Crystal Structure and Hirshfeld Surface Analysis of Bis(Triethanolamine)Nickel(II) Dinitrate Complex and a Revelation of Its Characteristics via Spectroscopic, Electrochemical and DFT Studies Towards a Promising Precursor for Metal Oxides Synthesis

Abstract

Metal complexes with chelating ligands are known as promising precursors for the synthesis of targeted metal oxides via thermal decomposition pathways. Triethanolamine (TEA) is a versatile ligand possessing a variety of coordination modes to metal ions. Understanding the crystal structure is beneficial for the rational design of the metal complex precursors. Herein, a bis(triethanolamine)nickel (II) dinitrate (named as Ni-TEA) crystal was synthesized and thoroughly investigated. X-ray crystallography revealed that Ni(II) ions adopt a distorted octahedral geometry surrounded by two neutral TEA ligands via two N and four O coordinates. Hirshfeld surface analysis indicated the major contribution of the intermolecular hydrogen-bonding between —OH groups of TEA in the crystal packing. Moreover, several O–H stretching peaks in Fourier transformed infrared spectroscopy (FTIR) spectra emphasizes the various chemical environments of —OH groups due to the formation of the hydrogen-bonding framework. The Density-functional theory (DFT) calculation revealed the electronic properties of the crystal. Furthermore, the Ni-TEA complex is presumably useful for metal oxide synthesis via thermal decomposition at a moderate temperature (380 °C). Cyclic voltammetry indicated the possible oxidative reaction of the Ni-TEA complex at a lower potential than nickel(II) nitrate and TEA ligand, highlighting its promising utility for the synthesis of mixed valence oxides such as spinel structures.

Keywords

• metal complex
• triethanolamine
• coordination chemistry
• crystal structure
• hydrogen bonding
• Hirshfeld surface analysis