Li3CuF5 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Cu(1)F6 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-65°. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one F(3) and two equivalent F(2) atoms. Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and edges with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) 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 in a trigonal planar geometry to one Li(2) and two equivalent Cu(1) atoms.
Li3CuF5 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Cu(1)F6 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-65°. There is one shorter (1.85 Å) and one longer (1.89 Å) Li(1)-F(1) bond length. Both Li(1)-F(2) bond lengths are 1.94 Å. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one F(3) and two equivalent F(2) atoms. The Li(2)-F(3) bond length is 1.91 Å. Both Li(2)-F(2) bond lengths are 1.86 Å. Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and edges with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. Both Cu(1)-F(1) bond lengths are 1.89 Å. Both Cu(1)-F(2) bond lengths are 2.47 Å. Both Cu(1)-F(3) bond lengths are 1.98 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) 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 in a trigonal planar geometry to one Li(2) and two equivalent Cu(1) atoms.