Li2CuF5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Cu(1)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two 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 49-58°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), and two equivalent F(5) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the second Cu site, Cu(2) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cu(1) atom. In the second F site, F(2) 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(2)Li3Cu trigonal pyramid,  an edgeedge with one F(2)Li3Cu trigonal pyramid, and edges with two equivalent F(4)Li2Cu2 trigonal pyramids. In the third F site, F(3) is bonded in a 3-coordinate 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(2)Li3Cu trigonal pyramid, corners with two equivalent F(4)Li2Cu2 trigonal pyramids, and edges with two equivalent F(2)Li3Cu trigonal pyramids. In the fifth F site, F(5) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Cu(2) atom.
Li2CuF5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Cu(1)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two 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 49-58°. The Li(1)-F(3) bond length is 2.34 Å. The Li(1)-F(4) bond length is 2.08 Å. There is one shorter (1.92 Å) and one longer (1.97 Å) Li(1)-F(1) bond length. There is one shorter (2.12 Å) and one longer (2.22 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), and two equivalent F(5) atoms. The Li(2)-F(2) bond length is 1.87 Å. The Li(2)-F(3) bond length is 2.33 Å. The Li(2)-F(4) bond length is 2.14 Å. There is one shorter (1.95 Å) and one longer (2.07 Å) Li(2)-F(5) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. Both Cu(1)-F(1) bond lengths are 1.93 Å. Both Cu(1)-F(2) bond lengths are 1.90 Å. Both Cu(1)-F(4) bond lengths are 1.99 Å. In the second Cu site, Cu(2) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. Both Cu(2)-F(3) bond lengths are 1.79 Å. Both Cu(2)-F(4) bond lengths are 2.34 Å. Both Cu(2)-F(5) bond lengths are 1.82 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cu(1) atom. In the second F site, F(2) 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(2)Li3Cu trigonal pyramid,  an edgeedge with one F(2)Li3Cu trigonal pyramid, and edges with two equivalent F(4)Li2Cu2 trigonal pyramids. In the third F site, F(3) is bonded in a 3-coordinate 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(2)Li3Cu trigonal pyramid, corners with two equivalent F(4)Li2Cu2 trigonal pyramids, and edges with two equivalent F(2)Li3Cu trigonal pyramids. In the fifth F site, F(5) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Cu(2) atom.