DOE OSTI2020
LiCuF4 crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are four 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 1.92–2.56 Å. In the second Li1+ site, Li1+ is bonded in a 4-coordinate geometry to five F1- atoms. There are a spread of Li–F bond distances ranging from 1.94–2.56 Å. In the third Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five F1- atoms. There are a spread of Li–F bond distances ranging from 1.96–2.46 Å. In the fourth 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 1.91–2.57 Å. There are four inequivalent Cu3+ sites. In the first Cu3+ site, Cu3+ is bonded to six F1- atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 1–12°. There are a spread of Cu–F bond distances ranging from 1.81–1.94 Å. In the second Cu3+ site, Cu3+ is bonded to six F1- atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 1–12°. There are a spread of Cu–F bond distances ranging from 1.88–1.94 Å. In the third Cu3+ site, Cu3+ is bonded to six F1- atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 1–12°. There is three shorter (1.88 Å) and three longer (1.94 Å) Cu–F bond length. In the fourth Cu3+ site, Cu3+ is bonded to six F1- atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 1–8°. There are a spread of Cu–F bond distances ranging from 1.81–1.95 Å. There are sixteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a linear geometry to two Cu3+ atoms. In the second F1- site, F1- is bonded to three Li1+ and one Cu3+ atom to form a mixture of edge and corner-sharing FLi3Cu tetrahedra. In the third F1- site, F1- is bonded in a water-like geometry to one Li1+ and one Cu3+ atom. In the fourth F1- site, F1- is bonded to three Li1+ and one Cu3+ atom to form a mixture of edge and corner-sharing FLi3Cu trigonal pyramids. In the fifth F1- site, F1- is bonded in a bent 120 degrees geometry to one Li1+ and one Cu3+ atom. In the sixth F1- site, F1- is bonded in a distorted T-shaped geometry to one Li1+ and two equivalent Cu3+ atoms. In the seventh F1- site, F1- is bonded in a T-shaped geometry to one Li1+ and two equivalent Cu3+ atoms. In the eighth F1- site, F1- is bonded in a T-shaped geometry to one Li1+ and two equivalent Cu3+ atoms. In the ninth F1- site, F1- is bonded in a distorted T-shaped geometry to one Li1+ and two equivalent Cu3+ atoms. In the tenth F1- site, F1- is bonded in a bent 120 degrees geometry to one Li1+ and one Cu3+ atom. In the eleventh F1- site, F1- is bonded to three Li1+ and one Cu3+ atom to form a mixture of edge and corner-sharing FLi3Cu trigonal pyramids. In the twelfth F1- site, F1- is bonded in a water-like geometry to one Li1+ and one Cu3+ atom. In the thirteenth F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Cu3+ atoms. In the fourteenth F1- site, F1- is bonded to three Li1+ and one Cu3+ atom to form a mixture of edge and corner-sharing FLi3Cu tetrahedra. In the fifteenth F1- site, F1- is bonded in a linear geometry to two Cu3+ atoms. In the sixteenth F1- site, F1- is bonded in a linear geometry to two Cu3+ atoms.