Bis(diethyl­enetriamine-κ3 N,N′,N′′)nickel(II) bis­(1,2-dicyanoethene-1,2-dithiolato-κ2 S,S′)nickel(II)

Dao-Peng Zhang; Hai-Long Wang; Li-Fang Zhang; Zhong-Hai Ni

doi:10.1107/S1600536808028663

. 2008 Sep 13;64(Pt 10):m1264–m1265. doi: 10.1107/S1600536808028663

Bis(diethylenetriamine-κ³ N,N′,N′′)nickel(II) bis(1,2-dicyanoethene-1,2-dithiolato-κ² S,S′)nickel(II)

Dao-Peng Zhang ^a, Hai-Long Wang ^a, Li-Fang Zhang ^a,^*, Zhong-Hai Ni ^a

PMCID: PMC2959400 PMID: 21201018

Abstract

The title compound, [Ni(C₄H₁₃N₃)₂][Ni(C₄N₂S₂)₂], has been synthesized by the reaction of Ni(ClO₄)₂·6H₂O, diethylenetriamine (deta) and Na₂[Ni(mnt)₂] [mnt = maleonitriledithiolate(2-)] in methanol. The structure is composed of a [Ni(deta)₂]²⁺ cation and a [Ni(mnt)₂]²⁻ anion. The coordination geometry of the Ni^II ion in the cation is slightly distorted octahedral, defined by six N atoms from two deta ligands, while the Ni^II ion in the anion is four-coordinated by four S atoms from two mnt ligands in a slightly distorted square-planar geometry. The cations and anions are connected by N—H⋯N hydrogen bonds.

Related literature

For related literature, see: Bois et al. (1998 ▶); Keum et al. (1992 ▶); Miller et al. (1989 ▶); Ren et al. (2001 ▶); Robertson & Cronin (2002 ▶); Simmons et al. (1962 ▶).

Experimental

Crystal data

[Ni(C₄H₁₃N₃)₂][Ni(C₄N₂S₂)₂]
M _r = 604.13
Monoclinic,
a = 9.589 (3) Å
b = 16.910 (5) Å
c = 16.146 (4) Å
β = 97.491 (4)°
V = 2595.8 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 273 (2) K
0.19 × 0.17 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.717, T _max = 0.766
13610 measured reflections
5065 independent reflections
3393 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.109
S = 0.99
5065 reflections
329 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; 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/S1600536808028663/hy2151sup1.cif

e-64-m1264-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028663/hy2151Isup2.hkl

e-64-m1264-Isup2.hkl^{(248.1KB, hkl)}

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

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

Ni1—S1	2.1739 (12)
Ni1—S2	2.1617 (12)
Ni1—S3	2.1732 (12)
Ni1—S4	2.1658 (12)
Ni2—N5	2.164 (3)
Ni2—N6	2.065 (3)
Ni2—N7	2.150 (4)
Ni2—N8	2.145 (3)
Ni2—N9	2.071 (4)
Ni2—N10	2.151 (3)

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S2—Ni1—S4	87.98 (5)
S2—Ni1—S3	168.77 (5)
S4—Ni1—S3	92.72 (4)
S2—Ni1—S1	92.58 (4)
S4—Ni1—S1	170.10 (4)
S3—Ni1—S1	88.65 (4)
N6—Ni2—N9	177.56 (15)
N6—Ni2—N8	98.00 (14)
N9—Ni2—N8	81.73 (14)
N6—Ni2—N7	82.24 (16)
N9—Ni2—N7	95.37 (17)
N8—Ni2—N7	95.96 (15)
N6—Ni2—N10	98.69 (14)
N9—Ni2—N10	81.72 (14)
N8—Ni2—N10	163.04 (16)
N7—Ni2—N10	89.25 (16)
N6—Ni2—N5	81.47 (14)
N9—Ni2—N5	100.96 (15)
N8—Ni2—N5	91.32 (13)
N7—Ni2—N5	162.93 (16)
N10—Ni2—N5	88.20 (14)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯N4ⁱ	0.86 (3)	2.30 (4)	3.098 (6)	154 (3)
N5—H5B⋯N2ⁱⁱ	0.86 (3)	2.48 (3)	3.186 (5)	140 (4)
N7—H7A⋯N3ⁱⁱⁱ	0.86 (4)	2.56 (3)	3.207 (7)	134 (3)
N8—H8B⋯N3ⁱⁱⁱ	0.86 (3)	2.48 (4)	3.164 (6)	138 (3)
N9—H9A⋯N1^iv	0.86 (2)	2.58 (3)	3.387 (6)	156 (5)
N10—H10C⋯N2ⁱⁱ	0.87 (3)	2.34 (3)	3.198 (5)	173 (5)

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

Acknowledgments

This work was supported by the Natural Science Foundation of China (No. 20701027) and the Postdoctoral Scientific Foundation of China (No. 200704211076).

supplementary crystallographic information

Comment

Bidentate dithiolate ligands form well square-planar complexes with nickel ions in different oxidation states. Due to their unique properties and potential applications in such areas as conducting and magnetic materials, nearinfrared dyes, nonlinear optical materials (Robertson & Cronin, 2002), the ion-pair complexes formed from [M(mnt)₂]^n- (M = Ni, Pd, Pt or Cu) and transition metal complex cations have been intensively studied (Bois et al., 1998; Miller et al., 1989; Ren et al., 2001). We report here a new ion-pair complex.

The title compound is composed of a [Ni(deta)₂]²⁺ cation and a [Ni(mnt)₂]^2- anion [deta = diethylenetriamine; mnt = maleonitriledithiolate(2-)] (Fig. 1). In the cation, the Ni^II ion has a slightly distorted octahedral geometry, formed by six N atoms from two deta ligands, with the Ni—N distances in a range from 2.065 (3) to 2.164 (3) Å (Table 1), which are consistent with the corresponding values in [Ni(en)₃][Ni(mnt)₂] (en = ethylenediamine) (Keum et al., 1992). The Ni^II ion in the anion is four-coordinated by four S atoms and these five atoms form a square plane with a mean deviation of 0.161 (6) Å. The Ni—S bond lengths [2.1617 (12)–2.1739 (12) Å] are also in agreement with those found in the above complex. The cations and anions are connected by N—H···N hydrogen bonds (Table 2).

Experimental

The synthesis procedure of the title compound was as following: Ni(ClO₄)₂.6H₂O (0.037 g, 0.10 mmol) was dissolved in methanol (10 ml) at room temperature with stirring and then deta (0.021 g, 0.20 mmol) was added. A solution of Na₂[Ni(mnt)₂] (0.033 g, 0.10 mmol) (Simmons et al., 1962) in methanol (10 ml) was slowly added to the above solution and the mixture was stirred for another 30 min. After filtering, the filtrate was undisturbed for about two weeks at room temperature in air to produce blue crystals suitable for X-ray diffraction (yield 61.75%, 0.037 g). Analysis, calculated for C₁₆H₂₆N₁₀Ni₂S₄: C 31.81, H 4.34, N 23.19%; found: C 31.76, H 4.31, N 23.24%.