Li3CuF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), two equivalent F(2), and two equivalent F(3) 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 corners with six equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-47°. Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CuF6 octahedra that share corners with six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-47°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Cu(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(1), and one Cu(1) atom. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and one Cu(1) atom to form distorted corner-sharing FLi3Cu tetrahedra.
Li3CuF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), two equivalent F(2), and two equivalent F(3) atoms. The Li(1)-F(1) bond length is 2.00 Å. There is one shorter (2.00 Å) and one longer (2.46 Å) Li(1)-F(2) bond length. There is one shorter (1.97 Å) and one longer (2.12 Å) Li(1)-F(3) bond length. 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 corners with six equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-47°. Both Li(2)-F(1) bond lengths are 1.96 Å. Both Li(2)-F(2) bond lengths are 2.02 Å. Both Li(2)-F(3) bond lengths are 2.15 Å. Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CuF6 octahedra that share corners with six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-47°. Both Cu(1)-F(1) bond lengths are 1.92 Å. Both Cu(1)-F(2) bond lengths are 1.92 Å. Both Cu(1)-F(3) bond lengths are 1.94 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Cu(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(1), and one Cu(1) atom. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and one Cu(1) atom to form distorted corner-sharing FLi3Cu tetrahedra.