Li5CuF6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, edges with three equivalent Li(3)F6 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. In the second Li site, Li(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with three equivalent Li(2)F6 octahedra, edges with three equivalent Cu(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the third Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, edges with four equivalent Li(2)F6 octahedra, and edges with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. Cu(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form CuF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, and edges with six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Cu(1) atom to form a mixture of corner and edge-sharing FLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Cu(1) atom to form a mixture of corner and edge-sharing FLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Li5CuF6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, edges with three equivalent Li(3)F6 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. Both Li(1)-F(2) bond lengths are 2.08 Å. There are two shorter (1.99 Å) and two longer (2.16 Å) Li(1)-F(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with three equivalent Li(2)F6 octahedra, edges with three equivalent Cu(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Li(2)-F(2) bond lengths are 2.10 Å. There are two shorter (2.06 Å) and two longer (2.08 Å) Li(2)-F(1) bond lengths. In the third Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, edges with four equivalent Li(2)F6 octahedra, and edges with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. Both Li(3)-F(2) bond lengths are 1.96 Å. All Li(3)-F(1) bond lengths are 2.12 Å. Cu(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form CuF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, and edges with six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. Both Cu(1)-F(2) bond lengths are 2.27 Å. All Cu(1)-F(1) bond lengths are 2.19 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Cu(1) atom to form a mixture of corner and edge-sharing FLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Cu(1) atom to form a mixture of corner and edge-sharing FLi5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-6°.