Li4CuF5 is Caswellsilverite-like structured and crystallizes in the tetragonal I4/m space group. Li(1) is bonded to one F(2) and five equivalent F(1) atoms to form LiF6 octahedra that share  a cornercorner with one Cu(1)F6 octahedra, corners with five equivalent Li(1)F6 octahedra, edges with three equivalent Cu(1)F6 octahedra, and edges with nine equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. 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 Cu(1)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, and edges with twelve equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are two inequivalent F sites. In the first F site, F(1) is bonded to five equivalent Li(1) and one Cu(1) atom to form FLi5Cu octahedra that share  a cornercorner with one F(2)Li4Cu2 octahedra, corners with five equivalent F(1)Li5Cu octahedra, edges with three equivalent F(2)Li4Cu2 octahedra, and edges with nine equivalent F(1)Li5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second F site, F(2) is bonded to four equivalent Li(1) and two equivalent Cu(1) atoms to form FLi4Cu2 octahedra that share corners with two equivalent F(2)Li4Cu2 octahedra, corners with four equivalent F(1)Li5Cu octahedra, and edges with twelve equivalent F(1)Li5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Li4CuF5 is Caswellsilverite-like structured and crystallizes in the tetragonal I4/m space group. Li(1) is bonded to one F(2) and five equivalent F(1) atoms to form LiF6 octahedra that share  a cornercorner with one Cu(1)F6 octahedra, corners with five equivalent Li(1)F6 octahedra, edges with three equivalent Cu(1)F6 octahedra, and edges with nine equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. The Li(1)-F(2) bond length is 2.20 Å. There are a spread of Li(1)-F(1) bond distances ranging from 1.99-2.15 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 Cu(1)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, and edges with twelve equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Cu(1)-F(2) bond lengths are 2.05 Å. All Cu(1)-F(1) bond lengths are 2.32 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to five equivalent Li(1) and one Cu(1) atom to form FLi5Cu octahedra that share  a cornercorner with one F(2)Li4Cu2 octahedra, corners with five equivalent F(1)Li5Cu octahedra, edges with three equivalent F(2)Li4Cu2 octahedra, and edges with nine equivalent F(1)Li5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second F site, F(2) is bonded to four equivalent Li(1) and two equivalent Cu(1) atoms to form FLi4Cu2 octahedra that share corners with two equivalent F(2)Li4Cu2 octahedra, corners with four equivalent F(1)Li5Cu octahedra, and edges with twelve equivalent F(1)Li5Cu octahedra. The corner-sharing octahedral tilt angles range from 0-6°.