3-(2-Thioxo-1,3-dithiol-4-ylsulfan­yl)­propane­nitrile

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

doi:10.1107/S1600536808031711

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2078

doi:10.1107/S1600536808031711

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3-(2-Thioxo-1,3-dithiol-4-ylsulfanyl)propanenitrile

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

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

(Received 19 September 2008; accepted 1 October 2008; online 4 October 2008)

The title compound, C₆H₅NS₄, consists of a planar 2-thioxo-1,3-dithiol-4-ylsulfanyl unit [maximum deviation from the ring plane = 0.0325 (2) Å], with a cyanoethylsulfanyl substituent in the 4-position. In the crystal structure, weak intermolecular C—H⋯S hydrogen bonds together with S⋯N interactions [3.260 (5) Å] form two-dimensional layers in the bc plane.

Related literature

For background to the chemistry of dithiole-2-thiones and tetrathiafulvenes, see: Chen et al. (2005 ); Fabre (2004 ); Segura & Martin (2001 ). For the preparation of the title compound, see: Liu et al. (2002 ). For a related structure, see: Jia et al. (2001 ).

Experimental

Crystal data

C₆H₅NS₄
M_r = 219.35
Monoclinic, P 2₁ /c
a = 5.2961 (9) Å
b = 10.8917 (19) Å
c = 16.031 (3) Å
β = 97.302 (2)°
V = 917.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 295 (2) K
0.35 × 0.27 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.728, T_max = 0.808
6626 measured reflections
1710 independent reflections
1525 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.072
S = 1.07
1710 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5B⋯S3ⁱ	0.97	2.86	3.813 (2)	167
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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/S1600536808031711/sj2541sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031711/sj2541Isup2.hkl

checkCIF report

Comment top

Tetrathiafulvalenes (TTFs) and their charge-transfer salts have become an interesting topic of research, due to their high electrical conductivity and superconducting properties (Segura & Martin, 2001). 1,3-Dithiole-2-thiones, important precursors to TTF derivatives, have also attracted attention (Chen, et al.; 2005; Fabre, 2004). In 2001, 4-alkylthio-1,3- dithiole-2-thione, a key kind of 1,3-dithiole-2-thiones was developed by a facile approach (Jia, et al., 2001). We report here the structure of the title compound (Fig. 1), which was prepared by the reaction of di(tetraethylammonium) bis(1,3-dithiol-2- thione-4,5-dithiolate)zincate and 3-bromopropionitrile in the presence of pyridine hydrochloride.

The atoms of the five-membered dithiole ring and the doubly-bonded atom S3 are nearly coplanar, with a maximum deviation from the least-squares plane of only 0.0325 (2) Å (S1). However, S4 deviates considerably from the plane, 0.0775 (4) Å, which is very similar to the structure of 4,5-bis(2-cyanoethylthio)-1,3-dithiol-2-one (Liu, et al., 2002). The cyanoethylsulfanyl group is substituted on the C2 atom of the dithiole ring. The C4—S4 bond length (1.8191 (19) Å) is typical of a single bond, while the other C—S bond lengths range from 1.650 (2) Å to 1.7435 (19) Å, suggesting a degree of conjugation in the dithiol-2-thione system. In the crystal structure weak intermolecular C5—H5B···S3 hydrogen bonds, Table 1, together with S···N (3.260 (5) Å) interactions form two dimensional layers in the bc plane (Fig. 2).

Related literature top

For background to the chemistry of dithiole-2-thiones and tetrathiafulvenes, see: Chen et al. (2005); Fabre (2004); Segura & Martin (2001). For the preparation of the title compound, see: Liu et al. (2002). For a related structure, see: Jia et al. (2001).

Experimental top

The title compound was prepared according to the literature (Jia, et al., 2001). Orange block-like single crystals were obtained from slow evaporation of a dichloromethane solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. Crystal packing of the title compound viewed down the a axis.

3-(2-Thioxo-1,3-dithiol-4-ylsulfanyl)propanenitrile top

Crystal data top

C₆H₅NS₄	F(000) = 448
M_r = 219.35	D_x = 1.588 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3529 reflections
a = 5.2961 (9) Å	θ = 2.6–27.9°
b = 10.8917 (19) Å	µ = 0.97 mm⁻¹
c = 16.031 (3) Å	T = 295 K
β = 97.302 (2)°	Block, yellow
V = 917.2 (3) Å³	0.35 × 0.27 × 0.23 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1710 independent reflections
Radiation source: fine-focus sealed tube	1525 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.728, T_max = 0.808	k = −12→13
6626 measured reflections	l = −19→19

