Bis[1-(3-cyano­benz­yl)pyridinium] bis­(1,2-dicyano­ethene-1,2-dithiol­ato)nickelate(II)

Hua Xian; Hai-Bao Duan

doi:10.1107/S1600536810051263

. 2010 Dec 11;67(Pt 1):m70. doi: 10.1107/S1600536810051263

Bis[1-(3-cyanobenzyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II)

Hua Xian ^a, Hai-Bao Duan ^a,^*

PMCID: PMC3050285 PMID: 21522588

Abstract

In the ionic title complex, (C₁₃H₁₁N₂)₂[Ni(C₄N₂S₂)₂], the Ni^II ion is located on an inversion centre so the asymmetric unit contains one-half [Ni(mnt)₂]²⁻ dianion (mnt²⁻ is maleonitriledithiolate) and one 1-(3-cyanobenzyl)pyridinium cation ([CNBzPy]⁺). The Ni^II ion in the [Ni(mnt)₂]²⁻ anion is coordinated by four S atoms of two mnt²⁻ ligands, and exhibits square-planar coordination geometry. In the [CNBzPy]⁺ cation, the benzene and pyridine rings are twisted with respect to the C/C/N plane incorporating the methylene C atom that links them. The crystal structure is stabilized by Coulombic interactions.

Related literature

For background to the development of new functional molecule-based materials, see: Robertson & Cronin (2002 ▶). For the applications of molecular solids based on M[dithiolene]₂ complexes in molecular-based materials showing magnetic, superconducting and optical properties, see: Ni et al. (2004 ▶, 2005 ▶); Nishijo et al. (2000 ▶). For bond lengths and angles in related structures, see: Ren et al. (2004 ▶).

Experimental

Crystal data

(C₁₃H₁₁N₂)₂[Ni(C₄N₂S₂)₂]
M _r = 729.57
Monoclinic,
a = 11.633 (3) Å
b = 8.709 (2) Å
c = 16.692 (4) Å
β = 91.278 (5)°
V = 1690.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 293 K
0.4 × 0.3 × 0.2 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.702, T _max = 0.741
13953 measured reflections
3068 independent reflections
2154 reflections with I > 2σ(I)
R _int = 0.092

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.130
S = 1.18
3068 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810051263/bx2332sup1.cif

e-67-00m70-sup1.cif^{(16.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051263/bx2332Isup2.hkl

e-67-00m70-Isup2.hkl^{(150.6KB, hkl)}

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

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

Ni1—S1	2.1710 (13)
Ni1—S2	2.1713 (14)

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S1—Ni1—S2	87.64 (5)
S1ⁱ—Ni1—S2	92.36 (5)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Natural Science Foundation of Higher Learning Institutions of Abhui Provice, China, for financial support (grant No. KJ2009B275Z).

supplementary crystallographic information

Comment

Molecular solids based on transition metal dithiolene complexes have attracted intense interest in recent years, not only owing to the fundamental research of magnetic interactions and magneto-structural correlations but also to the development of new functional molecule-based materials (Robertson & Cronin, 2002), Much work has been performed in molecular solids based on M[dithiolene]₂ complexes owing to their application as building blocks in molecular-based materials showing magnetic, superconducting, and optical properties (Nishijo et al., 2000; Ni et al., 2005). Herein we report the crystal structure of the title compound (I).

The molecular structure of (I) is illustrated in Fig. 1.The asymmetric unit is formed by with one half anion and one cation.The Ni ^IIion is coordinated by four sulfur atoms of two mnt^2- ligands, and exhibits square-planar coordination geometry. The crystal structure is stabilized by coulombic interactions. The bond lengths and angles are in good agreement with related compounds [Ni(mnt)₂]^2-Table 1, (Ni et al., 2004; Ren et al., 2004).

Experimental

Disodium maleonitriledithiolate (456 mg, 2.5 mmol) and nickel chloride hexahydrate (297 mg, 1.25 mmol) were mixed under stirring in water (20 mL) at room temperature. Subsequently, a solution of 1-(3-cyanobenzyl)pyridinium iodide (488 mg, 2.5 mmol) in methanol (10 mL) was added to the mixture, and the red precipitate that was immediately formed was filtered off, and washed with methanol. The crude product was recrystallized in acetone (20 mL) to give red block crystals. Anal. Calcd. for C₃₄H₂₂N₈NiS₄: C, 55.98; H, 3.04; N, 15.36%. Found: C, 56.00; H, 3.08; N, 15.33%.