supplementary materials
4-Thioxo-3,5-dithia-1,7-heptanedioic acid
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.
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.
H atoms were allowed to ride on their respective parent atoms with C—H and
O—H distances of 0.97 and 0.82 Å, respectively, and were included in the
refinement with isotropic displacement parameters Uiso(H) =
1.2Ueq (C) and Uiso(H) = 1.5Ueq(O), respectively.
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).
3,5-Dithia-4-thioxo-1,7-heptanedioic acid
top
Crystal data top
| C5H6O4S3 | F(000) = 464 |
| Mr = 226.28 | Dx = 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 | Rint = 0.021 |
| ω scans | θmax = 27.4°, θmin = 3.6° |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002) | h = −24→19 |
| Tmin = 0.912, Tmax = 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(Fo2) + (0.095P)2]
where P = (Fo2 + 2Fc2)/3 |
| 967 reflections | (Δ/σ)max = 0.001 |
| 56 parameters | Δρmax = 0.45 e Å−3 |
| 0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
| C5H6O4S3 | V = 851.7 (11) Å3 |
| Mr = 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) |
| Tmin = 0.912, Tmax = 1.000 | Rint = 0.021 |
| 2955 measured reflections | θmax = 27.4° |
Refinement top
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.120 | Δρmax = 0.45 e Å−3 |
| S = 1.00 | Δρmin = −0.31 e Å−3 |
| 967 reflections | Absolute structure: ? |
| 56 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| 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, °) 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 codes: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, °) 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 codes: (ii) x, −y, z+1/2. |
Table 1
Selected geometric parameters (Å, °) 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) |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O2i | 0.82 | 1.82 | 2.631 (3) | 168. |
| Symmetry codes: (i) x, −y, z+1/2. |
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).
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
El-Bindary, A. A., Shehatta, I. S. & Mabrouk, E. M. (1994). Monatsh. Chem. 125, 373–384.
Ng, S. W. (1995). Acta Cryst. C51, 2150–2152.
Reid, E. E. (1962). Organic Chemistry of Bivalent Sulfur, Vol. IV. New York: Chemical Publishing.
Rigaku (2002). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Strube, R. E. (1963). Org. Synth. Coll. Vol. Volume number? pp. 967–969.
![[Figure 1]](./si2112fig1thm.gif)
![[Figure 2]](./si2112fig2thm.gif)
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 trithiocarbodiglycolate2- 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).