Bis[1-(4-cyano­benz­yl)pyrazinium] bis­(1,2-dicyano­ethene-1,2-dithiol­ato)nickelate(II)

Hui Zhang; Wen-Bo Pei; Shan-Shan Yu; Xiao-Ming Ren

doi:10.1107/S1600536811022550

. 2011 Jun 18;67(Pt 7):m943. doi: 10.1107/S1600536811022550

Bis[1-(4-cyanobenzyl)pyrazinium] bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II)

Hui Zhang ^a, Wen-Bo Pei ^a, Shan-Shan Yu ^b, Xiao-Ming Ren ^a,^*

PMCID: PMC3152075 PMID: 21836926

Abstract

The asymmetric unit of the title complex, (C₁₂H₁₀N₃)₂[Ni(C₄N₂S₂)₂], consists of one 1-(4-cyanobenzyl)pyrazinium cation and one half of an [Ni(mnt)₂]²⁻ dianion (mnt²⁻ is 1,2-dicyanoethene-1,2-dithiolate). The Ni²⁺ ion is located on an inversion center and is coordinated by four S atoms from two mnt²⁻ ligands, exhibiting a square-planar coordination geometry. The cation adopts a conformation where both the pyrazine ring and the benzene ring are twisted with respect to the C—C—N reference plane by 16.5 (2) and 69.8 (1)°, respectively.

Related literature

For general background to square-planar bis-1,2-dithiolato complexes of transition metals showing potential application as magnetic or conducting materials and other properties, see: Bigoli et al. (2002 ▶); Duan et al. (2010 ▶); Pei et al. (2011 ▶). For the synthesis, see: Davison & Holm (1967 ▶).

Experimental

Crystal data

(C₁₂H₁₀N₃)₂[Ni(C₄N₂S₂)₂]
M _r = 731.53
Monoclinic,
a = 7.115 (3) Å
b = 13.623 (6) Å
c = 17.186 (8) Å
β = 101.671 (5)°
V = 1631.4 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) ▶ T _min = 0.807, T _max = 0.875
8060 measured reflections
2871 independent reflections
2586 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.074
S = 1.06
2871 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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/S1600536811022550/im2295sup1.cif

e-67-0m943-sup1.cif^{(16.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022550/im2295Isup2.hkl

e-67-0m943-Isup2.hkl^{(141KB, hkl)}

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

Acknowledgments

The authors thank the Science and Technology Department of Jiangsu Province, China (grant No. BK2007184).

supplementary crystallographic information

Comment

Bis-1,2-dithiolene complexes of transition metals have been widely studied because of their novel properties and applications in the areas of conducting and magnetic materials, dyes, nonlinear optics, catalysis and others. These applications arise due to a combination of functional properties, specific geometries and intermolecular interactions. (Bigoli et al., 2002; Duan et al., 2010; Pei et al., 2011). Herein we report the crystal structure of the title compound (Fig. 1).

An asymmetric unit consists of one half [Ni(mnt)₂]^2- dianion and one 1-N-(4'-cyano-benzyl)-pyrazinium cation. In the [Ni(mnt)₂]^2- moiety, the Ni atom is situated at a inversion center and is coordinated by four S atoms from two mnt^2- ligands, forming a square-planar coordination geometry. The cation adopts a conformation where the bond lengths and bond angles were normal, and both the pyrazine ring and the phenyl ring are twisted with respect to the C8—C12—N4 reference plane with the corresponding dihedral angles of 16.5 (2)° and 69.8 (1)°.

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) and heated to boiling for about 20 min. After the red solution was filtered an aqueous solution of 1-N-(4'-cyano-benzyl)-pyrazinium chloride (579 mg, 2.5 mmol) was added dropwise to the filtrate. The immediately formed dark red precipitate was filtered off, washed with water and dried in vacuum (yield: 722 mg, 79%). Block shaped single crystals suitable for X-ray analysis were obtained via recrystallization of the corresponding complex in acetone.