5-(4,5-Diiodo-1,3-dithiol-2-yl­idene)-4′,5′-bis­(methyl­sulfan­yl)-2,2′-bi-1,3-dithiole-4(5H)-thione

Kazumasa Ueda; Kenji Yoza

doi:10.1107/S1600536809042573

. 2009 Oct 23;65(Pt 11):o2831. doi: 10.1107/S1600536809042573

5-(4,5-Diiodo-1,3-dithiol-2-ylidene)-4′,5′-bis(methylsulfanyl)-2,2′-bi-1,3-dithiole-4(5H)-thione

Kazumasa Ueda ^a,^*, Kenji Yoza ^b

PMCID: PMC2970979 PMID: 21578421

Abstract

The molecular skeleton of the title molecule, C₁₁H₆I₂S₉, is nearly planar [maximum deviation 0.052 (3) Å] except for the two methyl groups. In the crystal, molecules related by translation along b axis are associated into columns through π–π interactions between the five-membered rings, with a centroid–centroid distance of 3.593 (5) Å. Interaction between adjacent columns is accomplished by short S⋯I contacts of 3.2099 (4) Å.

Related literature

For background to tetrathiafulvalenothioquinone-1,3-dithiolemethide derivatives, see: Iwamatsu et al. (2000 ▶); Wang et al. (2005 ▶, 2007 ▶); Hiraoka et al. (2005 ▶); Fujiwara et al. (2006 ▶, 2007 ▶). For details of the synthesis, see Iwamatsu et al. (1999 ▶). For intermolecular S⋯I contacts, see: Ahlsen & Strømme (1974 ▶); Herbstein & Schwortzer (1984 ▶); Freemanm et al. (1988 ▶); Bigoli et al. (1996 ▶). For van der Waals radii, see: Bondi (1964 ▶).

Experimental

Crystal data

C₁₁H₆I₂S₉
M _r = 680.50
Monoclinic,
a = 29.540 (7) Å
b = 5.3543 (13) Å
c = 25.163 (6) Å
β = 103.544 (3)°
V = 3869.2 (16) Å³
Z = 8
Mo Kα radiation
μ = 4.21 mm⁻¹
T = 93 K
0.55 × 0.18 × 0.01 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.205, T _max = 0.979
10568 measured reflections
4387 independent reflections
3536 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.090
S = 1.07
4387 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 3.45 e Å⁻³
Δρ_min = −2.31 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: XCIF (Bruker, 2001 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809042573/cv2627sup1.cif

e-65-o2831-sup1.cif^{(15.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042573/cv2627Isup2.hkl

e-65-o2831-Isup2.hkl^{(215KB, hkl)}

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

Acknowledgments

This work was supported by the Hamashin Regional Development Foundation and the Japan Chemical Innovation Institute.

supplementary crystallographic information

Comment

Charge transfer (CT) complexes of new donor molecules featuring a skeleton of tetrathiafulvalenothioquinone-1,3-dithiolemethide with magnetic metal ions are used for the preparation of magnetic molecular conductors, especially ferromagnetic semiconductors and metals (Wang et al., 2005, 2007; Hiraoka et al., 2005; Fujiwara et al., 2006, 2007). In the CT salts of an ethylendithiotetrathiafulvalenothioquinone-1,3-dithiolemethide donor with CuBr₂, the Cu atom (a Lewis acid) of CuBr₂ is bound to the S atom (a Lewis base) of a C=S group in the donor to form a new type of π/d molecular system (Iwamatsu et al., 2000). The introduction of Lewis acids, such as iodine atoms, as substituents in the molecular skeleton is expected to enhance intermolecular interaction through the formation of S···I contacts. These contacts are of special interest in these structures as they may increase the dimensionality of aggregation in the solid-state. In this context, the crystal structure of the title compound, (I), was investigated.

The molecular framework of (I), Fig. 1, except for two methylthio groups, is almost planar [maximum deviation 0.052 (3) Å]. The displacements of atoms S8, S9, I1 and I2 relative to the plane of the skeleton are -0.164 (3), -0.151 (3), 0.164 (3) and 0.277 (3) Å, respectively. The torsion angles of the two methylthio groups are -136.95° for C10—S8—C8—C9 and 80.97° for C11—S9—C9—C8. In the crystal structure, two different arrangements of the molecules are present. One arrangement has a dihedral angle of 48.41° to the ac plane, while the other has a dihedral angle of 131.51° to the ac plane. As a result, the molecules are stacked in the same orientations to form one-dimensional columns along the [110] and [1–10] directions (Fig. 2). Although the weak interaction between stacked molecules in the columns is accomplished through contacts between different sulfur atoms [S3···S5ⁱ = 3.5916 (6) Å; symmetry code: (i) +x, 1 + y, +z] is shorter than the sum of van der Waals radii of two sulfur atoms (3.60 Å), stacked molecules are separated by interplanar distances greater than 3.54 Å and have fairly poor overlap (Bondi, 1964). However, some effective side-by-side contacts are observed between molecules of adjacent columns. The interaction between columns is accomplished by contacts between sulfur and iodine atoms [S3···I1ⁱⁱ = 3.2099 (4) Å; symmetry code: (ii) 2 - x, -1 + y, 1/2 - z] along the a axis (Fig. 3). This distance is shorter than the sum of van der Waals radii of sulfur and iodine atoms (3.78 Å). In the two molecules bound by sulfur-iodine interaction, the C5—S3—I1ⁱⁱ—C1ⁱⁱ moieties are not planar and almost linear S3—I1ⁱⁱ—C1ⁱⁱfragments lie roughly perpendicular to the molecular skeleton [torsion angle of -81.47° for I1ⁱ—S3—C5—S5 and torsion angle of 97.60° for I1ⁱ—S3—C5—C4], and the dihedral angle of the molecules is 83.11°. Such sulfur-iodine interactions have been observed previously (Ahlsen et al.,1974; Herbstein et al., 1984; Freemanm et al., 1988; Bigoli et al., 1996).

Experimental

Compound (I) was synthesized by a modification of the method used for the preparation of bis(methylthio)tetrathiafulvalenothioquinone-1,3-dithiolemethide (Iwamatsu et al.,1999). Bis(tetraethylammonium)bis(2,3-bis(methylthio)tetrathiafulvalenyl-6,7-dithiolato)zinc (269 mg, 0.258 mmol) was reacted with 4,5-diiodo-2-methylthio-1,3-dithiole-2,3-dithiolium tetrafluoroborate (535 mg, 1.10 mmol) in THF-DMF (5:1 = 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 CS₂/n-hexane, (I) was obtained as black needles in 72% yield.