1-(3,4-Dichloro­benz­yl)pyridinium bis­(2-sulfanyl­idene-1,3-dithiole-4,5-dithiol­ato-κ2 S,S′)nickelate(III)

Guang-Xiang Liu

doi:10.1107/S160053681104267X

. 2011 Oct 22;67(Pt 11):m1570. doi: 10.1107/S160053681104267X

1-(3,4-Dichlorobenzyl)pyridinium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-κ² S,S′)nickelate(III)

Guang-Xiang Liu ^a,^*

PMCID: PMC3246987 PMID: 22219807

Abstract

The title compound, (C₁₂H₁₀Cl₂N)[Ni(C₃S₅)₂], is an ion-pair complex consisting of 1-(3,4-dichlorobenzyl)pyridinium cations and [Ni(dmit)₂] anions (dmit = 2-sulfanylidene-1,3-dithiole-4,5-dithiolate). In the anion, the Ni^III ion exhibits a square-planar coordination involving four S atoms from two dmit ligands. In the crystal, weak S⋯S [3.368 (2) and 3.482 (3) Å], Ni⋯S [3.680 (2) Å] and Cl⋯S [3.491 (2) Å] interactions and C—H⋯S hydrogen bonds lead to a three-dimensional supramolecular network.

Related literature

For general background to the network topologies and applications of bis(dithiolate)–metal complexes, see: Cassoux (1999 ▶). For the synthesis, structures and properties of related complexes containing dmit ligands, see: Akutagawa & Nakamura (2000 ▶); Liu et al. (2010 ▶); Li et al. (2006 ▶); Zang et al. (2006 ▶, 2009 ▶). For the synthesis of a starting material, see: Wang et al. (1998 ▶).

Experimental

Crystal data

(C₁₂H₁₀Cl₂N)[Ni(C₃S₅)₂]
M _r = 690.48
Triclinic,
a = 9.3711 (11) Å
b = 11.7210 (14) Å
c = 11.9640 (14) Å
α = 82.814 (1)°
β = 88.854 (1)°
γ = 76.644 (1)°
V = 1268.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.81 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.692, T _max = 0.761
9520 measured reflections
4692 independent reflections
4083 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.082
S = 1.04
4692 reflections
290 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.34 e Å⁻³

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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681104267X/rz2651sup1.cif

e-67-m1570-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104267X/rz2651Isup2.hkl

e-67-m1570-Isup2.hkl^{(229.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯S10ⁱ	0.93	2.82	3.622 (3)	145
C18—H18⋯S1ⁱⁱ	0.93	2.79	3.708 (3)	168

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 20971004), the Key Project of the Chinese Ministry of Education (grant No. 210102) and the Natural Science Foundation of Anhui Province (grant No. 11040606M45).

supplementary crystallographic information

Comment

Extensive research has been focused on the synthesis and characterization of bis(dithiolate)-metal complexes and their analogues, due to their properties and potential applications as conducting, magnetic and non-linear optical (NLO) materials (Cassoux, 1999). 2-Thioxo-1,3-dithiole-4,5-dithiolate (dmit) metal complexes are in fact excellent building blocks employed for the construction of molecular magnetic materials (Li et al., 2006; Liu et al., 2010; Zang et al., 2006, 2009) apart from their well known electric conductivity as molecular conductors (Akutagawa & Nakamura, 2000). Herein the crystal structure of the title compound, a new ion-pair complex, is reported.

The title compound comprises [Ni(dmit)₂]^- anions and 1-(3,4-dichlorobenzyl)pyridinium cations (Fig. 1). The Ni ion adopts a square-planar geometry coordinated by four S atoms from two dmit ligands, with Ni—S bond lengths ranging from 2.1518 (7) to 2.1714 (7) Å. The [Ni(dmit)₂]^- anions are in a parallel arrangement, with S···S interactions ranging from 3.474 (3) to 3.547 (3) Å. Two neighbouring anions are parallel in a face-to-face fashion with the shortest Ni···S distance of 3.680 (2) Å (Ni1—S2ⁱ) [symmetry code: (i) -x, -y, -z], indicating the existence of the Ni···S interactions. Adjacent [Ni(dmit)₂]^- anions are associated together through such Ni···S interactions resulting in a dimer. The dimers are linked together through S9···S3ⁱⁱ and S9···S5ⁱⁱ [symmetry code: (ii) x, 1 + y, z] interactions forming a one-dimensional chain structure, as depicted in Fig. 2. The (C₁₂H₁₀Cl₂N)⁺ cation has a Λ-shaped conformation, and the dihedral angles formed by the C12/C13/N1 plane with the benzene and pyridinium rings are 85.29 (2) and 77.84 (2)°, respectively. Cations and the anions are linked by S···Cl interactions and C—H···S hydrogen bonds to generate a three-dimensional supramolecular structure (Fig. 3).

Experimental

4,5-Di(thiobenzoyl)-1,3-dithiole-2-thione (812 mg, 2 mmol; Wang et al., 1998) was suspended in methanol (10 ml). Sodium methoxide in methanol (prepared form 184 mg of sodium in 10 ml of methanol) was added to the above mixture under argon atmosphere at room temperature from 30 min to give a dark red solution. To this solution, NiCl~2~.6H~2Õ (238 mg, 1 mmol) was added. After 30 min, a solution of I~2~ (127 mg, 1 mmol) and NaI (150 mg, 1 mmol) in methanol (20 ml) was added (the monoanionic [Ni(dmit)~2~]^-^ are obtained from the dianionic [Ni(dmit)~2~]^2-^ by I~3~^-^ oxidation). After another 10 min, a solution of 1-(3,4-dichlorobenzyl)pyridinium bromide [(DiClPy)Br] (317 mg, 1 mmol) in methanol (20 ml) was added to the reaction mixture. The solution was stirred for 30 min and cooled in a refrigerator overnight. The resultant dark green crystalline solid was collected by filtration, and purified by recrystallization using a mixed solution of acetonitrile and benzene (1:1 v/v).