Li5Cu3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a body-centered cubic geometry to eight equivalent F(2) atoms. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent F(2) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles are 45°. In the second Cu site, Cu(2) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles are 45°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Cu(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one Cu(2) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Cu(1) and one Cu(2) atom.
Li5Cu3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a body-centered cubic geometry to eight equivalent F(2) atoms. All Li(1)-F(2) bond lengths are 2.49 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent F(2) atoms. There are two shorter (2.02 Å) and two longer (2.16 Å) Li(2)-F(2) bond lengths. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles are 45°. Both Cu(1)-F(1) bond lengths are 1.87 Å. All Cu(1)-F(3) bond lengths are 1.87 Å. In the second Cu site, Cu(2) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedral tilt angles are 45°. Both Cu(2)-F(3) bond lengths are 1.90 Å. All Cu(2)-F(2) bond lengths are 1.93 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Cu(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one Cu(2) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Cu(1) and one Cu(2) atom.