Bis(3,5,7-triaza-1-azoniatricyclo­[3.3.1.13,7]deca­ne) bis­(1,2-dicyano­ethene-1,2-dithiol­ato)nickelate(II)

Chen Pan; Bin Cai; Wen-Bo Pei

doi:10.1107/S160053681101645X

. 2011 May 7;67(Pt 6):m730. doi: 10.1107/S160053681101645X

Bis(3,5,7-triaza-1-azoniatricyclo[3.3.1.1^3,7]decane) bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II)

Chen Pan ^a, Bin Cai ^a, Wen-Bo Pei ^a,^*

PMCID: PMC3120553 PMID: 21754626

Abstract

The asymmetric unit of the title complex, (C₆H₁₃N₄)₂[Ni(C₄N₂S₂)₂], comprises one 1-azonia-3,5,7-triazatricyclo[3.3.1.1^3,7]decane cation and one half of an [Ni(mnt)₂]²⁻ (mnt²⁻ is maleonitriledithiolate or 1,2-dicyanoethene-1,2-dithiolate) dianion. The Ni²⁺ ion is located on a center of inversion and is coordinated by four S atoms from two mnt²⁻ ligands in a square-planar coordination mode. Intermolecular N—H⋯N hydrogen-bond interactions link one anion and two cations in the crystal structure.

Related literature

For general background to square-planar M[dithiolene]₂ complexes acting as magnetic materials or showing non-linear optical properties, see: Duan et al. (2010 ▶). For the synthesis, see: Pei et al. (2010 ▶). For related structures, see: Ren et al. (2002 ▶). For related literature on spectroscopic properties, see: Bigoli et al. (2002 ▶).

Experimental

Crystal data

(C₆H₁₃N₄)₂[Ni(C₄N₂S₂)₂]
M _r = 621.50
Monoclinic,
a = 10.2274 (9) Å
b = 10.7676 (10) Å
c = 12.7030 (11) Å
β = 112.212 (2)°
V = 1295.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.15 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick 2002 ▶) T _min = 0.819, T _max = 0.847
7528 measured reflections
2530 independent reflections
1784 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.075
S = 1.00
2530 reflections
173 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.33 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 datablocks I, global. DOI: 10.1107/S160053681101645X/im2281sup1.cif

e-67-0m730-sup1.cif^{(16.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101645X/im2281Isup2.hkl

e-67-0m730-Isup2.hkl^{(124.3KB, 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
N6—H1⋯N1ⁱ	0.87 (4)	2.37 (4)	2.941 (5)	124 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Doctorial Innovation Fund of Nanjing University of Technology (grant No. BSCX200908).

supplementary crystallographic information

Comment

Square-planar M[dithiolene]₂ complexes have been widely studied due to their novel properties and application in the areas of conducting and magnetic materials, dyes, non-linear optics, catalysis and others. These applications arise due to a combination of functional properties, specific geometries and intermolecular interactions (Duan et al., 2010; Pei et al., 2010). Herein we report the crystal structure of the title compound.

The molecular structure of (I) is illustrated in Fig. 1., bond distances and bond angles are given as Supplementary Material. The N—H···N hydrogen bond properties are given in Table 1.

In the asymmetric unit of the title complex, (C₆H₁₃N₄)₂(C₈N₄NiS₄), (I), one 1-azonia-3,5,7-triaza-tricyclo[3.3.1.1^3,7]decane cation and one half of a [Ni(mnt)₂]^2- (mnt^2- = maleonitriledithiolate) dianion are observed. The Ni²⁺ ion is located on a crystallographic center of inversion and is coordinated by four S-atoms from two mnt^2- ligands in a square-planar coordination mode. Intermolecular N—H···N hydrogen bond interactions join together one anion and two cations of (I) in the crystal structure.

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 about 20 min. After filtering the red solution, an aequeous solution of hexamethylenetetramine hydrochloride (442 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. The crude product was recrystallized to give red crystals (yield: 645 mg, 83%). Single crystals with block shape suitable for X-ray analysis were obtained via recrystallization of the corresponding complex in acetone.