Li2CuF5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form distorted LiF6 octahedra that share corners with three equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(4), one F(5), and two equivalent F(1) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 57°. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Cu(2) atom to form distorted FLi3Cu trigonal pyramids that share  a cornercorner with one F(4)Li2Cu2 trigonal pyramid,  a cornercorner with one F(1)Li3Cu trigonal pyramid, corners with two equivalent F(5)Li3Cu trigonal pyramids,  an edgeedge with one F(1)Li3Cu trigonal pyramid,  an edgeedge with one F(5)Li3Cu trigonal pyramid, and edges with two equivalent F(4)Li2Cu2 trigonal pyramids. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Cu(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Cu(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Cu(1), and one Cu(2) atom to form distorted FLi2Cu2 trigonal pyramids that share  a cornercorner with one F(1)Li3Cu trigonal pyramid,  a cornercorner with one F(5)Li3Cu trigonal pyramid, corners with two equivalent F(4)Li2Cu2 trigonal pyramids, edges with two equivalent F(1)Li3Cu trigonal pyramids, and edges with two equivalent F(5)Li3Cu trigonal pyramids. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one Cu(1) atom to form distorted FLi3Cu trigonal pyramids that share  a cornercorner with one F(4)Li2Cu2 trigonal pyramid,  a cornercorner with one F(5)Li3Cu trigonal pyramid, corners with two equivalent F(1)Li3Cu trigonal pyramids,  an edgeedge with one F(1)Li3Cu trigonal pyramid,  an edgeedge with one F(5)Li3Cu trigonal pyramid, and edges with two equivalent F(4)Li2Cu2 trigonal pyramids.
Li2CuF5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form distorted LiF6 octahedra that share corners with three equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. The Li(1)-F(1) bond length is 2.05 Å. The Li(1)-F(2) bond length is 1.88 Å. The Li(1)-F(3) bond length is 1.92 Å. The Li(1)-F(4) bond length is 2.09 Å. There is one shorter (2.00 Å) and one longer (2.20 Å) Li(1)-F(5) bond length. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(4), one F(5), and two equivalent F(1) atoms. The Li(2)-F(2) bond length is 1.84 Å. The Li(2)-F(3) bond length is 1.94 Å. The Li(2)-F(4) bond length is 2.03 Å. The Li(2)-F(5) bond length is 1.96 Å. Both Li(2)-F(1) bond lengths are 2.20 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 57°. Both Cu(1)-F(2) bond lengths are 1.87 Å. Both Cu(1)-F(4) bond lengths are 1.91 Å. Both Cu(1)-F(5) bond lengths are 1.89 Å. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. Both Cu(2)-F(1) bond lengths are 1.81 Å. Both Cu(2)-F(3) bond lengths are 1.80 Å. Both Cu(2)-F(4) bond lengths are 2.17 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Cu(2) atom to form distorted FLi3Cu trigonal pyramids that share  a cornercorner with one F(4)Li2Cu2 trigonal pyramid,  a cornercorner with one F(1)Li3Cu trigonal pyramid, corners with two equivalent F(5)Li3Cu trigonal pyramids,  an edgeedge with one F(1)Li3Cu trigonal pyramid,  an edgeedge with one F(5)Li3Cu trigonal pyramid, and edges with two equivalent F(4)Li2Cu2 trigonal pyramids. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Cu(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Cu(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Cu(1), and one Cu(2) atom to form distorted FLi2Cu2 trigonal pyramids that share  a cornercorner with one F(1)Li3Cu trigonal pyramid,  a cornercorner with one F(5)Li3Cu trigonal pyramid, corners with two equivalent F(4)Li2Cu2 trigonal pyramids, edges with two equivalent F(1)Li3Cu trigonal pyramids, and edges with two equivalent F(5)Li3Cu trigonal pyramids. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one Cu(1) atom to form distorted FLi3Cu trigonal pyramids that share  a cornercorner with one F(4)Li2Cu2 trigonal pyramid,  a cornercorner with one F(5)Li3Cu trigonal pyramid, corners with two equivalent F(1)Li3Cu trigonal pyramids,  an edgeedge with one F(1)Li3Cu trigonal pyramid,  an edgeedge with one F(5)Li3Cu trigonal pyramid, and edges with two equivalent F(4)Li2Cu2 trigonal pyramids.