Bis[μ-(3-acetyl-2-hy­droxy-6-methyl-4H-pyran-4-one-κ3 O:O′,O′′)]diaqua­tetra­kis­(pyridine-κN)dicopper(II) diperchlorate

Ali Ourari; Wassila Derafa; Sofiane Bouacida; Djouhra Aggoun; Jean-Claude Daran

doi:10.1107/S1600536812041608

. 2012 Oct 13;68(Pt 11):m1356–m1357. doi: 10.1107/S1600536812041608

Bis[μ-(3-acetyl-2-hydroxy-6-methyl-4H-pyran-4-one-κ³ O:O′,O′′)]diaquatetrakis(pyridine-κN)dicopper(II) diperchlorate

Ali Ourari ^a, Wassila Derafa ^a, Sofiane Bouacida ^b,^c,^*, Djouhra Aggoun ^a, Jean-Claude Daran ^d

PMCID: PMC3515113 PMID: 23284340

Abstract

In the centrosymmetric binuclear cation of the title compound, [Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂, the Cu^II atoms are bridged by a pair of two dehydroacetate anions in a bis-/monodentate mode. The distorted octahedral N₂O₄ coordination sphere of the metal cation is completed by two pyridine N atoms and one O atom of a water molecule. The complex cations and the perchlorate counter anions are arranged in layers parallel to (100). O—H⋯O hydrogen bonds between the coordinating water molecules and the perchlorate anions constitute ribbons parallel to [10-1]. C—H⋯O hydrogen bonds are also observed.

Related literature

For the synthesis of similar compounds, see: Tan & Kok-Peng Ang (1988 ▶); El-Kubaisi & Ismail (1994 ▶); Danilova et al. (2003 ▶); Munde et al. (2010 ▶); Ourari et al. (2011 ▶). For applications of related compounds, see: Maiti et al. (1988 ▶); Mohan et al. (1981 ▶); Das & Livingstone (1976 ▶); Ourari et al. (2008 ▶, 2012 ▶).

Experimental

Crystal data

[Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂
M _r = 1012.70
Triclinic,
a = 9.9371 (4) Å
b = 10.3072 (4) Å
c = 10.4440 (5) Å
α = 99.624 (4)°
β = 90.540 (3)°
γ = 97.895 (4)°
V = 1044.09 (8) Å³
Z = 1
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 180 K
0.44 × 0.34 × 0.13 mm

Data collection

Agilent Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.505, T _max = 1.000
20280 measured reflections
4692 independent reflections
3889 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.140
S = 1.12
4692 reflections
288 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Click here for additional data file.^{(29.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812041608/wm2685sup1.cif

e-68-m1356-sup1.cif^{(29.8KB, cif)}

Click here for additional data file.^{(225.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041608/wm2685Isup2.hkl

e-68-m1356-Isup2.hkl^{(225.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.922 (3)
Cu1—O2	1.962 (3)
Cu1—N2	2.005 (3)
Cu1—N1	2.006 (3)
Cu1—O1W	2.325 (3)
Cu1—O4ⁱ	2.737 (3)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O12	0.83 (6)	2.13 (6)	2.934 (9)	165 (6)
O1W—H2W⋯O11ⁱⁱ	0.74 (6)	2.06 (6)	2.772 (9)	164 (6)
C9—H9⋯O13ⁱⁱⁱ	0.93	2.56	3.389 (7)	148

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

Acknowledgments

The authors thank the Algerian Ministère de l’Enseignement Supérieur et de la Recherche Scientifique for financial support.

supplementary crystallographic information

Comment

Dehydroacetic acid is used for the synthesis of heterocyclic compounds, some of them with therapeutic activities useful for treatment of human diseases (Das & Livingstone, 1976; Mohan et al., 1981; Maiti et al., 1988). Schiff bases, on the other hand, are widely applied in the synthesis transition metal coordination compounds (Tan & Kok-Peng Ang, 1988; El-Kubaisi & Ismail, 1994; Munde et al., 2010), showing catalytic activities particularly in the oxidation reactions carried out according to the cytochrome P450 model (Ourari et al., 2008, 2011, 2012). Thus, we attempted to synthesize Schiff base half-units in order to use them as starting materials to obtain unsymmetrical tetradentate Schiff base complexes according the Danilova method's (Danilova et al., 2003). Here we describe the formation of a new dinuclear complex, [Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂], (I), prepared from dehydroacetic acid, copper perchlorate and pyridine in methanolic solution.

The molecular structure of the complex binuclear and centrosymmetric cation of (I) is illustrated in Fig. 1. The connection mode of the copper cations exhibits dimers, i.e. two copper cations are bridged by two dehydroacetate anions in a bis-/monodentate fashion. The asymmetric unit of (I) contains only half of such a dimer. The distorted octahedral coordination sphere around the copper cation is completed by two pyridine ligands and one water molecule. The bond lengths range from 1.922 (3) to 2.325 (3) Å for the Cu—O distances with one more considerably longer bond for Cu—O4 of 2.737 (3) Å; the Cu—N bond lengths are 2.005 (3) and 2.006 (3) Å.

The crystal packing in (I) can be described by alterning layers of cations and tetrahedral perchlorate anions arranged parallel to (100) (Fig. 2). Intermolecular O—H···O hydrogen bonds (Table 2) between the coordinating water molecules and perchlorate anions constitute ribbons parallel to [101]; C—H···O hydrogen bonding interactions eventually links these constituents (Fig. 3).

Experimental

0.168 g (1 mmol) dehydroacetic acid and 0.373 g (1 mmol) copper bis-perchlorate hexahydrate were dissolved in 20 ml of methanol. To this solution 0.108 g (1 mmol) of 1,2-phenylendiamine was added with an excess of pyridine. The mixture was held under stirring and argon atmosphere for two hours. After that time a precipitate appeared that was recovered by filtration. The solid was washed several times with methanol before it was dried under vacuum (yield 64%). From the resulting filtrate crystals were obtained by slow evaporation.