supplementary materials


Acta Cryst. (2009). E65, o2479    [ doi:10.1107/S1600536809036770 ]

4-Bromo-5-[(2-bromoethyl)sulfanyl]-1,3-dithiole-2-thione

J.-J. Ding, Y.-H. Zhang, B.-T. Zhao and G.-R. Qu

Abstract top

The title compound, C5H4Br2S4, consists of a statistically planar, 4-bromo-1,3-dithiole-2-thione unit [maximum deviation from the ring plane 0.001 (2) Å], with a bromoethylsulfanyl substituent in the 5-position. In the crystal structure, weak intermolecular S...S [3.438 (15) and 3.522 (15) Å] and S...Br [3.422 (14) and 3.498 (14) Å] interactions generate a three-dimensional supramolecular architecture.

Comment top

Tetrathiafulvalene (TTF) and its derivatives have attracted great interest for their high electronic conductivity, superconductivity as well as supramolecular features (Segura & Martin, 2001; Jeppesen et al., 2004). The attachment of halogen atoms to TTF framework reduces the π-electron donating ability and this effect is additive with an increasing number of halogens on the TTF system (Wang et al., 1995), As important precursors to the halogenated TTF derivatives, 1,3-dithiole-2-(thi)ones involving bromine groups have also attracted attention (Batsanov et al., 2001; Alberola et al., 2006). We describe here the synthesis and structure of a novel 4-bromo-5-[(2-bromoethyl)sulfanyl]-1,3-dithiole-2-thione compound, (I) (Fig. 1).

As seen from Fig. 1, all five atoms of five-membered dithiole ring and three exocyclic S1, Br1 and S4 atoms are nearly coplanar with a maximum deviation from the least-squares plane of only 0.1045 Å (Br2). The C-S bond lengths range from 1.647 (4) to 1.814 (4) Å. The bond distances C1-S1 (1.647 (3)) Å, C2-S4 (1.753 (3)) Å, and Br2-C3(1.883 (4)) Å are relatively short which indicates a degree of conjugation of the S1, S4 and Br2 substituents with the 1,3-dithiol ring system. However, the C4-S4 bond is typical of a single bond with a bond length of 1.814 (4) Å. The structure of title compound is very similar to that of 3-(2-thioxo-1,3- dithiol-4-ylsulfanyl)propanenitrile (Zhao et al., 2008).

In the crystal structure, molecules of (I) form 1-dimensional chains by way of intermolecular S···S interactions along a axis (Fig.2). The distances between alternate S2 atoms are 3.438 (15) Å and 3.522 (15) Å, respectively. In addition, the 1-dimensional chains are interconnected by intermolecular S1···Br2 interactions (S1···Br2 = 3.422 (14) Å) to generate a 2-dimensional sheet (Fig. 3) in the ab plane. These are further linked by intermolecular Br1···S1 interactions (S1···Br1 = 3.498 (14) Å) to form a 3-dimensional supramolecular structure (Fig. 4).

Related literature top

For general background to the applications of halogenated 1,3-dithiole-2-thiones, see: Alberola et al. 2006; Batsanov et al. (2001); Jeppesen et al. (2004); Segura & Martin (2001); Wang et al. (1995). For a related structure, see: Zhao et al. (2008).

