The first 3D malonate bridged copper [Cu(O2C–CH2–CO2H)2·2H2O]: Structure, properties and electronic structure

A new inorganic-organic compound [Cu(O2C–CH2–CO2H)2·2H2O] ([Cumal]) was hydrothermally synthesized and characterized by IR spectroscopy, thermal analysis and single crystal X-ray diffraction. [Cumal] is the first three-dimensional compound existing in the system Cu(II)–malonic acid–H2O. Its framework is built up through carboxyl bridged copper where CuO6 octahedra are elongated with an almost D4h symmetry (4+2) due to the Jahn–Teller effect. The magnetic properties were studied by measuring its magnetic susceptibility in the temperature range of 2–300 K indicating the existence of weak ferromagnetic interactions. The electronic structure of [Cumal] was calculated within the density functional theory (DFT) framework. Structural features are well reproduced using DFT structural optimizations and the optical spectra, calculated within the dielectric formalism, explain very well the light blue colour of the compound. It is shown that a GGA+U approach with a Ueff value of about 6 eV is necessary for a better correlation with the experiment. - Graphical abstract: [Cu(O2C–CH2–CO2H)2·2H2O]: the first 3D hybrid organic–inorganic compound built up carboxyl groups. The network presents a diamond-like structure achieved via carboxyl. Highlights: ► A new organic–inorganic material with an unprecedented topology is synthesized. ► Crystallographic structure is determined using single crystal X-ray diffraction. ► Electronic structure is obtained from DFT, GGA+U calculation. ► Framework can be described as formed from CuC4 tetrahedron sharing four corners. ► This structure can be classified as an extended diamond structure.