Li5CuF6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(4)F6 octahedra,  a cornercorner with one Li(6)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Cu(2)F6 octahedra, edges with three equivalent Li(3)F6 octahedra, and  a faceface with one Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-51°. In the second Li site, Li(2) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form LiF6 octahedra that share  a cornercorner with one Cu(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with four equivalent Li(4)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and  a faceface with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-51°. In the third Li site, Li(3) is bonded to one F(3), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form LiF6 octahedra that share  a cornercorner with one Li(5)F6 octahedra,  a cornercorner with one Cu(1)F6 octahedra,  a cornercorner with one Cu(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Cu(2)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Li(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 3-50°. In the fourth Li site, Li(4) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra, edges with two equivalent Li(5)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. In the fifth Li site, Li(5) is bonded to two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(6)F6 octahedra, and faces with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. In the sixth Li site, Li(6) is bonded to two equivalent F(6) and four equivalent F(5) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with eight equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with four equivalent Li(5)F6 octahedra, and faces with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1) and four equivalent F(4) atoms to form CuF6 octahedra that share corners with four equivalent Li(3)F6 octahedra, corners with eight equivalent Li(1)F6 octahedra, edges with two equivalent Li(5)F6 octahedra, edges with four equivalent Li(4)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second Cu site, Cu(2) is bonded to one F(3), one F(6), two equivalent F(2), and two equivalent F(5) atoms to form CuF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(5)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and  a faceface with one Li(6)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(4), and one Cu(1) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Cu(2) atom to form edge-sharing FLi5Cu octahedra. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Cu(2) atom to form edge-sharing FLi5Cu octahedra. In the fourth F site, F(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Cu(1) atom. In the fifth F site, F(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a 6-coordinate geometry to one Li(6), two equivalent Li(3), two equivalent Li(5), and one Cu(2) atom.
Li5CuF6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(4)F6 octahedra,  a cornercorner with one Li(6)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Cu(2)F6 octahedra, edges with three equivalent Li(3)F6 octahedra, and  a faceface with one Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-51°. The Li(1)-F(1) bond length is 2.04 Å. The Li(1)-F(3) 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 2.19 Å. There is one shorter (2.03 Å) and one longer (2.07 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form LiF6 octahedra that share  a cornercorner with one Cu(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(5)F6 octahedra, corners with four equivalent Li(4)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and  a faceface with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-51°. The Li(2)-F(1) bond length is 2.12 Å. The Li(2)-F(3) bond length is 1.99 Å. Both Li(2)-F(2) bond lengths are 2.06 Å. Both Li(2)-F(4) bond lengths are 2.17 Å. In the third Li site, Li(3) is bonded to one F(3), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form LiF6 octahedra that share  a cornercorner with one Li(5)F6 octahedra,  a cornercorner with one Cu(1)F6 octahedra,  a cornercorner with one Cu(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Li(6)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Cu(2)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Li(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 3-50°. The Li(3)-F(3) bond length is 2.05 Å. The Li(3)-F(4) bond length is 2.02 Å. The Li(3)-F(5) bond length is 2.11 Å. The Li(3)-F(6) bond length is 2.08 Å. There is one shorter (1.98 Å) and one longer (2.16 Å) Li(3)-F(2) bond length. In the fourth Li site, Li(4) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra,  an edgeedge with one Li(6)F6 octahedra, edges with two equivalent Li(5)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. Both Li(4)-F(1) bond lengths are 2.11 Å. Both Li(4)-F(4) bond lengths are 2.14 Å. Both Li(4)-F(5) bond lengths are 2.01 Å. In the fifth Li site, Li(5) is bonded to two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(5)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(6)F6 octahedra, and faces with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. Both Li(5)-F(4) bond lengths are 2.10 Å. Both Li(5)-F(5) bond lengths are 2.02 Å. Both Li(5)-F(6) bond lengths are 2.05 Å. In the sixth Li site, Li(6) is bonded to two equivalent F(6) and four equivalent F(5) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with eight equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with four equivalent Li(5)F6 octahedra, and faces with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. Both Li(6)-F(6) bond lengths are 2.18 Å. All Li(6)-F(5) bond lengths are 2.10 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1) and four equivalent F(4) atoms to form CuF6 octahedra that share corners with four equivalent Li(3)F6 octahedra, corners with eight equivalent Li(1)F6 octahedra, edges with two equivalent Li(5)F6 octahedra, edges with four equivalent Li(4)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both Cu(1)-F(1) bond lengths are 2.27 Å. All Cu(1)-F(4) bond lengths are 2.22 Å. In the second Cu site, Cu(2) is bonded to one F(3), one F(6), two equivalent F(2), and two equivalent F(5) atoms to form CuF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(5)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and  a faceface with one Li(6)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. The Cu(2)-F(3) bond length is 2.21 Å. The Cu(2)-F(6) bond length is 2.18 Å. Both Cu(2)-F(2) bond lengths are 2.21 Å. Both Cu(2)-F(5) bond lengths are 2.24 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(4), and one Cu(1) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Cu(2) atom to form edge-sharing FLi5Cu octahedra. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Cu(2) atom to form edge-sharing FLi5Cu octahedra. In the fourth F site, F(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Cu(1) atom. In the fifth F site, F(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a 6-coordinate geometry to one Li(6), two equivalent Li(3), two equivalent Li(5), and one Cu(2) atom.