Li2Cu3F8 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 5-coordinate geometry to one F(4), two equivalent F(1), and two equivalent F(2) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing CuF6 octahedra. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing CuF6 octahedra. In the third Cu site, Cu(3) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing CuF6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded to two equivalent Li(1), one Cu(2), and one Cu(3) atom to form a mixture of distorted edge and corner-sharing FLi2Cu2 tetrahedra. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(3) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one Cu(3) atom.
Li2Cu3F8 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 5-coordinate geometry to one F(4), two equivalent F(1), and two equivalent F(2) atoms. The Li(1)-F(4) bond length is 1.94 Å. There is one shorter (2.03 Å) and one longer (2.13 Å) Li(1)-F(1) bond length. There is one shorter (2.28 Å) and one longer (2.41 Å) Li(1)-F(2) bond length. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing CuF6 octahedra. Both Cu(1)-F(1) bond lengths are 2.35 Å. Both Cu(1)-F(3) bond lengths are 1.96 Å. Both Cu(1)-F(4) bond lengths are 1.90 Å. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing CuF6 octahedra. Both Cu(2)-F(1) bond lengths are 1.91 Å. Both Cu(2)-F(2) bond lengths are 1.99 Å. Both Cu(2)-F(3) bond lengths are 2.28 Å. In the third Cu site, Cu(3) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing CuF6 octahedra. Both Cu(3)-F(2) bond lengths are 1.99 Å. Both Cu(3)-F(3) bond lengths are 1.91 Å. Both Cu(3)-F(4) bond lengths are 2.29 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded to two equivalent Li(1), one Cu(2), and one Cu(3) atom to form a mixture of distorted edge and corner-sharing FLi2Cu2 tetrahedra. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(3) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one Cu(3) atom.