Li3Cu2F8 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(3), one F(4), one F(5), one F(6), and one F(8) atom. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiF5 trigonal bipyramids that share  a cornercorner with one Cu(1)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra, and  an edgeedge with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-67°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(4), one F(5), one F(6), one F(7), and one F(8) atom. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(4), one F(6), one F(7), and one F(8) atom to form CuF6 octahedra that share  a cornercorner with one Li(2)F5 trigonal bipyramid, edges with two equivalent Cu(2)F6 octahedra, and  an edgeedge with one Li(2)F5 trigonal bipyramid. In the second Cu site, Cu(2) is bonded to one F(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form CuF6 octahedra that share corners with four equivalent Li(2)F5 trigonal bipyramids and edges with two equivalent Cu(1)F6 octahedra. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(2), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one Cu(1), and one Cu(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cu(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one Li(3), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one Cu(1) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(3), one Cu(1), and one Cu(2) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Cu(1), and one Cu(2) atom.
Li3Cu2F8 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(3), one F(4), one F(5), one F(6), and one F(8) atom. The Li(1)-F(3) bond length is 1.89 Å. The Li(1)-F(4) bond length is 2.34 Å. The Li(1)-F(5) bond length is 2.18 Å. The Li(1)-F(6) bond length is 1.91 Å. The Li(1)-F(8) bond length is 2.03 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiF5 trigonal bipyramids that share  a cornercorner with one Cu(1)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra, and  an edgeedge with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-67°. The Li(2)-F(1) bond length is 2.21 Å. The Li(2)-F(2) bond length is 1.90 Å. The Li(2)-F(3) bond length is 1.93 Å. The Li(2)-F(4) bond length is 2.29 Å. The Li(2)-F(5) bond length is 1.99 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(4), one F(5), one F(6), one F(7), and one F(8) atom. The Li(3)-F(4) bond length is 1.98 Å. The Li(3)-F(5) bond length is 2.05 Å. The Li(3)-F(6) bond length is 2.00 Å. The Li(3)-F(7) bond length is 1.92 Å. The Li(3)-F(8) bond length is 2.42 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(4), one F(6), one F(7), and one F(8) atom to form CuF6 octahedra that share  a cornercorner with one Li(2)F5 trigonal bipyramid, edges with two equivalent Cu(2)F6 octahedra, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The Cu(1)-F(1) bond length is 1.99 Å. The Cu(1)-F(2) bond length is 1.96 Å. The Cu(1)-F(4) bond length is 1.91 Å. The Cu(1)-F(6) bond length is 1.90 Å. The Cu(1)-F(7) bond length is 2.00 Å. The Cu(1)-F(8) bond length is 1.99 Å. In the second Cu site, Cu(2) is bonded to one F(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form CuF6 octahedra that share corners with four equivalent Li(2)F5 trigonal bipyramids and edges with two equivalent Cu(1)F6 octahedra. The Cu(2)-F(1) bond length is 1.98 Å. The Cu(2)-F(2) bond length is 2.09 Å. The Cu(2)-F(3) bond length is 1.88 Å. The Cu(2)-F(5) bond length is 1.91 Å. The Cu(2)-F(7) bond length is 2.02 Å. The Cu(2)-F(8) bond length is 2.31 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(2), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one Cu(1), and one Cu(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cu(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one Li(3), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one Cu(1) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(3), one Cu(1), and one Cu(2) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Cu(1), and one Cu(2) atom.