Materials Data on NaTi5(NCl)5 by Materials Project

Abstract

NaTi5(NCl)5 is beta indium sulfide-derived structured and crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Na1+ is bonded to six Cl1- atoms to form distorted NaCl6 pentagonal pyramids that share corners with eight TiN4Cl2 octahedra, corners with two equivalent NaCl6 pentagonal pyramids, and edges with two TiN4Cl2 octahedra. The corner-sharing octahedra tilt angles range from 42–60°. There are a spread of Na–Cl bond distances ranging from 2.81–3.02 Å. There are five inequivalent Ti+3.80+ sites. In the first Ti+3.80+ site, Ti+3.80+ is bonded to four N3- and two Cl1- atoms to form distorted TiN4Cl2 octahedra that share corners with two TiN4Cl2 octahedra, corners with two equivalent NaCl6 pentagonal pyramids, and edges with six TiN4Cl2 octahedra. The corner-sharing octahedra tilt angles range from 12–13°. There are a spread of Ti–N bond distances ranging from 1.98–2.04 Å. Both Ti–Cl bond lengths are 2.54 Å. In the second Ti+3.80+ site, Ti+3.80+ is bonded to four N3- and two Cl1- atoms to form distorted TiN4Cl2 octahedra that share corners with two TiN4Cl2 octahedra, corners with two equivalent NaCl6 pentagonal pyramids, and edges with six TiN4Cl2 octahedra. The corner-sharing octahedra tilt angles range from 13–14°. There are a spread of Ti–N bond distances ranging from 1.98–2.05 Å. Both Ti–Cl bond lengths are 2.54 Å. In the third Ti+3.80+ site, Ti+3.80+ is bonded to four N3- and two Cl1- atoms to form distorted TiN4Cl2 octahedra that share corners with two TiN4Cl2 octahedra, corners with two equivalent NaCl6 pentagonal pyramids, and edges with six TiN4Cl2 octahedra. The corner-sharing octahedra tilt angles range from 12–13°. There are a spread of Ti–N bond distances ranging from 1.99–2.04 Å. There are one shorter (2.53 Å) and one longer (2.54 Å) Ti–Cl bond lengths. In the fourth Ti+3.80+ site, Ti+3.80+ is bonded to four N3- and two Cl1- atoms to form distorted TiN4Cl2 octahedra that share corners with two TiN4Cl2 octahedra, a cornercorner with one NaCl6 pentagonal pyramid, edges with six TiN4Cl2 octahedra, and an edgeedge with one NaCl6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 12–13°. There are a spread of Ti–N bond distances ranging from 1.98–2.05 Å. There are one shorter (2.51 Å) and one longer (2.57 Å) Ti–Cl bond lengths. In the fifth Ti+3.80+ site, Ti+3.80+ is bonded to four N3- and two Cl1- atoms to form distorted TiN4Cl2 octahedra that share corners with two TiN4Cl2 octahedra, a cornercorner with one NaCl6 pentagonal pyramid, edges with six TiN4Cl2 octahedra, and an edgeedge with one NaCl6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 12–14°. There are a spread of Ti–N bond distances ranging from 1.97–2.05 Å. There are one shorter (2.51 Å) and one longer (2.58 Å) Ti–Cl bond lengths. There are five inequivalent N3- sites. In the first N3- site, N3- is bonded in a see-saw-like geometry to four Ti+3.80+ atoms. In the second N3- site, N3- is bonded in a see-saw-like geometry to four Ti+3.80+ atoms. In the third N3- site, N3- is bonded in a see-saw-like geometry to four Ti+3.80+ atoms. In the fourth N3- site, N3- is bonded in a see-saw-like geometry to four Ti+3.80+ atoms. In the fifth N3- site, N3- is bonded in a see-saw-like geometry to four Ti+3.80+ atoms. There are five inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 4-coordinate geometry to two equivalent Na1+ and two Ti+3.80+ atoms. In the second Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to one Na1+ and two Ti+3.80+ atoms. In the third Cl1- site, Cl1- is bonded in a distorted trigonal planar geometry to one Na1+ and two Ti+3.80+ atoms. In the fourth Cl1- site, Cl1- is bonded in a distorted trigonal planar geometry to one Na1+ and two Ti+3.80+ atoms. In the fifth Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to one Na1+ and two Ti+3.80+ atoms.