Materials Data on ZrP2NCl11 by Materials Project

Abstract

ZrCl5P2NCl6 crystallizes in the orthorhombic Cmce space group. The structure is zero-dimensional and consists of eight P2NCl6 clusters and four ZrCl5 clusters. In each P2NCl6 cluster, P5+ is bonded to one N3- and three Cl1- atoms to form corner-sharing PNCl3 tetrahedra. The P–N bond length is 1.57 Å. There is one shorter (1.97 Å) and two longer (1.98 Å) P–Cl bond length. N3- is bonded in a bent 150 degrees geometry to two equivalent P5+ atoms. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In each ZrCl5 cluster, Zr4+ is bonded to six Cl1- atoms to form edge-sharing ZrCl6 octahedra. There are a spread of Zr–Cl bond distances ranging from 2.41–2.68 Å. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a water-like geometry to two equivalent Zr4+ atoms. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Zr4+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Zr4+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Zr4+ atom.