trans-Di-μ-iodido-bis­[(3H-1,2-benzodithiole-3-thione)iodidomercury(II)]

El Adoui Laifa; Lamia Bendjeddou; Naouel Boudraa; Slimane Dahaoui; Claude Lecomte

doi:10.1107/S1600536809032152

. 2009 Aug 19;65(Pt 9):m1080–m1081. doi: 10.1107/S1600536809032152

trans-Di-μ-iodido-bis[(3H-1,2-benzodithiole-3-thione)iodidomercury(II)]

El Adoui Laifa ^a, Lamia Bendjeddou ^a,^*, Naouel Boudraa ^a, Slimane Dahaoui ^b, Claude Lecomte ^b

PMCID: PMC2970135 PMID: 21577433

Abstract

The complete molecule of the dinuclear title compound, [Hg₂I₄(C₇H₄S₃)₂], is generated by crystallographic inversion symmetry. The complex has a dimeric structure in which each Hg^II ion adopts a tetrahedral geometry and is coordinated by two bridging I atoms, one terminal iodide ion and one thiocarbonyl S atom (C=S) of the ligand. The square plane formed by the Hg and I atoms and their symmetry counterparts makes a dihedral angle of 89.66 (3)° with the DDT plane. There is no classical hydrogen bonding, but weak S⋯S interactions of 3.4452 (7) and 3.6859 (7) Å maintain the cohesion of the crystal structure.

Related literature

For S⋯S interactions in sulfur-rich organic donor–acceptor compounds or radical salts, see: Cassoux et al. (1991 ▶); Klinsberg & Schraber (1962 ▶). For the effects on the molecular packing and S⋯S contacts of modifying the structure of the organic molecule or changing the counter-ion or the co-crystallized solvent, see: Pullen & Olk (1999 ▶); Schlueter et al. (1996 ▶). In this context, a series of polymeric complexes has been reported with Ag⁺(Dai, Munakata, Kuroda-Sowa et al., 1997 ▶; Dai, Kudora-Sowa et al., 1997 ▶) and a tetra-nuclear CuI₄ cluster (Dai, Munakata, Wu et al., 1997 ▶). For comparison bond lengths and angles in related chloride-bridged dimeric Hg(II) complexes, see: Brodersen & Hummel (1987 ▶); Dean (1978 ▶).

Experimental

Crystal data

[Hg₂I₄(C₇H₄S₃)₂]
M _r = 1277.40
Triclinic,
a = 7.86285 (10) Å
b = 8.19304 (11) Å
c = 10.46506 (13) Å
α = 105.2917 (11)°
β = 98.3031 (10)°
γ = 105.6957 (11)°
V = 608.92 (2) Å³
Z = 1
Mo Kα radiation
μ = 18.18 mm⁻¹
T = 100 K
0.16 × 0.1 × 0.08 mm

Data collection

Oxford Diffraction SuperNova diffractometer with an Atlas detector
Absorption correction: analytical (Clark et al., 1995 ▶) T _min = 0.167, T _max = 0.347
44929 measured reflections
4951 independent reflections
4698 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.015
wR(F ²) = 0.037
S = 1.05
4951 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −1.55 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3I (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032152/bq2156sup1.cif

e-65-m1080-sup1.cif^{(13.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032152/bq2156Isup2.hkl

e-65-m1080-Isup2.hkl^{(237.6KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Hg1—S1	2.5169 (7)
Hg1—I2	2.6599 (2)
Hg1—I1	2.8148 (4)
Hg1—I1ⁱ	3.1002 (4)

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S1—Hg1—I2	138.842 (15)
S1—Hg1—I1	98.374 (17)
I2—Hg1—I1ⁱ	103.851 (13)
I1—Hg1—I1ⁱ	95.210 (10)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Technical support (X-ray measurements at SCDRX) from Université Henry Poincaré, Nancy 1 is gratefully acknowledged.

