LiBiF5 crystallizes in the tetragonal I-4 space group. Li(1) is bonded to four equivalent F(2) atoms to form LiF4 tetrahedra that share corners with four equivalent Bi(1)F6 octahedra. The corner-sharing octahedral tilt angles are 50°. Bi(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra and corners with four equivalent Li(1)F4 tetrahedra. The corner-sharing octahedra are not tilted. There are two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Bi(1) atoms. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(1) and one Bi(1) atom.
LiBiF5 crystallizes in the tetragonal I-4 space group. Li(1) is bonded to four equivalent F(2) atoms to form LiF4 tetrahedra that share corners with four equivalent Bi(1)F6 octahedra. The corner-sharing octahedral tilt angles are 50°. All Li(1)-F(2) bond lengths are 1.91 Å. Bi(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra and corners with four equivalent Li(1)F4 tetrahedra. The corner-sharing octahedra are not tilted. Both Bi(1)-F(1) bond lengths are 2.22 Å. All Bi(1)-F(2) bond lengths are 2.14 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Bi(1) atoms. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(1) and one Bi(1) atom.