DOE OSTI2020
Zr3N2O3 crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are six inequivalent Zr4+ sites. In the first Zr4+ site, Zr4+ is bonded to two N3- and four O2- atoms to form a mixture of distorted corner and edge-sharing ZrN2O4 octahedra. The corner-sharing octahedra tilt angles range from 30–52°. There are one shorter (2.15 Å) and one longer (2.23 Å) Zr–N bond lengths. There are a spread of Zr–O bond distances ranging from 2.11–2.25 Å. In the second Zr4+ site, Zr4+ is bonded to four N3- and two O2- atoms to form a mixture of distorted corner and edge-sharing ZrN4O2 octahedra. The corner-sharing octahedra tilt angles range from 25–52°. There are a spread of Zr–N bond distances ranging from 2.14–2.29 Å. There are one shorter (2.11 Å) and one longer (2.22 Å) Zr–O bond lengths. In the third Zr4+ site, Zr4+ is bonded to two N3- and four O2- atoms to form a mixture of distorted corner and edge-sharing ZrN2O4 octahedra. The corner-sharing octahedra tilt angles range from 24–37°. There are one shorter (2.15 Å) and one longer (2.22 Å) Zr–N bond lengths. There are one shorter (2.11 Å) and three longer (2.16 Å) Zr–O bond lengths. In the fourth Zr4+ site, Zr4+ is bonded to three N3- and three O2- atoms to form a mixture of distorted corner and edge-sharing ZrN3O3 octahedra. The corner-sharing octahedra tilt angles range from 25–41°. There are one shorter (2.14 Å) and two longer (2.19 Å) Zr–N bond lengths. There are a spread of Zr–O bond distances ranging from 2.09–2.32 Å. In the fifth Zr4+ site, Zr4+ is bonded to three N3- and three O2- atoms to form distorted ZrN3O3 octahedra that share corners with four ZrN2O4 octahedra and edges with six ZrN4O2 octahedra. The corner-sharing octahedra tilt angles range from 24–57°. There are two shorter (2.15 Å) and one longer (2.20 Å) Zr–N bond lengths. There are a spread of Zr–O bond distances ranging from 2.09–2.35 Å. In the sixth Zr4+ site, Zr4+ is bonded to two equivalent N3- and four O2- atoms to form a mixture of distorted corner and edge-sharing ZrN2O4 octahedra. The corner-sharing octahedra tilt angles range from 24–57°. Both Zr–N bond lengths are 2.16 Å. There are a spread of Zr–O bond distances ranging from 2.03–2.31 Å. There are four inequivalent N3- sites. In the first N3- site, N3- is bonded to four Zr4+ atoms to form distorted NZr4 tetrahedra that share corners with two equivalent NZr4 tetrahedra, corners with two NZr4 trigonal pyramids, and edges with two equivalent OZr4 trigonal pyramids. In the second N3- site, N3- is bonded to four Zr4+ atoms to form a mixture of distorted corner and edge-sharing NZr4 trigonal pyramids. In the third N3- site, N3- is bonded to four Zr4+ atoms to form distorted NZr4 trigonal pyramids that share a cornercorner with one NZr4 tetrahedra, corners with three NZr4 trigonal pyramids, edges with two equivalent NZr4 trigonal pyramids, and edges with two equivalent OZr4 trigonal pyramids. In the fourth N3- site, N3- is bonded to four Zr4+ atoms to form distorted NZr4 trigonal pyramids that share a cornercorner with one OZr4 trigonal pyramid, corners with two equivalent NZr4 trigonal pyramids, and edges with four NZr4 trigonal pyramids. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted T-shaped geometry to three Zr4+ atoms. In the second O2- site, O2- is bonded in a distorted T-shaped geometry to three Zr4+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to three Zr4+ atoms. In the fourth O2- site, O2- is bonded in a distorted T-shaped geometry to three Zr4+ atoms. In the fifth O2- site, O2- is bonded to four Zr4+ atoms to form distorted OZr4 trigonal pyramids that share a cornercorner with one NZr4 trigonal pyramid, corners with two equivalent OZr4 trigonal pyramids, edges with two equivalent NZr4 tetrahedra, and edges with two equivalent NZr4 trigonal pyramids. In the sixth O2- site, O2- is bonded in a 4-coordinate geometry to four Zr4+ atoms.