Poly[bis[μ4-N-(2-hydroxyiminopropionyl)-N′-(2-oxidoiminopropionyl)propane-1,3-diaminato]dimethanolcalciumdicopper(II)]

In the title compound, [CaCu2(C9H13N4O4)2(CH3OH)2]n, the CaII atom lies on an inversion center and is situated in a moderately distorted octahedral environment. The CuII atom is in a distorted square-pyramidal geometry, defined by four N atoms belonging to the amide and oxime groups of the triply deprotonated residue of N,N′-bis(2-hydroxyiminopropanoyl)propane-1,3-diamine (H4pap) and one oxime O atom from a neighboring Hpap ligand at the apical site, forming a dimeric [Cu2(Hpap)2]2− unit. Each dimeric unit connects four Ca atoms and each Ca atom links four [Cu2(Hpap)2]2− units through Ca—O(amide) bonds, leading to a three-dimensional framework. The crystal structure involves intra- and intermolecular O—H⋯O hydrogen bonds.

In the title compound, [CaCu 2 (C 9 H 13 N 4 O 4 ) 2 (CH 3 OH) 2 ] n , the Ca II atom lies on an inversion center and is situated in a moderately distorted octahedral environment. The Cu II atom is in a distorted square-pyramidal geometry, defined by four N atoms belonging to the amide and oxime groups of the triply deprotonated residue of N,N 0 -bis(2-hydroxyiminopropanoyl)propane-1,3-diamine (H 4 pap) and one oxime O atom from a neighboring Hpap ligand at the apical site, forming a dimeric [Cu 2 (Hpap) 2 ] 2À unit. Each dimeric unit connects four Ca atoms and each Ca atom links four [Cu 2 (Hpap) 2 ] 2À units through Ca-O(amide) bonds, leading to a three-dimensional framework. The crystal structure involves intra-and intermolecular O-HÁ Á ÁO hydrogen bonds.

Earlier, the crystal and molecular structures of mononuclear anionic copper(II) complexes with N,N'-bis(2-
The structure of the title compound is presented in Fig. 1. The ligand in the complex anion is coordinated in a tetradentate fashion forming three condensed chelate rings and being triply deprotonated. In the complex anion the Cu II atom is situated in a distorted square-pyramidal geometry. The basal plane is defined by four N atoms belonging to the deprotonated amide and oxime groups of the Hpap ligand, which adopt a pseudo-macrocyclic conformation due to the presence of an intramolecular  (Table 1) are normal for the complexes with N-coordinated amide and oxime groups (Fritsky et al., 1998;Fritsky et al., 2006). A noticeable difference between Cu-N(amide) and Cu-N(oxime) distances is observed.
The O1···O2 separation of the intramolecular hydrogen bond is equal to 2.610 (2) Å, which is close to the values reported for the analogous complexes with lithium and tetraphenylphosponium cations. The C═N, C═O, N-O and C-N bond supplementary materials sup-2 lengths are typical for 2-hydroxyiminopropanoic acid and its amide derivatives (Fritsky, 1999;Mokhir et al., 2002;Moroz et al., 2008).
The Ca II atom occupies a special position and is situated in moderately distorted octahedral environment (Fig. 1) (Table 2), lead to a three-dimensional framework (Fig. 2).

Experimental
A solution of N,N'-bis(2-hydroxyiminopropanoyl)propane-1,3-diamine (0.244 g, 1 mmol) in 10 ml of methanol was heated to 323 K and added with stirring to a solution of copper(II) chloride dihydrate (0.170 g, 1 mmol) in water (5 ml). Then an aqueous solution of calcium hydrocarbonate (4 ml, 1 M) was added. The obtained mixture was stirred at 323 K for 10 min and then filtered. The filtrate was cooled, filtered and set aside for crystallization at room temperature. The resulting dark-red crystals formed within 12 h were separated by filtration, washed with water and air-dried (yield 78%). N,N'-bis(2hydroxyiminopropanoyl)propane-1,3-diamine was prepared according to the reported procedure (Duda et al., 1997).