Li2Cu2F5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with five equivalent Li(2)F6 octahedra,  a cornercorner with one Cu(1)F5 trigonal bipyramid, corners with two equivalent Cu(2)F5 trigonal bipyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Cu(1)F5 trigonal bipyramids, and edges with two equivalent Cu(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-59°. In the second Li site, Li(2) is bonded to one F(3), one F(4), two equivalent F(2), and two equivalent F(5) atoms to form distorted LiF6 octahedra that share corners with five equivalent Li(1)F6 octahedra,  a cornercorner with one Cu(2)F5 trigonal bipyramid, corners with two equivalent Cu(1)F5 trigonal bipyramids, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Cu(1)F5 trigonal bipyramids, and edges with two equivalent Cu(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-59°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(5), and two equivalent F(3) atoms to form distorted CuF5 trigonal bipyramids that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Cu(1)F5 trigonal bipyramids, corners with two equivalent Cu(2)F5 trigonal bipyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Cu(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-69°. In the second Cu site, Cu(2) is bonded to one F(1), one F(4), one F(5), and two equivalent F(3) atoms to form distorted CuF5 trigonal bipyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(1)F5 trigonal bipyramids, corners with two equivalent Cu(2)F5 trigonal bipyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Cu(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-69°. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), one Cu(1), and one Cu(2) atom to form FLi2Cu2 tetrahedra that share corners with two equivalent F(3)Li2Cu4 octahedra, corners with two equivalent F(1)Li2Cu2 tetrahedra, corners with three equivalent F(2)Li3Cu tetrahedra, corners with three equivalent F(4)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra,  an edgeedge with one F(5)Li2Cu2 tetrahedra, and  an edgeedge with one F(4)Li3Cu tetrahedra. The corner-sharing octahedral tilt angles range from 35-57°. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Cu(1) atom to form FLi3Cu tetrahedra that share  a cornercorner with one F(3)Li2Cu4 octahedra, corners with two equivalent F(2)Li3Cu tetrahedra, corners with three equivalent F(1)Li2Cu2 tetrahedra, corners with three equivalent F(5)Li2Cu2 tetrahedra, corners with four equivalent F(4)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra, and  an edgeedge with one F(5)Li2Cu2 tetrahedra. The corner-sharing octahedral tilt angles are 16°. In the third F site, F(3) is bonded to one Li(1), one Li(2), two equivalent Cu(1), and two equivalent Cu(2) atoms to form FLi2Cu4 octahedra that share  a cornercorner with one F(2)Li3Cu tetrahedra,  a cornercorner with one F(4)Li3Cu tetrahedra, corners with two equivalent F(1)Li2Cu2 tetrahedra, corners with two equivalent F(5)Li2Cu2 tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra, edges with two equivalent F(1)Li2Cu2 tetrahedra, edges with two equivalent F(5)Li2Cu2 tetrahedra, edges with two equivalent F(2)Li3Cu tetrahedra, and edges with two equivalent F(4)Li3Cu tetrahedra. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one Cu(2) atom to form FLi3Cu tetrahedra that share  a cornercorner with one F(3)Li2Cu4 octahedra, corners with two equivalent F(4)Li3Cu tetrahedra, corners with three equivalent F(1)Li2Cu2 tetrahedra, corners with three equivalent F(5)Li2Cu2 tetrahedra, corners with four equivalent F(2)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra, and  an edgeedge with one F(1)Li2Cu2 tetrahedra. The corner-sharing octahedral tilt angles are 15°. In the fifth F site, F(5) is bonded to two equivalent Li(2), one Cu(1), and one Cu(2) atom to form FLi2Cu2 tetrahedra that share corners with two equivalent F(3)Li2Cu4 octahedra, corners with two equivalent F(5)Li2Cu2 tetrahedra, corners with three equivalent F(2)Li3Cu tetrahedra, corners with three equivalent F(4)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra,  an edgeedge with one F(1)Li2Cu2 tetrahedra, and  an edgeedge with one F(2)Li3Cu tetrahedra. The corner-sharing octahedral tilt angles range from 37-55°.
