Li2CuF5 crystallizes in the orthorhombic Pbam space group. Li(1) is bonded to one F(2), two equivalent F(1), and two equivalent F(3) atoms to form LiF5 square pyramids that share corners with four equivalent Cu(1)F6 octahedra, corners with two equivalent Li(1)F5 square pyramids, and edges with three equivalent Li(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 48-54°. Cu(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form CuF6 octahedra that share corners with eight equivalent Li(1)F5 square pyramids and edges with two equivalent Cu(1)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to four equivalent Li(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Cu(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Cu(1) atom.
Li2CuF5 crystallizes in the orthorhombic Pbam space group. Li(1) is bonded to one F(2), two equivalent F(1), and two equivalent F(3) atoms to form LiF5 square pyramids that share corners with four equivalent Cu(1)F6 octahedra, corners with two equivalent Li(1)F5 square pyramids, and edges with three equivalent Li(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 48-54°. The Li(1)-F(2) bond length is 2.12 Å. Both Li(1)-F(1) bond lengths are 1.96 Å. Both Li(1)-F(3) bond lengths are 1.98 Å. Cu(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form CuF6 octahedra that share corners with eight equivalent Li(1)F5 square pyramids and edges with two equivalent Cu(1)F6 octahedra. Both Cu(1)-F(3) bond lengths are 1.89 Å. All Cu(1)-F(2) bond lengths are 1.95 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to four equivalent Li(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Cu(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Cu(1) atom.