Experimental top

A solution of PPh3(3.04 g, 11.6 mmol) in dichloromethane (20 mL) was added dropwise to a solution of 4-(2-hydroxyethylsulfanyl)-1,3-dithiole-2-thione (1.67 g, 11.6 mmol) and CBr4 (3.84 g, 11.6 mmol), also in dichloromethane (50 mL), over 2 h. The mixture was then stirred for 8 h at room temperature. The resulting solution was washed with water and dried with Na2SO4. The solvent was then evaporated under reduced pressure and the crude product was purified by column chromatography on silica. (dichloromethane:petroleum ether= 2:3) to yield the title compound as yellow solid in 85 % yield. Yellow block-like single crystals were obtained from slow evaporation of a dichloromethane solution at room temperature.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with d(C-H) = 0.97 Å, Uiso = 1.2Ueq (C) for CH2 atoms.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. The 1-dimensional chain formed by S···S interactions, shown as dashed lines.
[Figure 3] Fig. 3. The 2-dimensional sheet formed by intermolecular S2···S2 and S1···Br2 interactions, shown as dashed lines.
[Figure 4] Fig. 4. The 3-dimensional network formed by intermolecular S2···S2, S1···Br2 and S1···Br1 interactions, shown as dashed lines.
4-Bromo-5-[(2-bromoethyl)sulfanyl]-1,3-dithiole-2-thione top
Crystal data top
C5H4Br2S4F(000) = 672
Mr = 352.14Dx = 2.233 Mg m3
Monoclinic, P21/cMelting point: 331 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 4.7892 (12) ÅCell parameters from 3116 reflections
b = 20.381 (5) Åθ = 3.6–26.1°
c = 10.809 (3) ŵ = 8.47 mm1
β = 96.922 (3)°T = 294 K
V = 1047.3 (5) Å3Block, yellow
Z = 40.44 × 0.17 × 0.06 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2391 independent reflections
Radiation source: fine-focus sealed tube1845 reflections with I > 2σ(I)
graphiteRint = 0.033
φ and ω scansθmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 66
Tmin = 0.117, Tmax = 0.613k = 2626
9101 measured reflectionsl = 1314
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0361P)2 + 0.5713P]
where P = (Fo2 + 2Fc2)/3
2391 reflections(Δ/σ)max = 0.001
100 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.81 e Å3
Crystal data top
C5H4Br2S4V = 1047.3 (5) Å3
Mr = 352.14Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.7892 (12) ŵ = 8.47 mm1
b = 20.381 (5) ÅT = 294 K
c = 10.809 (3) Å0.44 × 0.17 × 0.06 mm
β = 96.922 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2391 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1845 reflections with I > 2σ(I)
Tmin = 0.117, Tmax = 0.613Rint = 0.033
9101 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.081Δρmax = 0.38 e Å3
S = 1.05Δρmin = 0.81 e Å3
2391 reflectionsAbsolute structure: ?
100 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell esds are taken

into account individually in the estimation of esds in distances, angles

and torsion angles; correlations between esds in cell parameters are only

used when they are defined by crystal symmetry. An approximate (isotropic)

treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
Br10.33646 (9)0.39616 (2)0.03831 (4)0.05782 (14)
Br20.12031 (10)0.252098 (19)0.33275 (4)0.06158 (15)
S10.6869 (2)0.39508 (5)0.69591 (9)0.0506 (2)
S20.25370 (18)0.43827 (4)0.49022 (8)0.0406 (2)
S30.3149 (2)0.30064 (4)0.54490 (10)0.0517 (3)
S40.20103 (18)0.42118 (5)0.27552 (9)0.0481 (2)
C10.4319 (7)0.37956 (16)0.5834 (3)0.0379 (7)
C20.0385 (7)0.38613 (16)0.3924 (3)0.0379 (7)
C30.0692 (8)0.32205 (17)0.4204 (3)0.0439 (8)
C40.0261 (7)0.43820 (17)0.1567 (3)0.0432 (8)
H4A0.07370.46540.09230.052*
H4B0.19000.46230.19350.052*
C50.1193 (8)0.37586 (17)0.0993 (4)0.0458 (8)
H5A0.04410.34980.06860.055*
H5B0.23400.35030.16200.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0521 (2)0.0758 (3)0.0462 (3)0.00042 (19)0.00845 (17)0.00156 (19)
Br20.0753 (3)0.0501 (2)0.0572 (3)0.01945 (19)0.0007 (2)0.00821 (18)
S10.0503 (5)0.0586 (6)0.0406 (5)0.0006 (4)0.0045 (4)0.0014 (4)
S20.0410 (5)0.0369 (4)0.0424 (5)0.0004 (3)0.0003 (4)0.0019 (3)
S30.0659 (6)0.0388 (4)0.0483 (6)0.0032 (4)0.0021 (5)0.0048 (4)
S40.0341 (5)0.0628 (5)0.0462 (5)0.0083 (4)0.0001 (4)0.0038 (4)
C10.0390 (18)0.0420 (17)0.0342 (19)0.0010 (14)0.0098 (14)0.0002 (14)
C20.0346 (17)0.0441 (17)0.0349 (19)0.0009 (14)0.0039 (13)0.0031 (14)
C30.048 (2)0.0448 (18)0.039 (2)0.0081 (16)0.0068 (16)0.0056 (15)
C40.0414 (19)0.0425 (18)0.043 (2)0.0030 (15)0.0038 (15)0.0016 (15)
C50.045 (2)0.0448 (18)0.048 (2)0.0022 (15)0.0083 (16)0.0004 (16)
Geometric parameters (Å, °) top
Br1—C51.959 (4)S4—C41.814 (4)
Br2—C31.883 (3)C2—C31.345 (5)
S1—C11.647 (4)C4—C51.505 (5)
S2—C11.723 (3)C4—H4A0.9700
S2—C21.746 (3)C4—H4B0.9700
S3—C31.734 (4)C5—H5A0.9700
S3—C11.737 (3)C5—H5B0.9700
S4—C21.753 (4)
C1—S2—C298.40 (16)C5—C4—S4111.3 (2)
C3—S3—C197.02 (17)C5—C4—H4A109.4
C2—S4—C4101.05 (16)S4—C4—H4A109.4
S1—C1—S2124.7 (2)C5—C4—H4B109.4
S1—C1—S3122.9 (2)S4—C4—H4B109.4
S2—C1—S3112.34 (19)H4A—C4—H4B108.0
C3—C2—S2114.5 (3)C4—C5—Br1110.2 (2)
C3—C2—S4127.0 (3)C4—C5—H5A109.6
S2—C2—S4118.41 (19)Br1—C5—H5A109.6
C2—C3—S3117.7 (3)C4—C5—H5B109.6
C2—C3—Br2126.1 (3)Br1—C5—H5B109.6
S3—C3—Br2116.2 (2)H5A—C5—H5B108.1
C2—S2—C1—S1177.1 (2)S2—C2—C3—S30.9 (4)
C2—S2—C1—S32.4 (2)S4—C2—C3—S3177.7 (2)
C3—S3—C1—S1177.5 (2)S2—C2—C3—Br2178.3 (2)
C3—S3—C1—S22.0 (2)S4—C2—C3—Br24.9 (5)
C1—S2—C2—C32.0 (3)C1—S3—C3—C20.7 (3)
C1—S2—C2—S4179.1 (2)C1—S3—C3—Br2176.9 (2)
C4—S4—C2—C3102.6 (3)C2—S4—C4—C569.7 (3)
C4—S4—C2—S280.7 (2)S4—C4—C5—Br1175.02 (17)
Acknowledgements top

This work was supported by the Natural Science Foundation of China (grant No. 20872058).

references
References top

Alberola, A., Collis, R. J., Garcia, F. & Howard, R. E. (2006). Tetrahedron, 62, 8152–8157.

Batsanov, A. S., Bryce, M. R., Chesney, A., Howard, J. A. K., John, D. E., Moore, A. J., Wood, C. L., Gershtenman, H., Becker, J. Y., Khodorkovsky, V. Y., Ellern, A., Bernstein, J., Perepichka, I. F., Rotello, V., Gray, M. & Cuello, A. O. (2001). J. Mater. Chem. 11, 2181–2191.

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.

Jeppesen, J. O., Nielsen, M. B. & Becher, J. (2004). Chem. Rev. 104, 5115–5131.

Segura, J. L. & Martin, N. (2001). Angew. Chem. Int. Ed. 40, 1372–1409.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, C., Becker, J. Y., Bernstein, J., Ellern, A. & Khodorkovsky, V. (1995). J. Mater. Chem. 5, 1559–1562.

Zhao, B.-T., Ding, J.-J. & Qu, G.-R. (2008). Acta Cryst. E64, o2078.