Bis[(E)-1-(3,4-dichloro­benzyl­idene­amino)-4-methyl­pyridinium] bis­(maleonitrile­dithiol­ato)nickelate(II)

Jian-Lan Liu; Bing-Qian Yao; Qi Liu; Shao-Ming Zhang

doi:10.1107/S1600536809001159

. 2009 Jan 17;65(Pt 2):m203–m204. doi: 10.1107/S1600536809001159

Bis[(E)-1-(3,4-dichlorobenzylideneamino)-4-methylpyridinium] bis(maleonitriledithiolato)nickelate(II)

Jian-Lan Liu ^a, Bing-Qian Yao ^a, Qi Liu ^a, Shao-Ming Zhang ^a,^*

PMCID: PMC2968142 PMID: 21581801

Abstract

The asymmetric unit of the title compound, (C₁₃H₁₁Cl₂N₂)₂[Ni(C₄N₂S₂)₂], contains one-half of a centrosymmetric [Ni(mnt)₂] anion (where mnt is maleonitriledithiolate or 1,2-dicyano-1,2-ethylenedithiolate) and an (E)-1-(3,4-dichlorobenzylideneamino)-4-methylpyridinium cation. In the anion, the coordination around the Ni atom is a distorted square. In the cation, the aromatic rings are oriented at a dihedral angle of 7.81 (3)°. In the crystal structure, intermolecular C—H⋯N hydrogen bonds link the cations and anions. π–π Contacts between the nickel dithiolene and pyridine rings and between the benzene and pyridine rings, [centroid–centroid distances = 3.682 (3) and 3.643 (3) Å, respectively] may further stabilize the structure.

Related literature

For general background, see: Robertson & Cronin (2002 ▶); Cassoux et al. (1991 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

(C₁₃H₁₁Cl₂N₂)₂[Ni(C₄N₂S₂)₂]
M _r = 871.37
Monoclinic,
a = 10.7054 (10) Å
b = 13.8664 (13) Å
c = 12.5043 (12) Å
β = 95.803 (1)°
V = 1846.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 296 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.729, T _max = 0.895
15877 measured reflections
4273 independent reflections
3611 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.089
S = 1.08
4273 reflections
232 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.37 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 datablocks global, I. DOI: 10.1107/S1600536809001159/hk2608sup1.cif

e-65-0m203-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001159/hk2608Isup2.hkl

e-65-0m203-Isup2.hkl^{(209.4KB, hkl)}

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

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

Ni1—S1	2.1622 (5)
Ni1—S2	2.1838 (5)

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S1—Ni1—S2ⁱ	88.128 (19)
S1—Ni1—S2	91.872 (19)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯N2ⁱⁱ	0.93	2.51	3.413 (3)	163

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Symmetry code: (ii) Inline graphic .

Acknowledgments

The authors thank the Science and Technology Department of Jiangsu Province and the Natural Science Foundation of China for financial support (grant No. 10774076).

supplementary crystallographic information

Comment

Square-planar M[dithiolene]₂ complexes have attracted extensive interests in the areas of conducting and magnetic materials, dyes, non-linear optics and catalysis (Robertson et al., 2002; Cassoux et al., 1991). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) contains one-half of centrosymmetric [Ni(mnt)₂] (where mnt is maleonitriledithiolate) anion and a (E)-1-(3,4-di-chlorobenzylideneamino)-4-methylpyridinium cation. In the anion, the coordination around the Ni atom is a distorted square (Table 1). The bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (Ni1/S1/S2/C2/C3), B (N3/C5-C9) and C (C12-C17) are, of course, planar and they are oriented at dihedral angles of A/B = 16.69 (3)°, A/C = 13.47 (3)° and B/C = 7.81 (3)°.

In the crystal structure, intermolecular C-H···N hydrogen bonds (Table 2) link the cations and anions (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contacts between the nickel dithiolene and the pyridine rings and the benzene and the pyridine rings, Cg1—Cg3ⁱ and Cg3—Cg4ⁱⁱ [symmetry codes: (i) 1/2 + x, 1/2 - y, 1/2 + z; (ii) 1 - x, 1 - y, -z, where Cg1, Cg3 and Cg4 are centroids of the rings A (Ni1/S1/S2/C2/C3), B (N3/C5-C9) and C (C12-C17), respectively] may further stabilize the structure, with centroid-centroid distances of 3.682 (3) Å and 3.643 (3) Å.

Experimental

For the preparation of the title compound, disodium maleonitriledithiolate (458 mg, 2.46 mmol) and nickel chloride hexahydrate (230 mg, 0.96 mmol) were mixed by stirring in EtOH (20 ml) at room temperature. Subsequently, a solution of (E)-1-(3,4-di-chlorobenzylideneamino)-4-methylpyridinium iodide (2143 mg, 2.46 mmol) in EtOH (10 ml) was added to the mixture, and the red precipitate immediately formed was filtered off, and washed with EtOH. The crude product was recrystallized in acetone (20 ml) to give black crystals. Crystals suitable for X-ray analysis were obtained by diffusing diethyl ether into the solution of the title compound in acetone for 8 d. FT-IR data (KBr pellets, cm^-1): 2189 (s), 2920 (s),1631(s), 1485 (s), 1272 (s).