5-Isopropyl­idene-1,3-dithiolo[4,5-d][1,3]dithiole-2-thione

Tomura, M.; Yamashita, Y.

doi:10.1107/S160053680901335X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1050

doi:10.1107/S160053680901335X

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5-Isopropylidene-1,3-dithiolo[4,5-d][1,3]dithiole-2-thione

Masaaki Tomura ^a ^* and Yoshiro Yamashita ^b

^aInstitute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan, and ^bDepartment of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
^*Correspondence e-mail: tomura@ims.ac.jp

(Received 6 April 2009; accepted 8 April 2009; online 18 April 2009)

The title compound, C₇H₆S₅, contains a 5-ylidene-1,3-dithiolo[4,5-d][1,3]dithiole-2-thione framework, which is an important synthetic precursor of multi-dimensional organic superconductors and conductors. The molecular framework is planar with an r.m.s. deviation of 0.012 Å for the non-H atoms. In the crystal structure, molecules are linked by short intermolecular S⋯S interactions [3.501 (5) and 3.581 (4) Å], constructing a zigzag molecular tape network along the c axis.

Related literature

For general background, see: Williams et al. (1992 ); Ishiguro et al. (1998 ). For the synthesis of the title compound, see: Misaki et al. (1992 ). For related structures with a 5-ylidene-1,3-dithiolo[4,5-d][1,3]dithiole-2-thione framework, see: Bryce et al. (2000 ); Hock et al. (2002 ); Beck et al. (2006 ). For bond-length data, see: Allen et al. (1987 ). For values of van der Waals radii, see: Bondi (1964 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₇H₆S₅
M_r = 250.47
Triclinic, $[P \overline 1]$
a = 7.082 (6) Å
b = 7.126 (6) Å
c = 10.534 (10) Å
α = 86.12 (3)°
β = 84.77 (3)°
γ = 71.95 (2)°
V = 502.9 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 291 K
0.09 × 0.02 × 0.01 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: none
4550 measured reflections
2643 independent reflections
785 reflections with I > 2σ(I)
R_int = 0.117

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.246
S = 0.84
2643 reflections
112 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ); cell refinement: CrystalClear; data reduction: TEXSAN (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901335X/hg2498sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901335X/hg2498Isup2.hkl

checkCIF report

Comment top

Molecules containing an 5-ylidene-[1,3]dithiolo[4,5-d][1,3]dithiole-2-thione framework are important synthetic precursors of multi-dimensional organic superconductors and conductors. Intermolecular S···S interactions involving peripheral sulfir atoms may increase the dimensionality in solid states and suppress metal-insulator transitions (Williams et al., 1992; Ishiguro et al., 1998). A search for the molecular framework in the Cambridge Structural Database (Version 5.30; Allen, 2002) gave only three examples (Bryce et al., 2000; Hock et al., 2002; Beck et al., 2006). Thus, we report here the molecular and crystal structures of the title compound (I).

The compound (I) crystallizes in the P1 space group with one molecule in the asymmetric unit. The molecular structure is shown in Fig. 1. The bond lengths are within the normal ranges (Allen et al., 1987). The molecular framework is planar with an r.m.s. deviation of 0.012 Å from the least-squares plane. In the crystal structure, the molecules are linked via short intermolecular S···S interactions [3.581 (4) for S1—S1(-x, -y + 3, -z) and 3.501 (5) Å for S5—S5(-x, -y + 3, -z - 1)] to construct a zigzag molecular tape network along the c axis (Fig. 2). The S···S interactions are 0.5–2.8% shorter than the sum of the corresponding van der Waals radii (Bondi, 1964). The molecules also form a π-stacking along the a axis with an interplanar distance of 3.54 (1) Å.

Related literature top

For general background, see: Williams et al. (1992); Ishiguro et al. (1998). For the synthesis of the title compound, see: Misaki et al. (1992). For related structures with a 5-ylidene-[1,3]dithiolo[4,5-d][1,3]dithiole-2-thione framework, see: Bryce et al. (2000); Hock et al. (2002); Beck et al. (2006). For bond-length data, see: Allen et al. (1987). For values of van der Waals radii, see: Bondi (1964). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The title compound (I) was synthesized according to the literature method (Misaki et al., 1992). Brown crystals of (I) suitable for X-ray analysis were grown from a dichloromethane solution.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: TEXSAN (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing diagram of (I), viewed along the b axis. Dashed lines indicate intermolecular S···S interactions.

