Li3CuF6 crystallizes in the cubic Pn-3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to four equivalent F(1) atoms. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Cu(1)F6 octahedra and faces with two equivalent Li(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 39°. In the third Li site, Li(3) is bonded to twelve equivalent F(1) atoms to form distorted LiF12 cuboctahedra that share faces with four equivalent Li(2)F6 octahedra and faces with four equivalent Cu(1)F6 octahedra. Cu(1) is bonded to six equivalent F(1) atoms to form CuF6 octahedra that share corners with six equivalent Li(2)F6 octahedra and faces with two equivalent Li(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 39°. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), one Li(3), and one Cu(1) atom.
Li3CuF6 crystallizes in the cubic Pn-3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to four equivalent F(1) atoms. All Li(1)-F(1) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded to six equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Cu(1)F6 octahedra and faces with two equivalent Li(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 39°. All Li(2)-F(1) bond lengths are 2.02 Å. In the third Li site, Li(3) is bonded to twelve equivalent F(1) atoms to form distorted LiF12 cuboctahedra that share faces with four equivalent Li(2)F6 octahedra and faces with four equivalent Cu(1)F6 octahedra. All Li(3)-F(1) bond lengths are 2.62 Å. Cu(1) is bonded to six equivalent F(1) atoms to form CuF6 octahedra that share corners with six equivalent Li(2)F6 octahedra and faces with two equivalent Li(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 39°. All Cu(1)-F(1) bond lengths are 1.92 Å. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), one Li(3), and one Cu(1) atom.