Li2Cu2F5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with five equivalent Li(2)F6 octahedra,  a cornercorner with one Cu(1)F5 trigonal bipyramid, corners with two equivalent Cu(2)F5 trigonal bipyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Cu(1)F5 trigonal bipyramids, and edges with two equivalent Cu(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-59°. The Li(1)-F(2) bond length is 1.98 Å. The Li(1)-F(3) bond length is 2.36 Å. There is one shorter (2.08 Å) and one longer (2.11 Å) Li(1)-F(1) bond length. There is one shorter (2.09 Å) and one longer (2.13 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded to one F(3), one F(4), two equivalent F(2), and two equivalent F(5) atoms to form distorted LiF6 octahedra that share corners with five equivalent Li(1)F6 octahedra,  a cornercorner with one Cu(2)F5 trigonal bipyramid, corners with two equivalent Cu(1)F5 trigonal bipyramids, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Cu(1)F5 trigonal bipyramids, and edges with two equivalent Cu(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-59°. The Li(2)-F(3) bond length is 2.36 Å. The Li(2)-F(4) bond length is 1.97 Å. There is one shorter (2.07 Å) and one longer (2.16 Å) Li(2)-F(2) bond length. There is one shorter (2.06 Å) and one longer (2.12 Å) Li(2)-F(5) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(5), and two equivalent F(3) atoms to form distorted CuF5 trigonal bipyramids that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Cu(1)F5 trigonal bipyramids, corners with two equivalent Cu(2)F5 trigonal bipyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Cu(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-69°. The Cu(1)-F(1) bond length is 2.01 Å. The Cu(1)-F(2) bond length is 1.94 Å. The Cu(1)-F(5) bond length is 2.04 Å. There is one shorter (2.13 Å) and one longer (2.26 Å) Cu(1)-F(3) bond length. In the second Cu site, Cu(2) is bonded to one F(1), one F(4), one F(5), and two equivalent F(3) atoms to form distorted CuF5 trigonal bipyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Cu(1)F5 trigonal bipyramids, corners with two equivalent Cu(2)F5 trigonal bipyramids, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Cu(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-69°. The Cu(2)-F(1) bond length is 2.03 Å. The Cu(2)-F(4) bond length is 1.94 Å. The Cu(2)-F(5) bond length is 2.01 Å. There is one shorter (2.10 Å) and one longer (2.30 Å) Cu(2)-F(3) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), one Cu(1), and one Cu(2) atom to form FLi2Cu2 tetrahedra that share corners with two equivalent F(3)Li2Cu4 octahedra, corners with two equivalent F(1)Li2Cu2 tetrahedra, corners with three equivalent F(2)Li3Cu tetrahedra, corners with three equivalent F(4)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra,  an edgeedge with one F(5)Li2Cu2 tetrahedra, and  an edgeedge with one F(4)Li3Cu tetrahedra. The corner-sharing octahedral tilt angles range from 35-57°. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Cu(1) atom to form FLi3Cu tetrahedra that share  a cornercorner with one F(3)Li2Cu4 octahedra, corners with two equivalent F(2)Li3Cu tetrahedra, corners with three equivalent F(1)Li2Cu2 tetrahedra, corners with three equivalent F(5)Li2Cu2 tetrahedra, corners with four equivalent F(4)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra, and  an edgeedge with one F(5)Li2Cu2 tetrahedra. The corner-sharing octahedral tilt angles are 16°. In the third F site, F(3) is bonded to one Li(1), one Li(2), two equivalent Cu(1), and two equivalent Cu(2) atoms to form FLi2Cu4 octahedra that share  a cornercorner with one F(2)Li3Cu tetrahedra,  a cornercorner with one F(4)Li3Cu tetrahedra, corners with two equivalent F(1)Li2Cu2 tetrahedra, corners with two equivalent F(5)Li2Cu2 tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra, edges with two equivalent F(1)Li2Cu2 tetrahedra, edges with two equivalent F(5)Li2Cu2 tetrahedra, edges with two equivalent F(2)Li3Cu tetrahedra, and edges with two equivalent F(4)Li3Cu tetrahedra. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one Cu(2) atom to form FLi3Cu tetrahedra that share  a cornercorner with one F(3)Li2Cu4 octahedra, corners with two equivalent F(4)Li3Cu tetrahedra, corners with three equivalent F(1)Li2Cu2 tetrahedra, corners with three equivalent F(5)Li2Cu2 tetrahedra, corners with four equivalent F(2)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra, and  an edgeedge with one F(1)Li2Cu2 tetrahedra. The corner-sharing octahedral tilt angles are 15°. In the fifth F site, F(5) is bonded to two equivalent Li(2), one Cu(1), and one Cu(2) atom to form FLi2Cu2 tetrahedra that share corners with two equivalent F(3)Li2Cu4 octahedra, corners with two equivalent F(5)Li2Cu2 tetrahedra, corners with three equivalent F(2)Li3Cu tetrahedra, corners with three equivalent F(4)Li3Cu tetrahedra, edges with two equivalent F(3)Li2Cu4 octahedra,  an edgeedge with one F(1)Li2Cu2 tetrahedra, and  an edgeedge with one F(2)Li3Cu tetrahedra. The corner-sharing octahedral tilt angles range from 37-55°.