Ethyl­enediammonium tetra­kis({2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}nickel(II)) bis­(perchlorate) dimethyl­formamide monosolvate

Gervas Assey; Yilma Gultneh; Ray J Butcher

doi:10.1107/S1600536810017162

. 2010 May 15;66(Pt 6):m654–m655. doi: 10.1107/S1600536810017162

Ethylenediammonium tetrakis({2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}nickel(II)) bis(perchlorate) dimethylformamide monosolvate

Gervas Assey ^a, Yilma Gultneh ^a, Ray J Butcher ^a,^*

PMCID: PMC2979541 PMID: 21579300

Abstract

The title compound, (C₂H₁₀N₂)[Ni(C₁₆H₁₄N₂O₂)]₄(ClO₄)₂·C₃H₇NO, crystallizes with four Ni(salen) molecules {salen is 2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate}, one ethylenediammonium cation (actually two half-cations, each located on a center of inversion), two perchlorate anions and one dimethylformamide solvent molecule in the asymmetric unit. Each Ni^II cation in the Ni(salen) complex is four-coordinated by two imine N atoms and two phenolate O atoms from the tetradentate ligand. The Ni(salen) units form parallel slipped stacks with Ni⋯Ni separations of 3.4541 (4) and 3.6442 (6) Å. The crystal packing is stabilized by intermolecular hydrogen bonds between the ammonium H atoms and the perchlorate and salen O atoms, which generate a three-dimensional structure.

Related literature

For applications of nickel–Schiff base complexes in homogeneous and heterogeneous catalysis, see: Santos et al. (2000 ▶); Silva et al. (2002 ▶); Yoon & Burrows (1988 ▶); Mitra & Chatterjee (1999 ▶). For other properties of Ni(salen) complexes, see: Abe et al. (2006 ▶); Gaetani Manfredotti & Guastini (1983 ▶); Pahor et al. (1976 ▶); Prabhakar et al. (2006 ▶); Santos et al. (2000 ▶); Silva et al. (2002 ▶). For the structures of Ni(salen) co-crystallization complexes, see: Giacomelli et al. (1982 ▶); Ryazanov et al. (2001 ▶); Skovsgaard et al. (2005 ▶); Feng et al. (2007 ▶); Sun et al. (1991 ▶); Lutz (2003 ▶).

Experimental

Crystal data

(C₂H₁₀N₂)[Ni(C₁₆H₁₄N₂O₂)]₄·(ClO₄)₂·C₃H₇NO
M _r = 1634.12
Triclinic,
a = 15.0209 (11) Å
b = 15.0492 (13) Å
c = 18.2709 (8) Å
α = 85.990 (5)°
β = 86.506 (5)°
γ = 62.963 (8)°
V = 3667.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.16 mm⁻¹
T = 200 K
0.53 × 0.28 × 0.24 mm

Data collection

Oxford Diffraction Gemini R diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.832, T _max = 1.000
31940 measured reflections
13062 independent reflections
9248 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.110
S = 0.95
13062 reflections
936 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; 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/S1600536810017162/sj2787sup1.cif

e-66-0m654-sup1.cif^{(55.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017162/sj2787Isup2.hkl

e-66-0m654-Isup2.hkl^{(753.8KB, 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
N11S—H11B⋯O2A	0.91	1.97	2.877 (3)	173
N11S—H11B⋯O1A	0.91	2.45	2.949 (3)	115
N11S—H11D⋯O2D	0.91	2.00	2.876 (3)	162
N11S—H11D⋯O1D	0.91	2.48	3.132 (3)	128
N22S—H22A⋯O1B	0.91	1.97	2.830 (3)	157
N22S—H22A⋯O2B	0.91	2.34	2.884 (3)	118
N22S—H22B⋯O1C	0.91	1.98	2.853 (3)	160
N22S—H22B⋯O2C	0.91	2.45	3.118 (3)	130
N22S—H22C⋯O1SB	0.91	1.91	2.706 (5)	145
N22S—H22C⋯O1SA	0.91	1.90	2.778 (6)	161

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Acknowledgments

RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

supplementary crystallographic information

Comment

Schiff base complexes of transition metals are of paramount importance due to their application in homogeneous and heterogeneous catalysis (Santos et al. 2000; Silva et al. 2002). Nickel(II) Schiff bases have been described as being active catalytically in oxidation and reduction reactions both as homogeneous (Yoon & Burrows 1988) and heterogeneous catalysts (Mitra & Chatterjee 1999). [Ethylenebis(salicylideneiminato-κ⁴N,N',O,O']nickel(II) {Nisalen} complexes with mesomorphic properties, known as metallomesogens, have been synthesized and investigated (Abe et al. 2006). In addition, there have been several instances of Ni(salen) type species co-crystallizing with other salts and molecules (Giacomelli et al., 1982; Ryazanov et al., 2001; Skovsgaard et al., 2005; Feng et al., 2007; Sun et al., 1991; Lutz, 2003).

The work presented here describes the synthesis and structural characterization of Ni^II salen complex co-crystallizing with ethylenediammonium perchlorate and N,N'-dimethylformamide presented in Fig. 1. The asymmetric unit contains four neutral Ni(salen) molecules, ethylenediammonium perchlorate (actually two half ethylenediammonium cations lying on centers of inversion), and an N,N'-dimethylformamide solvate molecule. All species are linked together by an extensive series of hydrogen bonds between the ethylenediammonium cations and perchlorate anions, neutral Ni(salen) and N,N'-dimethylformamide molecules. This is a good example of molecular recognition. The Ni—O phenolate bond distances range from 1.8353 (15) to 1.8576 (14) Å and the Ni—N distances range from 1.836 (2) to 1.8497 (18) Å and are comparable to those found in literature for similar neutral Ni(salen) complexes reported earlier (Prabhakar et al. 2006). The coordination around Ni^II ions shows a slightly distorted square planer geometry. The Ni(salen) units form parallel slipped stacks with Ni—Ni separations of 3.4541 (4) and 3.6442 (6) Å.

Experimental

The ligand ethylenebis(salicylideneimine) was synthesized by reacting a solution of (5 g, 83.19 mmol) of ethylenediamine in 10 ml ethanol with a solution of (20.32 g, 166.38 mmol) salicylaldehyde in 40 ml ethanol. The mixture was refluxed for 24 hrs. The mixture was then evaporated under reduced pressure and yellow solids were obtained with a yield of 96.6%.

The complex was synthesized by reacting 1.36 g (3.73 mmol) of Ni(ClO₄)₂.6H₂O in methanol (10 ml) with 1 g (3.73 mmol) of ethylenebis(salicylideneimine) in CH₂Cl₂ (10 ml) for 24 hours while stirring with magnetic stirrer at room temperature. The mixture was evaporated under reduced pressure and brownish solids were obtained. These solids were dissolved in N,N'-dimethylformamide. The solution obtained was filtered and layered with diethyl ether. Brownish X-ray quality crystals were obtained after slow diffusion of the diethyl ether into the N,N'-dimethylformamide solution of the complex over a period of several days.