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

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

doi:10.1107/S1600536809036770

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2479

doi:10.1107/S1600536809036770

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

Jing-Jing Ding,^a Yong-Hua Zhang,^b Bang-Tun Zhao ^b ^* and Gui-Rong Qu ^a

^aCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453002, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: zbt@lynu.edu.cn

(Received 29 August 2009; accepted 11 September 2009; online 16 September 2009)

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.

Related literature

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

Crystal data

C₅H₄Br₂S₄
M_r = 352.14
Monoclinic, P 2₁ /c
a = 4.7892 (12) Å
b = 20.381 (5) Å
c = 10.809 (3) Å
β = 96.922 (3)°
V = 1047.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 8.47 mm⁻¹
T = 294 K
0.44 × 0.17 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.117, T_max = 0.613
9101 measured reflections
2391 independent reflections
1845 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.081
S = 1.05
2391 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036770/sj2640sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809036770/sj2640Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 30% probability level.
	Fig. 2. The 1-dimensional chain formed by S···S interactions, shown as dashed lines.
	Fig. 3. The 2-dimensional sheet formed by intermolecular S2···S2 and S1···Br2 interactions, shown as dashed lines.
	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

C₅H₄Br₂S₄	F(000) = 672
M_r = 352.14	D_x = 2.233 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 331 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.7892 (12) Å	Cell parameters from 3116 reflections
b = 20.381 (5) Å	θ = 3.6–26.1°
c = 10.809 (3) Å	µ = 8.47 mm⁻¹
β = 96.922 (3)°	T = 294 K
V = 1047.3 (5) Å³	Block, yellow
Z = 4	0.44 × 0.17 × 0.06 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2391 independent reflections
Radiation source: fine-focus sealed tube	1845 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −6→6
T_min = 0.117, T_max = 0.613	k = −26→26
9101 measured reflections	l = −13→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0361P)² + 0.5713P] where P = (F_o² + 2F_c²)/3
2391 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.81 e Å⁻³

Crystal data top

C₅H₄Br₂S₄	V = 1047.3 (5) Å³
M_r = 352.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.7892 (12) Å	µ = 8.47 mm⁻¹
b = 20.381 (5) Å	T = 294 K
c = 10.809 (3) Å	0.44 × 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)
T_min = 0.117, T_max = 0.613	R_int = 0.033
9101 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	Δρ_max = 0.38 e Å⁻³
2391 reflections	Δρ_min = −0.81 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.33646 (9)	0.39616 (2)	−0.03831 (4)	0.05782 (14)
Br2	−0.12031 (10)	0.252098 (19)	0.33275 (4)	0.06158 (15)
S1	0.6869 (2)	0.39508 (5)	0.69591 (9)	0.0506 (2)
S2	0.25370 (18)	0.43827 (4)	0.49022 (8)	0.0406 (2)
S3	0.3149 (2)	0.30064 (4)	0.54490 (10)	0.0517 (3)
S4	−0.20103 (18)	0.42118 (5)	0.27552 (9)	0.0481 (2)
C1	0.4319 (7)	0.37956 (16)	0.5834 (3)	0.0379 (7)
C2	0.0385 (7)	0.38613 (16)	0.3924 (3)	0.0379 (7)
C3	0.0692 (8)	0.32205 (17)	0.4204 (3)	0.0439 (8)
C4	0.0261 (7)	0.43820 (17)	0.1567 (3)	0.0432 (8)
H4A	−0.0737	0.4654	0.0923	0.052*
H4B	0.1900	0.4623	0.1935	0.052*
C5	0.1193 (8)	0.37586 (17)	0.0993 (4)	0.0458 (8)
H5A	−0.0441	0.3498	0.0686	0.055*
H5B	0.2340	0.3503	0.1620	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0521 (2)	0.0758 (3)	0.0462 (3)	0.00042 (19)	0.00845 (17)	0.00156 (19)
Br2	0.0753 (3)	0.0501 (2)	0.0572 (3)	−0.01945 (19)	−0.0007 (2)	−0.00821 (18)
S1	0.0503 (5)	0.0586 (6)	0.0406 (5)	−0.0006 (4)	−0.0045 (4)	0.0014 (4)
S2	0.0410 (5)	0.0369 (4)	0.0424 (5)	−0.0004 (3)	−0.0003 (4)	−0.0019 (3)
S3	0.0659 (6)	0.0388 (4)	0.0483 (6)	−0.0032 (4)	−0.0021 (5)	0.0048 (4)
S4	0.0341 (5)	0.0628 (5)	0.0462 (5)	0.0083 (4)	0.0001 (4)	−0.0038 (4)
C1	0.0390 (18)	0.0420 (17)	0.0342 (19)	0.0010 (14)	0.0098 (14)	0.0002 (14)
C2	0.0346 (17)	0.0441 (17)	0.0349 (19)	−0.0009 (14)	0.0039 (13)	−0.0031 (14)
C3	0.048 (2)	0.0448 (18)	0.039 (2)	−0.0081 (16)	0.0068 (16)	−0.0056 (15)
C4	0.0414 (19)	0.0425 (18)	0.043 (2)	0.0030 (15)	−0.0038 (15)	0.0016 (15)
C5	0.045 (2)	0.0448 (18)	0.048 (2)	−0.0022 (15)	0.0083 (16)	−0.0004 (16)