5-Isopropylidene-1,3-dithiolo[4,5-d][1,3]dithiole-2-thione top

Crystal data top

C₇H₆S₅	Z = 2
M_r = 250.47	F(000) = 256
Triclinic, P1	D_x = 1.654 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 7.082 (6) Å	Cell parameters from 843 reflections
b = 7.126 (6) Å	θ = 3.0–29.7°
c = 10.534 (10) Å	µ = 1.09 mm⁻¹
α = 86.12 (3)°	T = 291 K
β = 84.77 (3)°	Needle, brown
γ = 71.95 (2)°	0.09 × 0.02 × 0.01 mm
V = 502.9 (8) Å³

Data collection top

Rigaku/MSC Mercury CCD diffractometer	785 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.117
Confocal monochromator	θ_max = 31.1°, θ_min = 3.0°
Detector resolution: 14.63 pixels mm^-1	h = −9→9
ϕ and ω scans	k = −10→10
4550 measured reflections	l = −10→15
2643 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.072	H-atom parameters constrained
wR(F²) = 0.246	w = 1/[σ²(F_o²) + (0.0747P)²] where P = (F_o² + 2F_c²)/3
S = 0.84	(Δ/σ)_max < 0.001
2643 reflections	Δρ_max = 0.46 e Å⁻³
112 parameters	Δρ_min = −0.50 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.003 (3)

Crystal data top

C₇H₆S₅	γ = 71.95 (2)°
M_r = 250.47	V = 502.9 (8) Å³
Triclinic, P1	Z = 2
a = 7.082 (6) Å	Mo Kα radiation
b = 7.126 (6) Å	µ = 1.09 mm⁻¹
c = 10.534 (10) Å	T = 291 K
α = 86.12 (3)°	0.09 × 0.02 × 0.01 mm
β = 84.77 (3)°

Data collection top

Rigaku/MSC Mercury CCD diffractometer	785 reflections with I > 2σ(I)
4550 measured reflections	R_int = 0.117
2643 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.246	H-atom parameters constrained
S = 0.84	Δρ_max = 0.46 e Å⁻³
2643 reflections	Δρ_min = −0.50 e Å⁻³
112 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	0.1573 (3)	1.3556 (3)	−0.12379 (19)	0.0502 (6)
S2	0.2864 (3)	0.9827 (3)	−0.25144 (18)	0.0496 (6)
S3	0.1902 (3)	1.1364 (3)	0.13884 (18)	0.0452 (6)
S4	0.3259 (3)	0.7524 (3)	0.00739 (18)	0.0434 (6)
S5	0.1908 (4)	1.3598 (4)	−0.4066 (2)	0.0710 (9)
C1	0.2089 (11)	1.2401 (12)	−0.2662 (7)	0.048 (2)
C2	0.2080 (10)	1.1425 (11)	−0.0257 (7)	0.0427 (19)
C3	0.2706 (10)	0.8745 (11)	0.1547 (7)	0.0407 (18)
C4	0.2678 (9)	0.9729 (12)	−0.0871 (7)	0.0385 (17)
C5	0.2896 (10)	0.7741 (12)	0.2681 (8)	0.045 (2)
C6	0.2430 (11)	0.8811 (12)	0.3900 (7)	0.056 (2)
H6A	0.3602	0.8472	0.4365	0.084*
H6B	0.1395	0.8439	0.4405	0.084*
H6C	0.1994	1.0210	0.3711	0.084*
C7	0.3596 (11)	0.5529 (11)	0.2761 (7)	0.049 (2)
H7A	0.3818	0.5036	0.1917	0.073*
H7B	0.2603	0.5056	0.3239	0.073*
H7C	0.4816	0.5078	0.3179	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0512 (13)	0.0409 (13)	0.0522 (14)	−0.0080 (10)	−0.0035 (10)	0.0126 (10)
S2	0.0551 (14)	0.0473 (14)	0.0417 (12)	−0.0113 (11)	0.0001 (9)	0.0038 (10)
S3	0.0519 (13)	0.0337 (12)	0.0451 (12)	−0.0077 (10)	0.0010 (9)	−0.0006 (9)
S4	0.0513 (13)	0.0308 (12)	0.0429 (12)	−0.0058 (10)	−0.0014 (9)	0.0009 (9)
S5	0.0751 (18)	0.078 (2)	0.0561 (16)	−0.0221 (15)	−0.0135 (12)	0.0300 (13)
C1	0.049 (5)	0.044 (5)	0.047 (5)	−0.007 (4)	−0.011 (4)	0.012 (4)
C2	0.046 (5)	0.031 (5)	0.047 (5)	−0.008 (4)	−0.002 (4)	−0.003 (4)
C3	0.040 (4)	0.039 (5)	0.040 (4)	−0.010 (4)	0.004 (3)	−0.001 (3)
C4	0.032 (4)	0.038 (4)	0.040 (4)	−0.004 (3)	−0.006 (3)	0.006 (3)
C5	0.039 (4)	0.037 (5)	0.058 (5)	−0.014 (4)	0.013 (4)	−0.001 (4)
C6	0.066 (6)	0.050 (6)	0.051 (5)	−0.016 (5)	0.002 (4)	−0.005 (4)
C7	0.056 (5)	0.039 (5)	0.049 (5)	−0.016 (4)	0.002 (4)	0.014 (4)

