Li2BiF5 crystallizes in the tetragonal I4/m space group. Li(1) is bonded to four equivalent F(1) atoms to form LiF4 tetrahedra that share corners with four equivalent Bi(1)F6 octahedra and edges with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. Bi(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra and corners with eight equivalent Li(1)F4 tetrahedra. The corner-sharing octahedra are not tilted. There are two inequivalent F sites. In the first F site, F(2) is bonded in a linear geometry to two equivalent Bi(1) atoms. In the second F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Bi(1) atom.
Li2BiF5 crystallizes in the tetragonal I4/m space group. Li(1) is bonded to four equivalent F(1) atoms to form LiF4 tetrahedra that share corners with four equivalent Bi(1)F6 octahedra and edges with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. All Li(1)-F(1) bond lengths are 1.86 Å. Bi(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra and corners with eight equivalent Li(1)F4 tetrahedra. The corner-sharing octahedra are not tilted. Both Bi(1)-F(2) bond lengths are 2.38 Å. All Bi(1)-F(1) bond lengths are 2.27 Å. There are two inequivalent F sites. In the first F site, F(2) is bonded in a linear geometry to two equivalent Bi(1) atoms. In the second F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Bi(1) atom.