Poly[μ-aqua-diaquabis­[μ-2-cyano-2-(oxidoimino)­acetato]­copper(II)dipotassium]

Irina A Golenya; Yulia A Izotova; Natalia I Usenko; Valentina A Kalibabchuk; Natalia V Kotova

doi:10.1107/S1600536812036641

. 2012 Sep 26;68(Pt 10):m1303–m1304. doi: 10.1107/S1600536812036641

Poly[μ-aqua-diaquabis[μ-2-cyano-2-(oxidoimino)acetato]copper(II)dipotassium]

Irina A Golenya ^a, Yulia A Izotova ^b, Natalia I Usenko ^a, Valentina A Kalibabchuk ^c,^*, Natalia V Kotova ^a

PMCID: PMC3470173 PMID: 23125617

Abstract

In the title compound, [CuK₂(C₃N₂O₃)₂(H₂O)₃]_n, the Cu²⁺ atom is in a distorted square-pyramidal coordination geometry. Two N atoms belonging to the oxime groups and two O atoms belonging to the carboxylate groups of two trans-disposed doubly deprotonated residues of 2-cyano-2-(hydroxyimino)acetic acid make up the basal plane and the apical position is occupied by the water molecule. The neighboring Cu-containing moieties are linked into a three-dimensional framework by K—O and K—N contacts formed by two potassium cations with the carboxylate and the oxime O atoms and the nitrile N atoms of the ligand. The environments of the K⁺ cations are complemented to octa- and nonacoordinated, by K—O contacts with H₂O molecules. The crystal structure features O—H⋯O hydrogen bonds.

Related literature

For the use of mononuclear complexes in the preparation of polynuclear complexes, see: Kahn (1993 ▶); Goodwin et al. (2000 ▶); Krämer & Fritsky (2000 ▶); Fritsky et al. (2001 ▶, 2003 ▶); Wörl et al. (2005 ▶). For the use of derivatives of 2-hydroxyiminocarboxylic acids and their derivatives as versatile ligands, see: Dvorkin et al. (1990a ▶,b ▶); Lampeka et al. (1989 ▶); Skopenko et al. (1990 ▶); Sachse et al. (2008 ▶); Fritsky et al. (1998 ▶, 2006 ▶); Kanderal et al. (2005 ▶); Moroz et al. (2008 ▶, 2010 ▶, 2012 ▶). For metal complexes of 2-cyano-2-(hydroxyimino)acetic acid, see: Sliva et al. (1998 ▶); Mokhir et al. (2002 ▶); Eddings et al. (2004 ▶). For related structures, see: Duda et al. (1997 ▶); Fritsky et al. (2004 ▶); Onindo et al. (1995 ▶); Sliva et al. (1997 ▶); Świątek-Kozłowska et al. (2000 ▶); Kovbasyuk et al. (2004 ▶). For the synthesis of the ligand, see: Sliva et al. (1998 ▶).

Experimental

Crystal data

[CuK₂(C₃N₂O₃)₂(H₂O)₃]
M _r = 419.89
Monoclinic,
a = 8.767 (2) Å
b = 12.426 (3) Å
c = 13.159 (5) Å
β = 108.26 (3)°
V = 1361.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 100 K
0.24 × 0.16 × 0.07 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.657, T _max = 0.859
9166 measured reflections
3189 independent reflections
3006 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.062
S = 1.09
3189 reflections
205 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036641/hp2047sup1.cif

e-68-m1303-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036641/hp2047Isup2.hkl

e-68-m1303-Isup2.hkl^{(156.5KB, 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
O1W—H11W⋯O3A ⁱ	0.89	1.85	2.7257 (19)	171
O1W—H21W⋯O3ⁱⁱ	0.80	1.96	2.6910 (19)	151
O2W—H12W⋯O1ⁱⁱⁱ	0.81	2.19	2.993 (2)	173
O2W—H22W⋯O3A ⁱ	0.92	2.02	2.926 (2)	164

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

Acknowledgments

This work was supported by the State Fund for Fundamental Researches of Ukraine (grant No. F40.3/041), the Russian Fund for Basic Research (grants11–03-00262 and 11–03-90417) and the Federal Targeted Program Scientific and Scientific-Pedagogical Personnel of Innovative Russia in 2009–2013 (contract P1294 from 09/06/2010).

