Novel first-row transition-metal phosphates: hydrothermal synthesis and crystal structures

Acta Crystallogr C Struct Chem. 2022 May 1;78(Pt 5):287-294. doi: 10.1107/S2053229622003692. Epub 2022 Apr 11.

Abstract

Two new compounds, sodium copper nickel diorthophosphate, Na2CuNi(PO4)2 (I), and dimanganese copper diorthophosphate, Mn2Cu(PO4)2 (II), were synthesized hydrothermally, yielding single crystals, and were studied by X-ray diffraction. In the crystal structures, various transition metals of d-elements occupy symmetrically independent crystallographic positions with different coordination geometries. In the crystal structure of Na2NiCu(PO4)2, NiO6 and CuO6 octahedra share edges to form chains that PO4 groups link into a framework with cavities filled with Na atoms. Layered cationic fragments formed from dimers of MnO5 trigonal bipyramids and CuO4 square planes, sharing vertices, are connected through PO4 tetrahedra into a 3-periodic Mn2Cu(PO4)2 crystal structure. Structural correlations between Na2NiCu(PO4)2 and NaCuPO4 are discussed, and crystal-chemical details of the currently known exclusively synthetic mixed Mn/Cu and Ni/Cu phosphates are presented.

Keywords: coordination geometry; crystal structure; double-metal phosphate; hydrothermal synthesis; magnetic material; transition-metal phosphate.