supplementary crystallographic information

Comment

Sulfur-rich organic donor-acceptor compounds or radical salts are widely used as bricks in the crystal architecture of molecular materials. The S···S interaction or contact in this compounds is one of the most important contributors to their unique electronic properties (Klinsberg et al., 1962, Cassoux et al., 1991). It has been understood that intermolecular S···S interactions are providing the pass way of the electrons in the molecular conductor. Up to now great efforts have been made to design the molecular packing and to strengthen the S···S contacts by modifying the structure of the organic molecule itself, by changing the size of the conter ion and even the co-crystallized solvent molecules (Pullen et al., 1999; Schlueter et al., 1996). In this context a series of polymeric complexes have been reported with (Ag+) metal (Dai, Munakata, Kuroda-Sowa et al., 1997; Dai, Kudora-Sowa et al., 1997) and a tetra-nuclear cluster CuI4 (Dai, Munakata, Wu et al., 1997). In this paper an organic-inorganic hybrid compound is reported with the formula: [Hg₂I₄(DTT)₂](1),DTT=C₇H₄S₃, 4,5-benzo-1,2-dithiole-3-thione.

The complex [Hg₂ (C₁₄H₈S₆)I₄] is found to be a halogen-bridged dimer related by an inversion centre. An ORTEP view of the complex together with the atomic labeling scheme is given in Fig.1. The mercury atom is four-coordinated with significant distortion from tetrahedral. Two of these bonds are formed by two asymmetric iodide bridges, while the remaining two bonds are formed by a terminal iodide ion and thiocarbonyl sulfur atom of the ligand. The square-like plane formed by mercury and iodide atoms with their symmetry counterparts makes 89.66 (3)° dihedral angle with DDT plane.

The selected bond lengths and angles for the complex are listed in table (1) in which the data of the dimeric unit are comparable to those reported in the literature for related chloride bridged dimeric Hg(II) complexes (Brodersen et al., 1987; Dean, 1978).

Coordination modes of the C₇H₄S₃ ligand have been classified into four types (Dai, Kudora-Sowa et al., 1997). They are monodentate coordination by the thiocarbonyl group (type I), bridge formation by the sulfur of the thiocarbonyl group (type II), bidentate coordination by both thiocarbonyl group and thioether group (type III) and tridentate coordination by the thiocarbonyl sulfur (acting as a bridge) and the thioether sulfur (type IV).

Although the coordination of the ligand in type I has been found in complex: [Cu₄I₄(C₅H₄S₅)₄]∞ and{[Ag(C₅H₄S₅)₃]ClO₄CH₃CN}₂ (Dai, Kudora-Sowa et al., 1997; Dai, Munakata, Wu et al., 1997), other coordination types co-exist in these complexes.

[Hg₂(C₇H₄S₃)₂I₄] is the complex found in the coordination of the ligands only in type I. The S(2)—C(1)distance of 1.703 (2)Å in this compound is longer than that for the free ligand 1.645Å (Dai, Munakata, Kuroda-Sowa et al., 1997). This longer S(2)—C(1) distance attributes to the strong coordination of the thiocarbonyl sulfur to soft mercury(II) ion that weakens the S(2)—C(1) bond.

The absence of intermolecular hydrogen bonding shows that the molecules are retained to each other by Van der Walls interaction only. The second type of bonds arises from an S(2)—I(1) and S(3)—I(1) interaction with two different bond lengths, 3.4452 (7)Å and 3.6859 (7) Å respectively (Fig.2). These bonds maintain the cohesion of the crystalline structure.

Experimental

The reagent C₇H₄S₃ was prepared using a literature method (Klinsberg et al., 1962) and characterized. The solvent was dried and distilled by a standard method before use. All other chemicals were obtained from commercial sources and used without further purification. Infrared spectra were measured as KBr disc on a Nicolet 205 F T—IR spectrometer.

A solution of HgI₂ (2.5 m mol, 1,130 g) in acetone (15 ml) was added to a solution of C₇H₄S₃(2.5 m mol, 0,460 g) in acetone at room temperature under argon atmosphere. An orange precipitate was formed immediately and the mixture was stirred for 50 min. The precipitate was filtered, washed with petroleum ether (yield: 60%). Orange crystals for x-ray measurement were obtained by recrystaling the solid in THF. IR (KBr, cm^-1):n(C=C) 1447 ms, n(C=S) 991,3vs, n(Hg—S) 256,5 ms, n(Hg—I) 167,8vs.