Bis(3-acetyl-6-methyl-2-oxo-2H-pyran-4-olato)bis­(dimethyl sulfoxide)nickel(II)

Amel Djedouani; Sihem Boufas; Abderrahmen Bendaas; Magali Allain; Gilles Bouet

doi:10.1107/S1600536809034655

. 2009 Sep 12;65(Pt 10):m1205–m1206. doi: 10.1107/S1600536809034655

Bis(3-acetyl-6-methyl-2-oxo-2H-pyran-4-olato)bis(dimethyl sulfoxide)nickel(II)

Amel Djedouani ^a, Sihem Boufas ^b,^*, Abderrahmen Bendaas ^a, Magali Allain ^c, Gilles Bouet ^d

PMCID: PMC2970285 PMID: 21577732

Abstract

In the title compound, [Ni(C₈H₇O₄)₂{(CH₃)₂SO}₂], the Ni^II atom is located on a crystallographic centre of symmetry and has a distorted octahedral coordination geometry of type MO₆. The bidentate dehydroacetic acid (DHA) ligands occupy the equatorial plane of the complex in a trans configuration, and the dimethyl sulfoxide (DMSO) ligands are weakly coordinated through their O atoms in the axial positions.

Related literature

3-Acetyl-4-hydroxy-6-methyl-2-oxo-2H-pyran (dehydroacetic acid) (Arndt et al., 1936 ▶) is a versatile starting material for the synthesis of a wide variety of heterocyclic ring systems (Tan & Ang, 1988 ▶). It has been shown to possess modest antifungal properties, see: Rao et al. (1978 ▶). For natural fungicides possessing structures analogous to 5,6-dihydrodehydroacetic acid, see: Bartels-Keith (1960 ▶); Miyakado et al. (1982 ▶); Ayer et al. (1988 ▶). The complexes of DHA with copper and with several other transition metal cations are fungistatic, see: Rao et al. (1978 ▶). For the nickel–DHA complex, see: Casabò et al. (1987 ▶). The configuration of the complex molecule is similar to that found in [Zn(DHA)₂·2(DMSO) and Cd(DHA)₂·2(DMSO)] (Zucolotto Chalaça et al., 2002 ▶), [Cu(DHA)₂·2(DMSO)] (Djedouani et al., 2006 ▶) and bis(4,6-dibromo-2-formylphenolato-κ² O,O′)-bis(dimethyl sulfoxide)nickel(II) (Zhang et al., 2007 ▶). For Ni—O_DMSO distances in similar structures, see: Ma et al. (2003 ▶); Tahir et al. (2007 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

[Ni(C₈H₇O₄)₂(C₂H₆OS)₂]
M _r = 549.24
Monoclinic,
a = 11.3850 (10) Å
b = 6.2833 (4) Å
c = 19.7434 (15) Å
β = 123.525 (6)°
V = 1177.40 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.902, T _max = 0.902
14084 measured reflections
2628 independent reflections
1962 reflections with I > 2σ(I)
R _int = 0.071

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 1.11
2628 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.97 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034655/hg2559sup1.cif

e-65-m1205-sup1.cif^{(15.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034655/hg2559Isup2.hkl

e-65-m1205-Isup2.hkl^{(126.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ni1—O2	1.9849 (16)
Ni1—O3	2.0159 (15)
Ni1—O1	2.1255 (18)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O4ⁱⁱ	0.96	2.55	3.384 (4)	145
C2—H2B⋯O4ⁱⁱ	0.96	2.53	3.370 (4)	146
C2—H2C⋯O2ⁱⁱⁱ	0.96	2.46	3.378 (4)	160

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

Acknowledgments

This work was supported by Université Farhet Abbas de Sétif, Sétif, Algeria.

supplementary crystallographic information

Comment

3-Acetyl-4-hydroxy-6-methyl-2-oxo-2H-pyran (dehydroacetic acid) (Arndt et al., 1936) is a versatile starting material for the synthesis of a wide variety of heterocyclic ring systems (Tan & Ang, 1988). It has been shown to possess modest antifungal properties (Rao et al., 1978). The importance of similar pyrones as potential fungicides is reinforced by the existence of several natural fungicides possessing structures analogous to 5,6-dihydrodehydroacetic acid, such as alternaric acid (Bartels-Keith, 1960), the podoblastins (Miyakado et al., 1982) and lachnelluloic acid (Ayer et al., 1988). Also, it has been shown that the complexes of DHA with copper and with several other transition metal cations are fungistatic (Rao et al., 1978). This has motivated our study of the structural characterization of complexes of dehydroacetic acid. The complex of DHA with nickel was previously reported by Casabò et al. (1987), but their characterization of the compound was based only on thermal and elemental analysis, and on IR and NMR spectroscopy.

We present here the crystal structure determination of the title complex, [Ni(DHA)₂.2(DMSO)], (I) (DMSO = dimethylsulfoxide). The nature of the title compound, (I), was established by an X-ray structure determination and is shown in Fig. 1

The Ni atom lies on a crystallographic centre of symmetry with the ligands bonded to nickel in an all-trans fashion. The configuration of the complex molecule is similar to that found in [Zn(DHA)₂. 2(DMSO); Cd(DHA)2.2(DMSO)] (Zucolotto Chalaça et al., 2002), [Cu(DHA)₂. 2(DMSO)] (Djedouani et al., 2006), with (DHA: dehydroacetic acid) and Bis(4,6-dibromo-2-formylphenolato-κ²O,O')-bis(dimethyl sulfoxide)nickel(II), [Ni(C₇H₃Br₂O₂)₂(C₂H₆OS)₂] (Zhang et al., 2007).

The coordination polyhedron around the Ni atom is a slightly distorted octahedron (Table 1), with the O atoms of the DMSO groups in axial positions; and the Ni—O_DMSO distance is in agreement with literature values: [2.1139 (12) Å - 1.9897 (13) Å (Tahir et al., 2007), 1.998 (3) Å - 2.105 (3) Å (Zhang et al. 2007), 2.030 (2) Å- 2.057 (2)Å (Ma et al., 2003)].

The orientation of the DMSO molecule can be described by the torsion angles O3—Ni—O1—S [43.32 (4) °] and O2—Ni—O1—S [-137.70 (4) °]. The packing of (I) is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 2) which form a three-dimensional network (Fig. 2).

Experimental

Compound (I) was prepared by the reaction of dehydroacetic acid with nickel (II) chloride hexahydrate in the presence of sodium acetate (Casabò et al. 1987). Crystals of (I) were grown by slow evaporation of a dimethylsulfoxide solution..