Li2Cu3F8 crystallizes in the triclinic P1 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(4), and one F(6) atom to form distorted LiF4 tetrahedra that share corners with three equivalent Cu(1)F5 trigonal bipyramids and  an edgeedge with one Cu(3)F5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one F(3), one F(5), one F(7), and one F(8) atom to form distorted LiF4 tetrahedra that share corners with three equivalent Cu(3)F5 trigonal bipyramids and  an edgeedge with one Cu(1)F5 trigonal bipyramid. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(5), one F(6), and one F(7) atom to form distorted CuF5 trigonal bipyramids that share corners with three equivalent Li(1)F4 tetrahedra, corners with two equivalent Cu(3)F5 trigonal bipyramids,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Cu(3)F5 trigonal bipyramid. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to one F(3), one F(4), one F(5), and one F(6) atom. In the third Cu site, Cu(3) is bonded to one F(2), one F(5), one F(6), one F(7), and one F(8) atom to form distorted CuF5 trigonal bipyramids that share corners with three equivalent Li(2)F4 tetrahedra, corners with two equivalent Cu(1)F5 trigonal bipyramids,  an edgeedge with one Li(1)F4 tetrahedra, and  an edgeedge with one Cu(1)F5 trigonal bipyramid. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one Cu(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one Cu(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(2) and one Cu(2) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one Cu(2) atom. In the fifth F site, F(5) is bonded to one Li(2), one Cu(1), one Cu(2), and one Cu(3) atom to form a mixture of corner and edge-sharing FLiCu3 trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(1), one Cu(1), one Cu(2), and one Cu(3) atom to form a mixture of corner and edge-sharing FLiCu3 trigonal pyramids. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(2), one Cu(1), and one Cu(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(2) and one Cu(3) atom.
Li2Cu3F8 crystallizes in the triclinic P1 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(4), and one F(6) atom to form distorted LiF4 tetrahedra that share corners with three equivalent Cu(1)F5 trigonal bipyramids and  an edgeedge with one Cu(3)F5 trigonal bipyramid. The Li(1)-F(1) bond length is 1.83 Å. The Li(1)-F(2) bond length is 1.86 Å. The Li(1)-F(4) bond length is 1.81 Å. The Li(1)-F(6) bond length is 2.16 Å. In the second Li site, Li(2) is bonded to one F(3), one F(5), one F(7), and one F(8) atom to form distorted LiF4 tetrahedra that share corners with three equivalent Cu(3)F5 trigonal bipyramids and  an edgeedge with one Cu(1)F5 trigonal bipyramid. The Li(2)-F(3) bond length is 1.81 Å. The Li(2)-F(5) bond length is 2.12 Å. The Li(2)-F(7) bond length is 1.87 Å. The Li(2)-F(8) bond length is 1.83 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(5), one F(6), and one F(7) atom to form distorted CuF5 trigonal bipyramids that share corners with three equivalent Li(1)F4 tetrahedra, corners with two equivalent Cu(3)F5 trigonal bipyramids,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Cu(3)F5 trigonal bipyramid. The Cu(1)-F(1) bond length is 1.85 Å. The Cu(1)-F(2) bond length is 1.92 Å. The Cu(1)-F(5) bond length is 2.15 Å. The Cu(1)-F(6) bond length is 2.05 Å. The Cu(1)-F(7) bond length is 2.23 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to one F(3), one F(4), one F(5), and one F(6) atom. The Cu(2)-F(3) bond length is 1.86 Å. The Cu(2)-F(4) bond length is 1.86 Å. The Cu(2)-F(5) bond length is 2.02 Å. The Cu(2)-F(6) bond length is 2.01 Å. In the third Cu site, Cu(3) is bonded to one F(2), one F(5), one F(6), one F(7), and one F(8) atom to form distorted CuF5 trigonal bipyramids that share corners with three equivalent Li(2)F4 tetrahedra, corners with two equivalent Cu(1)F5 trigonal bipyramids,  an edgeedge with one Li(1)F4 tetrahedra, and  an edgeedge with one Cu(1)F5 trigonal bipyramid. The Cu(3)-F(2) bond length is 2.20 Å. The Cu(3)-F(5) bond length is 2.06 Å. The Cu(3)-F(6) bond length is 2.18 Å. The Cu(3)-F(7) bond length is 1.92 Å. The Cu(3)-F(8) bond length is 1.85 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one Cu(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one Cu(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(2) and one Cu(2) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one Cu(2) atom. In the fifth F site, F(5) is bonded to one Li(2), one Cu(1), one Cu(2), and one Cu(3) atom to form a mixture of corner and edge-sharing FLiCu3 trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(1), one Cu(1), one Cu(2), and one Cu(3) atom to form a mixture of corner and edge-sharing FLiCu3 trigonal pyramids. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(2), one Cu(1), and one Cu(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(2) and one Cu(3) atom.