Aqua[1-(pyridin-2-yl)ethanone oximato][1-(2-pyridin-2-yl)ethanone oxime]­copper(II) perchlorate mono­hydrate

Baoyun Zhong; Shengli Li; Guifang Chen

doi:10.1107/S1600536812023872

. 2012 Jun 13;68(Pt 7):m874. doi: 10.1107/S1600536812023872

Aqua[1-(pyridin-2-yl)ethanone oximato][1-(2-pyridin-2-yl)ethanone oxime]copper(II) perchlorate monohydrate

Baoyun Zhong ^a, Shengli Li ^b, Guifang Chen ^b,^*

PMCID: PMC3393154 PMID: 22807722

Abstract

In the title compound, [Cu(C₇H₇N₂O)(C₇H₈N₂O)(H₂O)]ClO₄·H₂O, the Cu^II ion is five-coordinated by the N atoms from the 1-(pyridin-2-yl)ethanone oximate and 1-(pyridin-2-yl)ethanone oxime ligands and by the water O atom in a distorted square-pyramidal geometry. The two organic ligands are linked by an intramolecular O—H⋯O hydrogen bond. In the crystal, molecules and ions are linked by O—H⋯O hydrogen-bonding interactions, forming chains along the a axis. The perchlorate O atoms are disordered in a 0.58 (2):0.42 (2) ratio.

Related literature

For the coordination chemistry of oximes, see: Chaudhuri (2003 ▶); Pavlishchuk et al. (2003 ▶). For related structures, see: Qiu et al. (2011 ▶); Wu & Wu (2008 ▶); Zuo et al. (2007 ▶). For the properties of related complexes, see: Davidson et al. (2007 ▶); Clerac et al. (2002 ▶).

Experimental

Crystal data

[Cu(C₇H₇N₂O)(C₇H₈N₂O)(H₂O)]ClO₄·H₂O
M _r = 470.32
Monoclinic,
a = 6.3526 (7) Å
b = 15.7199 (14) Å
c = 9.8235 (9) Å
β = 101.235 (1)°
V = 962.20 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.32 mm⁻¹
T = 298 K
0.45 × 0.40 × 0.39 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.587, T _max = 0.626
4732 measured reflections
2284 independent reflections
2062 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.096
S = 1.00
2284 reflections
292 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ▶)
Flack parameter: 0.00 (2)

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 ▶), Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023872/aa2060sup1.cif

e-68-0m874-sup1.cif^{(28.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023872/aa2060Isup2.hkl

e-68-0m874-Isup2.hkl^{(112.2KB, 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
O1—H1⋯O2	0.82	1.63	2.421 (7)	163
O3—H3C⋯O2ⁱ	0.85	1.92	2.757 (6)	170
O3—H3D⋯O8ⁱ	0.85	1.82	2.658 (8)	170
O8—H8C⋯O6ⁱⁱ	0.85	1.86	2.660 (7)	157
O8—H8D⋯O4ⁱⁱⁱ	0.85	2.11	2.862 (7)	148

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

supplementary crystallographic information

Comment

There is a new interest in the coordination chemistry of oximes (Davidson et al., 2007; Pavlishchuk et al., 2003; Chaudhuri, 2003). 2-pyridyl oximes are a subclass of oximes whose anions are versatile ligands for a variety of research objectives and have been key ligands in several areas of molecular magnetism, including single-molecule and single-chain magnets (Clerac et al., 2002).

In the title complex (Fig. 1) the Cu²⁺ center is five-coordinated by N atoms from two 1-(pyridin-2-yl)ethanone oxime ligands (one of them is deprotonated) and one water molecule. The two 1-(pyridin-2-yl)ethanone oxime ligands are coordinated to copper to form two five-membered CuC₂N₂ rings and a strong intramolecular hydrogen bond exists between the OH group and the negatively charged oxygen of the other ligand which is shorter than reported in the literature (Qiu et al., 2011; Wu et al. 2008). The copper atom adopts a distorted 4+1 square-pyramidal coordination mode with the distortion parameter being 0.005, which is smaller than the values reported in the literature (Qiu et al., 2011; Wu et al., 2008). Another water molecule and the perchlorate anion are not coordinated but they take part in the formation of H-bonds (Table 1). The perclorate O atoms are disordered between two orientations around the central Cl atom with the occupancies 0.42 (2) (O4/O7) and 0.58 (2) (O4A/O7A).

Experimental

A solution of Cu(ClO₄)₂ (0.1311 g, 0.5 mmol) in H₂O (10 ml) was added to a solution of 1-(pyridin-2-yl)ethanone oxime (0.068 g, 0.5 mmol) in MeCN (10 ml). After 0.5 h stirring, solid NaOAc (0.082 g, 1 mmol) was added slowly, and the reaction mixture was kept under magnetic stirring for another 6h. A small quantity of undissolved material was removed by filtration and the solution was left to slowly evaporate, and after one month, green crystals suitable for X-ray diffraction were obtained. (20.5%, m.p. 310-315 K). FTIR (KBr) v (cm^-l): 3448 (O—H); 1597, (Cδb N); 2917, 1437, (C—H); 1157, 1177, 1260 (N—O).