Geometric parameters (Å, º) top

Br1—C5	1.959 (4)	S4—C4	1.814 (4)
Br2—C3	1.883 (3)	C2—C3	1.345 (5)
S1—C1	1.647 (4)	C4—C5	1.505 (5)
S2—C1	1.723 (3)	C4—H4A	0.9700
S2—C2	1.746 (3)	C4—H4B	0.9700
S3—C3	1.734 (4)	C5—H5A	0.9700
S3—C1	1.737 (3)	C5—H5B	0.9700
S4—C2	1.753 (4)

C1—S2—C2	98.40 (16)	C5—C4—S4	111.3 (2)
C3—S3—C1	97.02 (17)	C5—C4—H4A	109.4
C2—S4—C4	101.05 (16)	S4—C4—H4A	109.4
S1—C1—S2	124.7 (2)	C5—C4—H4B	109.4
S1—C1—S3	122.9 (2)	S4—C4—H4B	109.4
S2—C1—S3	112.34 (19)	H4A—C4—H4B	108.0
C3—C2—S2	114.5 (3)	C4—C5—Br1	110.2 (2)
C3—C2—S4	127.0 (3)	C4—C5—H5A	109.6
S2—C2—S4	118.41 (19)	Br1—C5—H5A	109.6
C2—C3—S3	117.7 (3)	C4—C5—H5B	109.6
C2—C3—Br2	126.1 (3)	Br1—C5—H5B	109.6
S3—C3—Br2	116.2 (2)	H5A—C5—H5B	108.1

C2—S2—C1—S1	177.1 (2)	S2—C2—C3—S3	−0.9 (4)
C2—S2—C1—S3	−2.4 (2)	S4—C2—C3—S3	−177.7 (2)
C3—S3—C1—S1	−177.5 (2)	S2—C2—C3—Br2	−178.3 (2)
C3—S3—C1—S2	2.0 (2)	S4—C2—C3—Br2	4.9 (5)
C1—S2—C2—C3	2.0 (3)	C1—S3—C3—C2	−0.7 (3)
C1—S2—C2—S4	179.1 (2)	C1—S3—C3—Br2	176.9 (2)
C4—S4—C2—C3	−102.6 (3)	C2—S4—C4—C5	69.7 (3)
C4—S4—C2—S2	80.7 (2)	S4—C4—C5—Br1	175.02 (17)

Experimental details

Crystal data
Chemical formula	C₅H₄Br₂S₄
M_r	352.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	4.7892 (12), 20.381 (5), 10.809 (3)
β (°)	96.922 (3)
V (Å³)	1047.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.47
Crystal size (mm)	0.44 × 0.17 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.117, 0.613
No. of measured, independent and observed [I > 2σ(I)] reflections	9101, 2391, 1845
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.081, 1.05
No. of reflections	2391
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.81

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

References

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