Li3Cu2(SO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 68-69°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form CuO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent S(1)O4 tetrahedra. In the second Cu site, Cu(2) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form CuO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent S(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-52°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Cu(2), and one S(1) atom to form corner-sharing OLi2CuS tetrahedra. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Cu(1) and one S(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(2), and one S(1) atom.
Li3Cu2(SO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 68-69°. The Li(1)-O(3) bond length is 1.95 Å. The Li(1)-O(4) bond length is 1.95 Å. There is one shorter (2.02 Å) and one longer (2.24 Å) Li(1)-O(1) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form CuO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent S(1)O4 tetrahedra. All Cu(1)-O(2) bond lengths are 2.11 Å. All Cu(1)-O(3) bond lengths are 2.25 Å. In the second Cu site, Cu(2) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form CuO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent S(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. All Cu(2)-O(1) bond lengths are 2.17 Å. All Cu(2)-O(4) bond lengths are 2.20 Å. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-52°. The S(1)-O(1) bond length is 1.53 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(3) bond length is 1.49 Å. The S(1)-O(4) bond length is 1.49 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Cu(2), and one S(1) atom to form corner-sharing OLi2CuS tetrahedra. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Cu(1) and one S(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(2), and one S(1) atom.