Synthesis and crystal structure of Mg0.5NbO2: An ion-exchange reaction with Mg2+ between trigonal [NbO2]− layers

A new layered niobate, Mg0.5NbO2, was synthesized from LiNbO2 through a cation-exchange reaction with Mg2+ at 450–550 °C. This is the first example of a topotactic reaction with an aliovalent cation between trigonal [NbO2]− layers. It is proposed to be isostructural with LiNbO2 (space group; P63/mmc) with lattice parameters of a=2.9052(6) Å, c=10.625(15) Å. The lattice parameters and formation energy of Mg0.5NbO2 crystallized in LiNbO2 form and other layered CaNb2O4 one were calculated by density functional theory. - Graphical abstract: A new layered niobate, Mg0.5NbO2, was synthesized from LiNbO2 through a cation-exchange reaction with Mg2+ at 450–550 °C. It is isostructural with LiNbO2 with lattice parameters of a=2.9052(6) Å, c=10.625(15) Å. Mg2+ are described in spheres located between [NbO2]− trigonal layers and its occupancy is 0.5. Highlights: ► A new layered niobate, Mg0.5NbO2, was synthesized from LiNbO2. ► Cation-exchange reaction converted two monovalent Li+ into one divalent Mg2+ at 450–550 °C. ► Mg0.5NbO2 was isostructural with LiNbO2 (space group; P63/mmc). ► Its lattice parameters were a=2.9052(6) Å and c=10.625(15) Å. ► Synthesized Mg0.5NbO2 was calculated to be thermodynamically more favorable.