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0339P)² + 0.3313P] where P = (F_o² + 2F_c²)/3
1710 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₆H₅NS₄	V = 917.2 (3) Å³
M_r = 219.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.2961 (9) Å	µ = 0.97 mm⁻¹
b = 10.8917 (19) Å	T = 295 K
c = 16.031 (3) Å	0.35 × 0.27 × 0.23 mm
β = 97.302 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1710 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1525 reflections with I > 2σ(I)
T_min = 0.728, T_max = 0.808	R_int = 0.023
6626 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	Δρ_max = 0.19 e Å⁻³
1710 reflections	Δρ_min = −0.34 e Å⁻³
100 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	0.21596 (10)	1.03249 (5)	0.12572 (3)	0.05315 (17)
S2	0.34613 (11)	0.99269 (5)	0.30276 (3)	0.05650 (17)
S3	−0.06717 (11)	1.17189 (6)	0.24268 (4)	0.05929 (17)
S4	0.60268 (9)	0.85154 (5)	0.07595 (3)	0.05352 (16)
N1	−0.1988 (4)	0.62697 (19)	−0.06631 (14)	0.0688 (5)
C1	0.1519 (3)	1.07055 (18)	0.22542 (12)	0.0433 (4)
C2	0.4470 (3)	0.92099 (17)	0.15433 (12)	0.0422 (4)
C3	0.5061 (4)	0.90441 (19)	0.23696 (12)	0.0493 (5)
H3	0.6287	0.8476	0.2583	0.059*
C4	0.3347 (4)	0.79990 (19)	0.00199 (12)	0.0486 (5)
H4A	0.2071	0.8642	−0.0051	0.058*
H4B	0.3921	0.7852	−0.0522	0.058*
C5	0.2159 (4)	0.6842 (2)	0.03091 (14)	0.0573 (5)
H5A	0.3375	0.6174	0.0321	0.069*
H5B	0.1748	0.6959	0.0876	0.069*
C6	−0.0165 (4)	0.65095 (19)	−0.02465 (14)	0.0531 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0531 (3)	0.0661 (3)	0.0389 (3)	0.0149 (2)	0.0007 (2)	0.0015 (2)
S2	0.0672 (4)	0.0630 (3)	0.0382 (3)	0.0049 (3)	0.0027 (2)	0.0019 (2)
S3	0.0548 (3)	0.0623 (4)	0.0621 (3)	0.0057 (2)	0.0123 (3)	−0.0081 (3)
S4	0.0401 (3)	0.0667 (3)	0.0525 (3)	0.0006 (2)	0.0008 (2)	−0.0142 (2)
N1	0.0643 (12)	0.0674 (12)	0.0708 (13)	−0.0096 (10)	−0.0057 (10)	−0.0105 (10)
C1	0.0420 (10)	0.0451 (10)	0.0424 (10)	−0.0085 (8)	0.0044 (8)	−0.0009 (8)
C2	0.0372 (9)	0.0432 (10)	0.0444 (10)	−0.0041 (7)	−0.0018 (7)	−0.0035 (8)
C3	0.0510 (11)	0.0464 (11)	0.0487 (11)	0.0034 (9)	−0.0009 (9)	0.0016 (9)
C4	0.0529 (11)	0.0505 (11)	0.0402 (10)	0.0001 (9)	−0.0022 (8)	−0.0024 (8)
C5	0.0569 (12)	0.0593 (13)	0.0531 (12)	−0.0052 (10)	−0.0030 (10)	0.0069 (10)
C6	0.0549 (12)	0.0503 (12)	0.0541 (12)	−0.0041 (9)	0.0070 (10)	−0.0044 (9)

Geometric parameters (Å, º) top

S1—C1	1.7262 (19)	C2—C3	1.334 (3)
S1—C2	1.7435 (19)	C3—H3	0.9300
S2—C3	1.727 (2)	C4—C5	1.508 (3)
S2—C1	1.729 (2)	C4—H4A	0.9700
S3—C1	1.650 (2)	C4—H4B	0.9700
S4—C2	1.759 (2)	C5—C6	1.470 (3)
S4—C4	1.8191 (19)	C5—H5A	0.9700
N1—C6	1.133 (3)	C5—H5B	0.9700

C1—S1—C2	97.91 (9)	C5—C4—H4A	109.1
C3—S2—C1	97.39 (9)	S4—C4—H4A	109.1
C2—S4—C4	101.59 (9)	C5—C4—H4B	109.1
S3—C1—S1	122.76 (12)	S4—C4—H4B	109.1
S3—C1—S2	125.08 (12)	H4A—C4—H4B	107.9
S1—C1—S2	112.15 (11)	C6—C5—C4	111.69 (18)
C3—C2—S1	115.08 (15)	C6—C5—H5A	109.3
C3—C2—S4	125.36 (15)	C4—C5—H5A	109.3
S1—C2—S4	119.25 (11)	C6—C5—H5B	109.3
C2—C3—S2	117.36 (16)	C4—C5—H5B	109.3
C2—C3—H3	121.3	H5A—C5—H5B	107.9
S2—C3—H3	121.3	N1—C6—C5	178.4 (2)
C5—C4—S4	112.31 (14)

C2—S1—C1—S2	3.39 (12)	C4—S4—C2—S1	−52.73 (13)
C3—S2—C1—S3	178.04 (13)	S1—C2—C3—S2	0.7 (2)
C3—S2—C1—S1	−3.08 (12)	S4—C2—C3—S2	174.29 (11)
C1—S1—C2—C3	−2.54 (17)	C1—S2—C3—C2	1.47 (18)
C1—S1—C2—S4	−176.53 (11)	C2—S4—C4—C5	−78.01 (17)
C4—S4—C2—C3	133.94 (18)	S4—C4—C5—C6	173.85 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···S3ⁱ	0.97	2.86	3.813 (2)	167

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₅NS₄
M_r	219.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	5.2961 (9), 10.8917 (19), 16.031 (3)
β (°)	97.302 (2)
V (Å³)	917.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.35 × 0.27 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.728, 0.808
No. of measured, independent and observed [I > 2σ(I)] reflections	6626, 1710, 1525
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.07
No. of reflections	1710
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.34

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···S3ⁱ	0.97	2.86	3.813 (2)	167

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

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

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