Materials Data on Li14Mn5F24 by Materials Project

Abstract

Li14Mn5F24 crystallizes in the orthorhombic Pbam space group. The structure is three-dimensional. there are six inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with six LiF6 octahedra, edges with two equivalent MnF6 octahedra, and edges with eight LiF6 octahedra. The corner-sharing octahedra tilt angles range from 6–9°. There are two shorter (2.09 Å) and four longer (2.10 Å) Li–F bond lengths. In the second Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with four equivalent MnF4 tetrahedra and edges with six LiF6 octahedra. There is two shorter (1.90 Å) and four longer (2.06 Å) Li–F bond length. In the third Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with three equivalent LiF6 octahedra, corners with two equivalent MnF4 tetrahedra, an edgeedge with one MnF6 octahedra, and edges with seven LiF6 octahedra. The corner-sharing octahedra tilt angles range from 0–5°. There are a spread of Li–F bond distances ranging from 1.95–2.22 Å. In the fourth Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with five LiF6 octahedra, a cornercorner with one MnF4 tetrahedra, an edgeedge with one MnF6 octahedra, and edges with six LiF6 octahedra. The corner-sharing octahedra tilt angles range from 0–52°. There are a spread of Li–F bond distances ranging from 2.01–2.23 Å. In the fifth Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with five LiF6 octahedra, corners with two equivalent MnF4 tetrahedra, and edges with five LiF6 octahedra. The corner-sharing octahedra tilt angles range from 9–51°. There are a spread of Li–F bond distances ranging from 1.97–2.34 Å. In the sixth Li1+ site, Li1+ is bonded to six F1- atoms to form distorted LiF6 octahedra that share corners with six LiF6 octahedra, corners with two equivalent MnF4 tetrahedra, an edgeedge with one MnF6 octahedra, and edges with four LiF6 octahedra. The corner-sharing octahedra tilt angles range from 6–52°. There are a spread of Li–F bond distances ranging from 1.98–2.37 Å. There are three inequivalent Mn2+ sites. In the first Mn2+ site, Mn2+ is bonded to six F1- atoms to form MnF6 octahedra that share edges with twelve LiF6 octahedra. There are two shorter (2.10 Å) and four longer (2.13 Å) Mn–F bond lengths. In the second Mn2+ site, Mn2+ is bonded to four F1- atoms to form MnF4 tetrahedra that share corners with twelve LiF6 octahedra. The corner-sharing octahedra tilt angles range from 50–70°. There are a spread of Mn–F bond distances ranging from 2.01–2.06 Å. In the third Mn2+ site, Mn2+ is bonded in a rectangular see-saw-like geometry to four F1- atoms. There are a spread of Mn–F bond distances ranging from 1.95–2.10 Å. There are nine inequivalent F1- sites. In the first F1- site, F1- is bonded to three Li1+ and one Mn2+ atom to form FLi3Mn tetrahedra that share corners with four FLi4Mn square pyramids, corners with three FLi3Mn tetrahedra, and an edgeedge with one FLi6 octahedra. In the second F1- site, F1- is bonded to four Li1+ and one Mn2+ atom to form FLi4Mn square pyramids that share corners with three equivalent FLi4Mn square pyramids, a cornercorner with one FLi3Mn tetrahedra, edges with two equivalent FLi6 octahedra, edges with four FLi4Mn square pyramids, and edges with two FLi3Mn tetrahedra. In the third F1- site, F1- is bonded to four Li1+ and one Mn2+ atom to form FLi4Mn square pyramids that share a cornercorner with one FLi4Mn square pyramid, corners with two equivalent FLi3Mn tetrahedra, edges with two equivalent FLi6 octahedra, edges with four equivalent FLi4Mn square pyramids, and edges with two FLi3Mn tetrahedra. In the fourth F1- site, F1- is bonded to three Li1+ and one Mn2+ atom to form FLi3Mn tetrahedra that share corners with two equivalent FLi6 octahedra, corners with four FLi3Mn tetrahedra, and edges with three FLi4Mn square pyramids. The corner-sharing octahedral tilt angles are 10°. In the fifth F1- site, F1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Mn2+ atom. In the sixth F1- site, F1- is bonded to six Li1+ atoms to form FLi6 octahedra that share a cornercorner with one FLi6 octahedra, corners with four FLi3Mn tetrahedra, edges with six FLi4Mn square pyramids, and an edgeedge with one FLi3Mn tetrahedra. The corner-sharing octahedral tilt angles are 0°. In the seventh F1- site, F1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Mn2+ atom. In the eighth F1- site, F1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Mn2+ atom. In the ninth F1- site, F1- is bonded to three Li1+ and one Mn2+ atom to form FLi3Mn tetrahedra that share corners with two equivalent FLi6 octahedra, corners with two equivalent FLi3Mn tetrahedra, and edges with three FLi4Mn square pyramids. The corner-sharing octahedral tilt angles are 6°.