Li3BiF6 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share faces with two equivalent Li(3)F6 octahedra and faces with two equivalent Bi(1)F6 octahedra. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra, edges with two equivalent Bi(1)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. Bi(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted BiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Bi(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Bi(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one Bi(1) atom.
Li3BiF6 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(2) atoms. Both Li(1)-F(1) bond lengths are 2.13 Å. Both Li(1)-F(2) bond lengths are 1.95 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share faces with two equivalent Li(3)F6 octahedra and faces with two equivalent Bi(1)F6 octahedra. Both Li(2)-F(1) bond lengths are 2.13 Å. Both Li(2)-F(2) bond lengths are 2.14 Å. Both Li(2)-F(3) bond lengths are 1.89 Å. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra, edges with two equivalent Bi(1)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. Both Li(3)-F(1) bond lengths are 2.01 Å. Both Li(3)-F(2) bond lengths are 1.94 Å. Both Li(3)-F(3) bond lengths are 2.10 Å. Bi(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted BiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. Both Bi(1)-F(1) bond lengths are 2.32 Å. Both Bi(1)-F(2) bond lengths are 2.33 Å. Both Bi(1)-F(3) bond lengths are 2.30 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Bi(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Bi(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one Bi(1) atom.