Li3Cu4SnO8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, and edges with two equivalent Sn(1)O6 octahedra. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and four equivalent O(2) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. In the second Cu site, Cu(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CuO6 octahedra that share edges with two equivalent Sn(1)O6 octahedra and edges with four equivalent Li(1)O6 octahedra. In the third Cu site, Cu(3) is bonded in a distorted square co-planar geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Sn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form SnO6 octahedra that share edges with two equivalent Cu(2)O6 octahedra and edges with four equivalent Li(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Cu(3), and one Sn(1) atom to form distorted OLi3Cu2Sn octahedra that share corners with six equivalent O(1)Li3Cu2Sn octahedra and edges with four equivalent O(3)Li2Cu3 trigonal bipyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Cu(1), one Cu(2), one Cu(3), and one Sn(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one Cu(2), and two equivalent Cu(3) atoms to form distorted OLi2Cu3 trigonal bipyramids that share corners with five equivalent O(3)Li2Cu3 trigonal bipyramids and edges with four equivalent O(1)Li3Cu2Sn octahedra.
Li3Cu4SnO8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, and edges with two equivalent Sn(1)O6 octahedra. Both Li(1)-O(1) bond lengths are 2.20 Å. Both Li(1)-O(2) bond lengths are 2.13 Å. Both Li(1)-O(3) bond lengths are 2.25 Å. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and four equivalent O(2) atoms. Both Li(2)-O(1) bond lengths are 2.60 Å. All Li(2)-O(2) bond lengths are 2.08 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. All Cu(1)-O(2) bond lengths are 1.94 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CuO6 octahedra that share edges with two equivalent Sn(1)O6 octahedra and edges with four equivalent Li(1)O6 octahedra. Both Cu(2)-O(3) bond lengths are 1.95 Å. All Cu(2)-O(2) bond lengths are 2.20 Å. In the third Cu site, Cu(3) is bonded in a distorted square co-planar geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Cu(3)-O(1) bond lengths are 1.95 Å. Both Cu(3)-O(2) bond lengths are 2.61 Å. Both Cu(3)-O(3) bond lengths are 1.96 Å. Sn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form SnO6 octahedra that share edges with two equivalent Cu(2)O6 octahedra and edges with four equivalent Li(1)O6 octahedra. Both Sn(1)-O(1) bond lengths are 2.15 Å. All Sn(1)-O(2) bond lengths are 2.07 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Cu(3), and one Sn(1) atom to form distorted OLi3Cu2Sn octahedra that share corners with six equivalent O(1)Li3Cu2Sn octahedra and edges with four equivalent O(3)Li2Cu3 trigonal bipyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Cu(1), one Cu(2), one Cu(3), and one Sn(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one Cu(2), and two equivalent Cu(3) atoms to form distorted OLi2Cu3 trigonal bipyramids that share corners with five equivalent O(3)Li2Cu3 trigonal bipyramids and edges with four equivalent O(1)Li3Cu2Sn octahedra.