supplementary crystallographic information

Comment

Many reported mononuclear complexes of 3 d-metals contains vacant donor atoms or chelate centers, so that they can be considered as ligands for preparation of homo- and heteropolynuclear systems which are widely used in bioinorganic modeling, catalysis and in molecular magnetism (Kahn, 1993; Goodwin et al., 2000; Krämer et al., 2000; Fritsky et al., 2001; Fritsky et al., 2003; Wörl et al., 2005). Polydentate ligands containing oxime and carboxylic groups attract particular attention due to their potential for the bridging mode of coordination and mediation of strong magnetic exchange interactions between metal ions (Lampeka et al., 1989; Dvorkin et al., 1990a, 1990b; Skopenko et al., 1990; Sachse et al., 2008; Moroz et al., 2008, 2010, 2012) and for preparation of metal complexes with efficient stabilization of unusually high oxidation states of 3 d-metal ions like copper(III) and nickel(III) (Fritsky et al., 1998; Kanderal et al., 2005; Fritsky et al., 2006). 2-cyano-2-(hydroxyimino)acetic acid (aaco) is an efficient chelating ligand for Cu(II) and Ni(II) ions (Sliva et al., 1998; Mokhir et al., 2002). To date, only one heterometallic complex containing this ligand K₂[Pd(aaco-2H)₂].4H₂O has been structurally characterized (Eddings et al., 2004). Herein we report the second heterometallic complex based on 2-cyan-2-hydroxyiminoacetic acid.

The title compound, [K₂Cu(C₃N₂O₃)₂(H₂O)₃]_n, has an ionic structure containing 2- charged Cu(II)-centered complex anions, potassium cations and water molecules (Fig. 1). The Cu atom is in a distorted square-pyramidal geometry, defined by two N atoms belonging to the oxime groups and two O atoms belonging to the carboxylic groups of two trans-disposed doubly deprotonated residues of 2-cyano-2-(hydroxyimino)acetic acid. The apical position is occupied by the water molecule O1W which also serves as a bridge between Cu1 and K1 ions. The coordination bond lengths Cu—N and Cu—O (Table 1) are typical for square-pyramidal Cu(II) complexes with deprotonated oxime and carboxylate donors (Sliva et al., 1997; Kanderal et al., 2005). The bite angles around the central atom deviate from an ideal square-planar configuration [e.g. O2—Cu1—N1 = 82.89 (6)°], which is a consequence of the formation of five-membered chelate rings. The bond lengths C—O, N—O and C—N in the coordinated 2-oximinocarboxylate ligand are typical for copper(II) complexes with cyanoximes and carboxylates (Onindo et al., 1995; Duda et al., 1997; Fritsky et al., 2004;).

The potassium cations K1 and K2 are bound to the copper(II) complex anion in a chelate fashion via the oxime oxygen (O1A and O1, respectively) and the carboxylic oxygen (O2 and O2A, respectively) atoms. Such coordination of two potassium cations from the different side of the complex anion results in a closed metallamacrocylic framework. Both potassium cations also forms additional K—O and K—N contacts with the carboxylic and the oxime O atoms and the nitrile N atoms of the neighboring Cu complex anions thus uniting them in a three-dimensional framework (Fig. 2). The environments of K1 and K2 potassium cation are complemented to octa- and nona-coordinated, respectively, by K—O contacts with H₂O molecules. The K—O and K—N bond lengths are normal for potassium cations and close to those reported in the structures of the carboxylate and the oximate complexes (Fritsky et al., 1998; Świątek-Kozłowska et al., 2000; Kovbasyuk et al., 20040). The crystal structure involves intermolecular O—H···O hydrogen bonds where the water molecules act as donors, and the carboxylic and the oxime O atoms act as acceptors (Table 2).

Experimental

Cu(NO₃)₂.3H₂O (0.242 g, 1 mmol) was dissolved in water (3 ml) and added to the methanolic solution (15 ml) of 2-cyano-2-(hydroxyimino)acetic acid (0.228 g, 2 mmol), synthesizsed according to Sliva et al., 1998). To the obtained mixture, aqueous solution of potassium hydroxide (1M, 4 ml) was added with vigorous stirring at room temperature. The obtained transparent solution was stirred 20 min. and then set aside for crystallization at ambient temperature. Bright brown crystals were separated by filtration after 72 h, washed with cold water (10 ml) and dried (yield 78%). Analysis calculated for C₆H₆Cu K₂N₄O₉: C 17.16, H 1.44, N 13.34%; found: C 17.10, H 1.53, N 13.42%.