 10 ml water in order to synthesize the Co complexes with trithiocarbodiglycolic acid as the ligand. After stirring for about 8 h, the mixed solution was filtered. The filtrate was allowed to stand at room temperature. Colorless crystals of the title complex but not the Co complex with the trithiocarbodiglycolic acid as the ligand were obtained over a period of 10 d.

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecule structure in the title compound, showing 30% displacement ellipsoids for non-H atoms. Symmetry code, i: 1 - x, y, 1/2 - z.
	Fig. 2. A view of the 1-D chain of the title compound along the c direction. Dashed lines represent the hydrogen bonds.

3,5-Dithia-4-thioxo-1,7-heptanedioic acid top

Crystal data top

C₅H₆O₄S₃	F(000) = 464
M_r = 226.28	D_x = 1.765 Mg m⁻³
Monoclinic, C2/c	Melting point: not measured K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 18.899 (14) Å	Cell parameters from 24 reflections
b = 5.965 (4) Å	θ = 3.6–27.4°
c = 7.565 (6) Å	µ = 0.84 mm⁻¹
β = 92.992 (2)°	T = 293 K
V = 851.7 (11) Å³	Prism, colourless
Z = 4	0.15 × 0.12 × 0.08 mm

Data collection top

Rigaku Mercury CCD diffractometer	967 independent reflections
Radiation source: rotating-anode generator	868 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.4°, θ_min = 3.6°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	h = −24→19
T_min = 0.912, T_max = 1.000	k = −7→7
2955 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.095P)²] where P = (F_o² + 2F_c²)/3
967 reflections	(Δ/σ)_max = 0.001
56 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₅H₆O₄S₃	V = 851.7 (11) Å³
M_r = 226.28	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.899 (14) Å	µ = 0.84 mm⁻¹
b = 5.965 (4) Å	T = 293 K
c = 7.565 (6) Å	0.15 × 0.12 × 0.08 mm
β = 92.992 (2)°

Data collection top

Rigaku Mercury CCD diffractometer	967 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	868 reflections with I > 2σ(I)
T_min = 0.912, T_max = 1.000	R_int = 0.021
2955 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.00	Δρ_max = 0.45 e Å⁻³
967 reflections	Δρ_min = −0.31 e Å⁻³
56 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	0.5000	0.03720 (12)	0.2500	0.0393 (3)
S2	0.43050 (3)	0.48194 (8)	0.31113 (7)	0.0294 (2)
O1	0.29989 (9)	−0.0371 (2)	0.2569 (2)	0.0384 (4)
H1A	0.3130	−0.0788	0.3566	0.058*
O2	0.32991 (7)	0.2197 (2)	0.06832 (17)	0.0343 (4)
C1	0.5000	0.3111 (4)	0.2500	0.0247 (6)
C2	0.36648 (10)	0.2799 (3)	0.3739 (2)	0.0301 (5)
H2A	0.3895	0.1737	0.4552	0.036*
H2B	0.3300	0.3562	0.4365	0.036*
C3	0.33171 (9)	0.1520 (3)	0.2204 (2)	0.0282 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0395 (5)	0.0202 (4)	0.0581 (6)	0.000	0.0010 (4)	0.000
S2	0.0287 (4)	0.0241 (3)	0.0358 (4)	−0.00075 (17)	0.0046 (2)	−0.00350 (18)
O1	0.0469 (10)	0.0370 (9)	0.0304 (8)	−0.0136 (7)	−0.0073 (7)	0.0040 (6)
O2	0.0414 (8)	0.0352 (8)	0.0260 (8)	−0.0019 (6)	−0.0006 (6)	0.0023 (6)
C1	0.0298 (13)	0.0225 (12)	0.0213 (13)	0.000	−0.0033 (10)	0.000
C2	0.0319 (10)	0.0343 (10)	0.0244 (10)	−0.0068 (8)	0.0033 (7)	−0.0038 (8)
C3	0.0258 (9)	0.0295 (9)	0.0293 (10)	0.0010 (8)	0.0006 (7)	−0.0019 (8)

Geometric parameters (Å, º) top

S1—C1	1.634 (3)	O2—C3	1.219 (2)
S2—C1	1.7438 (18)	C2—C3	1.510 (3)
S2—C2	1.789 (2)	C2—H2A	0.9700
O1—C3	1.314 (2)	C2—H2B	0.9700
O1—H1A	0.8200

C1—S2—C2	101.88 (11)	S2—C2—H2A	108.7
C3—O1—H1A	109.5	C3—C2—H2B	108.7
S1—C1—S2ⁱ	125.75 (7)	S2—C2—H2B	108.7
S1—C1—S2	125.75 (7)	H2A—C2—H2B	107.6
S2ⁱ—C1—S2	108.50 (15)	O2—C3—O1	119.50 (18)
C3—C2—S2	114.18 (15)	O2—C3—C2	123.21 (19)
C3—C2—H2A	108.7	O1—C3—C2	117.24 (17)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱⁱ	0.82	1.82	2.631 (3)	168

Symmetry code: (ii) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₆O₄S₃
M_r	226.28
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.899 (14), 5.965 (4), 7.565 (6)
β (°)	92.992 (2)
V (Å³)	851.7 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.15 × 0.12 × 0.08

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2002)
T_min, T_max	0.912, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2955, 967, 868
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.120, 1.00
No. of reflections	967
No. of parameters	56
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.31

Computer programs: CrystalClear (Rigaku, 2002), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

S1—C1	1.634 (3)	O1—C3	1.314 (2)
S2—C1	1.7438 (18)	O2—C3	1.219 (2)
S2—C2	1.789 (2)	C2—C3	1.510 (3)

C1—S2—C2	101.88 (11)	O2—C3—O1	119.50 (18)
S1—C1—S2	125.75 (7)	O2—C3—C2	123.21 (19)
C3—C2—S2	114.18 (15)	O1—C3—C2	117.24 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.82	1.82	2.631 (3)	168.2

Symmetry code: (i) x, −y, z+1/2.

Acknowledgements

We gratefully acknowledge financial support from the Natural Science Foundation of China (grant No. 20801026) and the Natural Science Foundation of Jiangxi Province (grant No. 2007GZH1510).

References

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