High-Pressure Synthesis of Melilite-type Rare-Earth Nitridophosphates RE2P3N7 and a Ba2Cu[Si2O7]-type Polymorph.

High-pressure metathesis was proposed to be a gateway to the elusive class of rare-earth nitridophosphates. With this method the first ternary compounds of this class with sum formula RE2P3N7 were prepared, a melilite-type with RE = Pr, Nd, Sm, Eu, Ho, Yb (Ho2P3N7: P4̅21m, a = 7.3589(2), c = 4.9986(2) Å, Z = 2) and a Ba2Cu[Si2O7] structure type with RE = La, Ce, Pr (Pr2P3N7: monoclinic, C2/c, a = 7.8006(3), b = 10.2221(3), c = 7.7798(3) Å, β = 111.299(1)°, Z = 4). The phase relation between the two structure types was prior unknown and is here evidenced by experimental data as well as density functional theory calculations performed for the Pr2P3N7 compounds. Adequate classification of both structures types with regard to Liebau nomenclature, vertex symbol, and point symbol is made. Additionally, the tiling patterns of the monolayered structures are deducted. We demonstrate that high-pressure metathesis offers a systematic access to rare-earth nitridophosphates with an atomic ratio of P/N between 1/2 and 1/4.