Geometric parameters (Å, º) top

S1—C1	1.716 (8)	C3—C5	1.346 (10)
S1—C2	1.738 (8)	C5—C6	1.496 (10)
S2—C4	1.723 (7)	C5—C7	1.497 (10)
S2—C1	1.744 (8)	C6—H6A	0.9600
S3—C2	1.725 (8)	C6—H6B	0.9600
S3—C3	1.775 (8)	C6—H6C	0.9600
S4—C4	1.758 (7)	C7—H7A	0.9600
S4—C3	1.783 (7)	C7—H7B	0.9600
S5—C1	1.652 (7)	C7—H7C	0.9600
C2—C4	1.341 (10)

S1···S1ⁱ	3.581 (4)	S5···S5ⁱⁱ	3.501 (5)

C1—S1—C2	96.7 (4)	C3—C5—C6	120.7 (8)
C4—S2—C1	94.9 (4)	C3—C5—C7	121.2 (7)
C2—S3—C3	94.4 (3)	C6—C5—C7	118.1 (7)
C4—S4—C3	94.3 (4)	C5—C6—H6A	109.5
S5—C1—S1	123.5 (5)	C5—C6—H6B	109.5
S5—C1—S2	122.1 (5)	H6A—C6—H6B	109.5
S1—C1—S2	114.4 (4)	C5—C6—H6C	109.5
C4—C2—S3	119.7 (6)	H6A—C6—H6C	109.5
C4—C2—S1	115.0 (6)	H6B—C6—H6C	109.5
S3—C2—S1	125.3 (5)	C5—C7—H7A	109.5
C5—C3—S3	123.3 (6)	C5—C7—H7B	109.5
C5—C3—S4	122.0 (6)	H7A—C7—H7B	109.5
S3—C3—S4	114.6 (4)	C5—C7—H7C	109.5
C2—C4—S2	118.9 (6)	H7A—C7—H7C	109.5
C2—C4—S4	117.0 (6)	H7B—C7—H7C	109.5
S2—C4—S4	124.1 (5)

C2—S1—C1—S5	180.0 (5)	S3—C2—C4—S2	−179.5 (4)
C2—S1—C1—S2	−0.9 (5)	S1—C2—C4—S2	−0.4 (8)
C4—S2—C1—S5	179.9 (5)	S3—C2—C4—S4	−0.3 (8)
C4—S2—C1—S1	0.8 (5)	S1—C2—C4—S4	178.8 (3)
C3—S3—C2—C4	0.3 (6)	C1—S2—C4—C2	−0.2 (6)
C3—S3—C2—S1	−178.7 (5)	C1—S2—C4—S4	−179.3 (5)
C1—S1—C2—C4	0.8 (6)	C3—S4—C4—C2	0.1 (6)
C1—S1—C2—S3	179.8 (5)	C3—S4—C4—S2	179.2 (4)
C2—S3—C3—C5	179.6 (7)	S3—C3—C5—C6	−0.2 (10)
C2—S3—C3—S4	−0.2 (4)	S4—C3—C5—C6	179.7 (5)
C4—S4—C3—C5	−179.8 (7)	S3—C3—C5—C7	−179.5 (5)
C4—S4—C3—S3	0.1 (4)	S4—C3—C5—C7	0.3 (10)

Symmetry codes: (i) −x, −y+3, −z; (ii) −x, −y+3, −z−1.

Experimental details

Crystal data
Chemical formula	C₇H₆S₅
M_r	250.47
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	7.082 (6), 7.126 (6), 10.534 (10)
α, β, γ (°)	86.12 (3), 84.77 (3), 71.95 (2)
V (Å³)	502.9 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.09 × 0.02 × 0.01

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4550, 2643, 785
R_int	0.117
(sin θ/λ)_max (Å⁻¹)	0.727

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.246, 0.84
No. of reflections	2643
No. of parameters	112
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.50

Computer programs: CrystalClear (Rigaku/MSC, 2006), TEXSAN (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Acknowledgements

The authors thank the Instrument Center of the Institute for Molecular Science for the X-ray structure analysis.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Beck, J., Daniels, J., Roloff, A. & Wagner, W. (2006). Dalton Trans. pp. 1174–1180. Web of Science CSD CrossRef Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Bryce, M. R., Finn, T., Moore, A. J. & Batsanov, A. S. (2000). Eur. J. Org. Chem. pp. 51–60. CrossRef Google Scholar
Hock, J., Gompper, R. & Polborn, K. (2002). Private communication (refcode VADDIO). CCDC, Cambridge, England. Google Scholar
Ishiguro, T., Yamaji, K. & Saito, G. (1998). Organic Superconductors, edited by P. Fulde, Springer Series Solid-State Science, Vol. 88. Berlin, Heidelberg: Springer. Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Misaki, Y., Nishikawa, H., Kawakami, K., Uehara, T. & Yamabe, T. (1992). Tetrahedron Lett. 33, 4321–4324. CrossRef CAS Web of Science Google Scholar
Rigaku/MSC (2004). TEXSAN. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2006). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Williams, J. M., Ferraro, J. R., Thorn, R. J., Carlson, K. D., Geiser, U., Wang, H. H., Kini, A. M. & Whangbo, M. H. (1992). Organic Superconductors. Englewood Cliffs, NJ: Prentice Hall. Google Scholar