DOI: 10.17188/1318176
title: Materials Data on Ca5(VN3)2 by Materials Project

description: Ca5(VN3)2 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are five inequivalent Ca2+ sites. In the first Ca2+ site, Ca2+ is bonded to four N3- atoms to form CaN4 trigonal pyramids that share corners with two equivalent CaN5 square pyramids, corners with two equivalent CaN5 trigonal bipyramids, corners with two equivalent CaN4 trigonal pyramids, an edgeedge with one CaN5 square pyramid, and edges with two equivalent CaN5 trigonal bipyramids. There are a spread of Ca–N bond distances ranging from 2.38–2.59 Å. In the second Ca2+ site, Ca2+ is bonded to five N3- atoms to form CaN5 square pyramids that share corners with two equivalent CaN5 square pyramids, a cornercorner with one CaN5 trigonal bipyramid, corners with two equivalent CaN4 trigonal pyramids, edges with two equivalent CaN5 square pyramids, and edges with three CaN5 trigonal bipyramids. There are a spread of Ca–N bond distances ranging from 2.41–2.64 Å. In the third Ca2+ site, Ca2+ is bonded to five N3- atoms to form CaN5 trigonal bipyramids that share a cornercorner with one CaN5 square pyramid, corners with two equivalent CaN5 trigonal bipyramids, edges with three CaN5 square pyramids, edges with two equivalent CaN5 trigonal bipyramids, and edges with two equivalent CaN4 trigonal pyramids. There are a spread of Ca–N bond distances ranging from 2.41–2.70 Å. In the fourth Ca2+ site, Ca2+ is bonded to five N3- atoms to form distorted CaN5 square pyramids that share corners with two equivalent CaN5 square pyramids, a cornercorner with one CaN5 trigonal bipyramid, edges with two equivalent CaN5 square pyramids, edges with three CaN5 trigonal bipyramids, and an edgeedge with one CaN4 trigonal pyramid. There are a spread of Ca–N bond distances ranging from 2.33–2.99 Å. In the fifth Ca2+ site, Ca2+ is bonded to five N3- atoms to form distorted CaN5 trigonal bipyramids that share a cornercorner with one CaN5 square pyramid, corners with two equivalent CaN5 trigonal bipyramids, corners with two equivalent CaN4 trigonal pyramids, edges with three CaN5 square pyramids, and edges with two equivalent CaN5 trigonal bipyramids. There are a spread of Ca–N bond distances ranging from 2.39–2.91 Å. There are two inequivalent V4+ sites. In the first V4+ site, V4+ is bonded in a trigonal planar geometry to three N3- atoms. There is two shorter (1.79 Å) and one longer (1.81 Å) V–N bond length. In the second V4+ site, V4+ is bonded in a trigonal planar geometry to three N3- atoms. There are a spread of V–N bond distances ranging from 1.72–1.88 Å. There are six inequivalent N3- sites. In the first N3- site, N3- is bonded in a distorted rectangular see-saw-like geometry to three Ca2+ and one V4+ atom. In the second N3- site, N3- is bonded to four Ca2+ and one V4+ atom to form distorted NCa4V square pyramids that share corners with three NCa4V square pyramids, corners with three equivalent NCa4V trigonal bipyramids, edges with two equivalent NCa5V octahedra, and an edgeedge with one NCa4V square pyramid. In the third N3- site, N3- is bonded to five Ca2+ and one V4+ atom to form NCa5V octahedra that share corners with two equivalent NCa5V octahedra, edges with four NCa4V square pyramids, and edges with two equivalent NCa4V trigonal bipyramids. The corner-sharing octahedral tilt angles are 13°. In the fourth N3- site, N3- is bonded to four Ca2+ and one V4+ atom to form NCa4V square pyramids that share corners with three NCa4V square pyramids, a cornercorner with one NCa4V trigonal bipyramid, edges with two equivalent NCa5V octahedra, an edgeedge with one NCa4V square pyramid, and an edgeedge with one NCa4V trigonal bipyramid. In the fifth N3- site, N3- is bonded in a 5-coordinate geometry to four Ca2+ and one V4+ atom. In the sixth N3- site, N3- is bonded to four Ca2+ and one V4+ atom to form distorted NCa4V trigonal bipyramids that share corners with four NCa4V square pyramids, corners with two equivalent NCa4V trigonal bipyramids, edges with two equivalent NCa5V octahedra, and an edgeedge with one NCa4V square pyramid.