2,5-Bis(1,3-dithiol-2-yl­idene)-1,3-dithiol­ane-4-thione

Kazumasa Ueda; Kenta Suzuki; Kei Kunimoto; Kenji Yoza

doi:10.1107/S1600536811051518

. 2011 Dec 10;68(Pt 1):o52. doi: 10.1107/S1600536811051518

2,5-Bis(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione

Kazumasa Ueda ^a,^b,^*, Kenta Suzuki ^b, Kei Kunimoto ^b, Kenji Yoza ^c

PMCID: PMC3254410 PMID: 22259554

Abstract

The asymmetric unit of the title compound, C₉H₄S₇, contains two independent molecules, in one of which the central five-membered ring is disordered over two orientations in a 0.924 (3):0.076 (3) ratio. The molecular skeleton is almost planar: the average distance of the atoms from their mean plane is 0.128 (7) Å in the ordered molecule, and 0.088 (5) and 0.123 (2) Å in the major and minor disorder components, respectively. The ordered and disordered molecules form separate columns by stacking along the b axis. Adjacent columns interact via short S⋯S [3.33 (2), 3.434 (3), 3.444 (2), 3.503 (2), 3.519 (3) and 3.53 (4) Å] and S⋯H [2.814 (2), 2.87 (7), 2.92 (2), 2.9269 (18), 2.93 (2), 2.94 (2), 2.939 (2), 2.967 (2) and 2.974 (1) Å] contacts.

Related literature

For background to 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione derivatives, see: Iwamatsu et al. (1999 ▶, 2000 ▶); Wang et al. (2005 ▶, 2007 ▶); Hiraoka et al. (2005 ▶); Fujiwara et al. (2006 ▶, 2007 ▶); Ueda & Yoza (2009a ▶,b ▶,c ▶). For the synthesis, see: Ueda et al. (2010 ▶). For van der Waals radii, see: Bondi (1964 ▶).

Experimental

Crystal data

C₉H₄S₇
M _r = 336.54
Monoclinic,
a = 17.669 (5) Å
b = 3.9110 (11) Å
c = 18.380 (5) Å
β = 108.177 (4)°
V = 1206.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 93 K
0.09 × 0.02 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.894, T _max = 0.975
6965 measured reflections
4975 independent reflections
3396 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.107
S = 0.98
4975 reflections
344 parameters
421 restraints
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ▶), 1849 Friedel pairs
Flack parameter: −0.18 (18)

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); 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: XCIF (Bruker, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811051518/fy2030sup1.cif

e-68-00o52-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051518/fy2030Isup2.hkl

e-68-00o52-Isup2.hkl^{(243.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811051518/fy2030Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Donor molecules featuring a skeleton of 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione (I) and 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-quinone (II) are used for the preparation of charge transfer (CT) complexes with magnetic metal anions (Wang et al., 2005, 2007; Hiraoka et al., 2005; Fujiwara et al., 2006, 2007). In CT salts these molecules can form unique crystal structures with channels in addition to the usual layer stacking structures as a result of intermolecular S···S contacts. Through an investigation of the unique molecular arrangements of the derivatives of (I) and (II) in their crystals, we found that the derivatives of (I) are stacked in the same orientation and the derivatives of (II) are alternately stacked in opposite directions (Ueda & Yoza, 2009a, 2009b, 2009c; Ueda et al., 2010). This result suggests that the stacking orientation of the derivatives is largely influenced by their molecular skeletons. To identify the stacking orientation of skeleton (I), we synthesized (I) and investigated its crystal structure.

The asymmetric unit contains two crystallographically independent molecules. One of the two independent molecules shows orientational disorder in the C=S containing five-membered ring with occupancies of 0.924 (3) (molecule A) and 0.076 (3) (molecule B). The other molecule of the asymmetric unit, molecule C, is ordered. The framework of (I) is almost planar: the mean deviation of the atoms from their mean plane is 0.088 (5) Å for A, 0.123 (2) Å for B and 0.128 (7) Å for C.

In the crystal structure, two different orientations of the molecules are present. Both orientations enclose a dihedral angle of about 27° with the ac plane, but the mean plane of the molecules is nearly parallel either with (011) or with (01–1) (Fig. 2). Molecules with the same orientation form stacks along the b axis. The stacked molecules are separated by interplanar distances greater than 3.54 Å and have a fairly poor overlap. However some effective side-by-side contacts are observed between molecules of adjacent columns (Fig. 3). The interaction between adjacent columns is accomplished through contacts between different sulfur atoms: S9···S3Bⁱ = 3.33 (2) Å [(i): 1–x, 1/2+y, 1–z]; S8···S3Aⁱⁱ = 3.434 (3) Å [(ii): x, 1+y, 1+z]; S6···S6ⁱⁱⁱ = 3.444 (2) Å [(iii):–x, 1/2+y, –z]; S3C···S10ⁱ = 3.503 (2) Å; S4···S9ⁱ = 3.519 (3) Å; S2B···S3A^iv = 3.53 (4) Å [(iv): x, 1+y, z]; and through contacts between sulfur and hydrogen atoms: S2C···H9Aⁱ = 2.814 (2) Å, S1B···H15A = 2.87 (7); S3B···H11A^iv = 2.92 (2) Å; S5···H6Aⁱ = 2.9269 (18) Å; S3B···H11A^v = 2.93 (2) Å [(v): x, y, z–1]; S3B···H12A^vi = 2.94 (2) Å [(vi): 1–x, –1/2+y, 1–z]; S2C···H9A^vii = 2.939 (2)Å [(vii): –x, –1/2+y, 1–z]; S3A···H8Aⁱⁱⁱ = 2.967 (2) Å; S3C···H14A^viii = 2.974 (1) Å [(viii): –x, 1/2+y, 1–z]. These distances are shorter than the sum of corresponding van der Waals radii, i.e., 3.60 Å for S···S and 3.00 Å for S···H (Bondi, 1964).

Experimental

Compound (I) was synthesized by a modification of the method used for the preparation of 2-[4,5-bis(ethylsulfanyl)-1,3-dithiol-2-ylidene]-5-(4,5-diiodo-1,3-dithiol-2-ylidene)-1,3-dithiolan-4-thione (Ueda et al., 2010). Bis(tetra-n-butylammonium)bis[2-(1,3-dithiol-2-ylidene)-1,3-dithiole-4,5-bis(thiolate)]zinc (194 mg, 0.170 mmol) reacted with 2-methylsulfanyl-1,3-dihiole-2-ylium tetrafluoroborate (89.3 mg, 0.378 mmol) in THF-DMF (4:1 = v/v) at room temperature under nitrogen, and stirring was carried out for 12 h. After separation of the reaction mixture by column chromatography on silica gel (eluent CS₂) followed by recrystallization from 1:10 CS₂/hexane, (I) was obtained as black needles in 79% yield.