Li6CuS4 crystallizes in the orthorhombic Imm2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(3) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to two equivalent S(1) and three equivalent S(2) atoms. In the third Li site, Li(3) is bonded to one S(3) and three equivalent S(2) atoms to form corner-sharing LiS4 tetrahedra. Cu(1) is bonded in a distorted trigonal planar geometry to one S(1) and two equivalent S(3) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), four equivalent Li(2), and one Cu(1) atom to form distorted edge-sharing SLi6Cu pentagonal bipyramids. In the second S site, S(2) is bonded in a 8-coordinate geometry to two equivalent Li(1), three equivalent Li(2), and three equivalent Li(3) atoms. In the third S site, S(3) is bonded in a 8-coordinate geometry to two equivalent Li(3), four equivalent Li(1), and two equivalent Cu(1) atoms.
Li6CuS4 crystallizes in the orthorhombic Imm2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(3) atoms. The Li(1)-S(1) bond length is 2.46 Å. Both Li(1)-S(2) bond lengths are 2.46 Å. Both Li(1)-S(3) bond lengths are 2.95 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to two equivalent S(1) and three equivalent S(2) atoms. Both Li(2)-S(1) bond lengths are 2.64 Å. There is one shorter (2.55 Å) and two longer (2.72 Å) Li(2)-S(2) bond lengths. In the third Li site, Li(3) is bonded to one S(3) and three equivalent S(2) atoms to form corner-sharing LiS4 tetrahedra. The Li(3)-S(3) bond length is 2.48 Å. There are two shorter (2.39 Å) and one longer (2.41 Å) Li(3)-S(2) bond length. Cu(1) is bonded in a distorted trigonal planar geometry to one S(1) and two equivalent S(3) atoms. The Cu(1)-S(1) bond length is 2.21 Å. Both Cu(1)-S(3) bond lengths are 2.25 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), four equivalent Li(2), and one Cu(1) atom to form distorted edge-sharing SLi6Cu pentagonal bipyramids. In the second S site, S(2) is bonded in a 8-coordinate geometry to two equivalent Li(1), three equivalent Li(2), and three equivalent Li(3) atoms. In the third S site, S(3) is bonded in a 8-coordinate geometry to two equivalent Li(3), four equivalent Li(1), and two equivalent Cu(1) atoms.