Crystal structures of two CuII compounds: catena-polychlorido­copper(II)-μ-N-eth­oxy(pyridin-2-yl)methyl­idene-N′-oxido(pyridin-3-yl)methyl­idenehydrazine-κ4NN′O:N′′ and di-μ-chlorido-1:4κ2Cl:Cl-2:3κ2Cl:Cl-di­chlorido-2κCl4κCl-bisμ3-eth­oxy(pyridin-2-yl)methano­lato-1:2:3κ3O:NO:O;1:3:4κ3O:O:NObis­μ2-eth­oxy(pyridin-2-yl)methano­lato-1:2κ3NO:O;3:4κ3NO:Otetracopper(II)

摘要

Two Cu^II complexes [Cu(C14H13N4O2)Cl]n, >I, and [Cu4(C8H10NO2)4Cl4]n, >II, have been synthesized. In the structure of the mononuclear complex >I, each ligand is coordinated to two metal centers. The basal plane around the Cu^II cation is formed by one chloride anion, one oxygen atom, one imino and one pyridine nitro­gen atom. The apical position of the distorted square-pyramidal geometry is occupied by a pyridine nitro­gen atom from a neighbouring unit, leading to infinite one-dimensional polymeric chains along the b-axis direction. Each chain is connected to adjacent chains by inter­molecular C—H⋯O and C—H⋯Cl inter­actions, leading to a three-dimensional network structure. The tetra­nuclear complex >II lies about a crystallographic inversion centre and has one core in which two Cu^II metal centers are mutually inter­connected via two enolato oxygen atoms while the other two Cu^II cations are linked by a chloride anion and an enolato oxygen. An open-cube structure is generated in which the two open-cube units, with seven vertices each, share a side composed of two Cu^II ions bridged by two enolato oxygen atoms acting in a μ3-mode. The Cu^II atoms in each of the two CuO3NCl units are connected by one μ2-O and two μ3-O atoms from deprotonated hydroxyl groups and one chloride anion to the three other Cu^II centres. Each of the penta­coordinated Cu^II cations has a distorted NO₃Cl square-pyramidal environment. The Cu^II atoms in each of the two CuO₂NCl₂ units are connected by μ₂-O and μ₃-O atoms from deprotonated alcohol hy­droxy groups and one chloride anion to two other Cu^II ions. Each of the penta­coordinated Cu^II cations has a distorted NO₂Cl₂ square-pyramidal environment. In the crystal, a series of intra­molecular C—H⋯O and C—H⋯Cl hydrogen bonds are observed in each tetra­nuclear monomeric unit, which is connected to four tetra­nuclear monomeric units by inter­molecular C—H⋯O hydrogen bonds, thus forming a planar two-dimensional structure in the (01) plane.