Li2CuF5 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one F(4), one F(5), and two equivalent F(3) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(7) and four equivalent F(6) atoms. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one F(4), one F(5), and two equivalent F(6) atoms. 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 corner-sharing CuF6 octahedra. The corner-sharing octahedra are not tilted. In the second Cu site, Cu(2) is bonded to one F(4), one F(7), two equivalent F(3), and two equivalent F(8) atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedra are not tilted. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Cu(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one Cu(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing FLi3Cu tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Cu(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Cu(1) atom. In the sixth F site, F(6) is bonded to one Li(4), two equivalent Li(3), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing FLi3Cu tetrahedra. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Li(3) and one Cu(2) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent Cu(2) atoms.
Li2CuF5 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one F(4), one F(5), and two equivalent F(3) atoms. The Li(1)-F(4) bond length is 2.21 Å. The Li(1)-F(5) bond length is 1.96 Å. Both Li(1)-F(3) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. The Li(2)-F(2) bond length is 1.89 Å. There are two shorter (2.00 Å) and two longer (2.19 Å) Li(2)-F(3) bond lengths. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(7) and four equivalent F(6) atoms. The Li(3)-F(7) bond length is 1.90 Å. There are two shorter (2.00 Å) and two longer (2.19 Å) Li(3)-F(6) bond lengths. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one F(4), one F(5), and two equivalent F(6) atoms. The Li(4)-F(4) bond length is 1.97 Å. The Li(4)-F(5) bond length is 2.20 Å. Both Li(4)-F(6) bond lengths are 1.97 Å. 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 corner-sharing CuF6 octahedra. The corner-sharing octahedra are not tilted. The Cu(1)-F(2) bond length is 1.85 Å. The Cu(1)-F(5) bond length is 1.92 Å. Both Cu(1)-F(1) bond lengths are 1.93 Å. Both Cu(1)-F(6) bond lengths are 1.92 Å. In the second Cu site, Cu(2) is bonded to one F(4), one F(7), two equivalent F(3), and two equivalent F(8) atoms to form corner-sharing CuF6 octahedra. The corner-sharing octahedra are not tilted. The Cu(2)-F(4) bond length is 1.90 Å. The Cu(2)-F(7) bond length is 1.84 Å. Both Cu(2)-F(3) bond lengths are 1.93 Å. Both Cu(2)-F(8) bond lengths are 1.93 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Cu(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one Cu(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing FLi3Cu tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Cu(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one Cu(1) atom. In the sixth F site, F(6) is bonded to one Li(4), two equivalent Li(3), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing FLi3Cu tetrahedra. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Li(3) and one Cu(2) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent Cu(2) atoms.