Li2SO4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with four equivalent S(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 four equivalent Li(1)O4 tetrahedra and corners with four equivalent Li(2)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Li(2) and one S(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one S(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one S(1) atom.
Li2SO4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 1.94 Å. There is one shorter (1.91 Å) and one longer (1.96 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with four equivalent S(1)O4 tetrahedra. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-O(3) bond length is 1.94 Å. There is one shorter (1.91 Å) and one longer (1.96 Å) Li(2)-O(1) bond length. 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 four equivalent Li(1)O4 tetrahedra and corners with four equivalent Li(2)O4 tetrahedra. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(3) bond length is 1.47 Å. The S(1)-O(4) bond length is 1.47 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Li(2) and one S(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one S(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one S(1) atom.