LiCu2F6 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with six equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(2), one F(5), two equivalent F(1), and two equivalent F(6) atoms to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. In the second Cu site, Cu(2) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra, and  an edgeedge with one Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Cu(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Cu(1), and one Cu(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cu(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Cu(2) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Cu(1), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Cu(2) and two equivalent Cu(1) atoms.
LiCu2F6 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with six equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. The Li(1)-F(1) bond length is 2.12 Å. The Li(1)-F(2) bond length is 2.10 Å. The Li(1)-F(4) bond length is 2.00 Å. The Li(1)-F(5) bond length is 2.15 Å. There is one shorter (1.98 Å) and one longer (2.05 Å) Li(1)-F(3) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(2), one F(5), two equivalent F(1), and two equivalent F(6) atoms to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. The Cu(1)-F(2) bond length is 1.95 Å. The Cu(1)-F(5) bond length is 1.97 Å. Both Cu(1)-F(1) bond lengths are 1.96 Å. There is one shorter (2.02 Å) and one longer (2.04 Å) Cu(1)-F(6) bond length. In the second Cu site, Cu(2) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra, and  an edgeedge with one Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. The Cu(2)-F(2) bond length is 1.98 Å. The Cu(2)-F(3) bond length is 1.88 Å. The Cu(2)-F(5) bond length is 1.97 Å. The Cu(2)-F(6) bond length is 2.04 Å. Both Cu(2)-F(4) bond lengths are 1.99 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Cu(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Cu(1), and one Cu(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cu(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Cu(2) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Cu(1), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Cu(2) and two equivalent Cu(1) atoms.