DOE OSTI2020
LiMnF5 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six F1- atoms. There are a spread of Li–F bond distances ranging from 1.92–2.67 Å. In the second Li1+ site, Li1+ is bonded to four F1- atoms to form distorted LiF4 trigonal pyramids that share corners with four MnF6 octahedra. The corner-sharing octahedra tilt angles range from 33–69°. There are a spread of Li–F bond distances ranging from 1.86–2.07 Å. In the third Li1+ site, Li1+ is bonded in a distorted rectangular see-saw-like geometry to four F1- atoms. There are a spread of Li–F bond distances ranging from 1.96–2.51 Å. There are three inequivalent Mn4+ sites. In the first Mn4+ site, Mn4+ is bonded to six F1- atoms to form MnF6 octahedra that share a cornercorner with one MnF6 octahedra, a cornercorner with one LiF4 trigonal pyramid, and an edgeedge with one MnF6 octahedra. The corner-sharing octahedral tilt angles are 44°. There are a spread of Mn–F bond distances ranging from 1.77–1.97 Å. In the second Mn4+ site, Mn4+ is bonded to six F1- atoms to form MnF6 octahedra that share a cornercorner with one MnF6 octahedra and corners with two equivalent LiF4 trigonal pyramids. The corner-sharing octahedral tilt angles are 38°. There are a spread of Mn–F bond distances ranging from 1.79–2.00 Å. In the third Mn4+ site, Mn4+ is bonded to six F1- atoms to form MnF6 octahedra that share corners with two MnF6 octahedra and a cornercorner with one LiF4 trigonal pyramid. The corner-sharing octahedra tilt angles range from 38–44°. There are a spread of Mn–F bond distances ranging from 1.81–1.91 Å. There are fifteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a bent 120 degrees geometry to one Li1+ and one Mn4+ atom. In the second F1- site, F1- is bonded in a water-like geometry to two equivalent Mn4+ atoms. In the third F1- site, F1- is bonded in a distorted bent 150 degrees geometry to two Mn4+ atoms. In the fourth F1- site, F1- is bonded in a bent 120 degrees geometry to one Li1+ and one Mn4+ atom. In the fifth F1- site, F1- is bonded in a single-bond geometry to one Mn4+ atom. In the sixth F1- site, F1- is bonded in a 1-coordinate geometry to two equivalent Li1+ and one Mn4+ atom. In the seventh F1- site, F1- is bonded in a linear geometry to one Li1+ and one Mn4+ atom. In the eighth F1- site, F1- is bonded in a bent 120 degrees geometry to one Li1+ and one Mn4+ atom. In the ninth F1- site, F1- is bonded in a distorted bent 150 degrees geometry to two Li1+ and one Mn4+ atom. In the tenth F1- site, F1- is bonded in a distorted trigonal non-coplanar geometry to two Li1+ and one Mn4+ atom. In the eleventh F1- site, F1- is bonded in a distorted bent 120 degrees geometry to one Li1+ and one Mn4+ atom. In the twelfth F1- site, F1- is bonded in a distorted bent 120 degrees geometry to one Li1+ and one Mn4+ atom. In the thirteenth F1- site, F1- is bonded in a water-like geometry to one Li1+ and one Mn4+ atom. In the fourteenth F1- site, F1- is bonded in a bent 150 degrees geometry to one Li1+ and one Mn4+ atom. In the fifteenth F1- site, F1- is bonded in a bent 150 degrees geometry to two Mn4+ atoms.