Li2SO4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent S(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 73-81°. S(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-50°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one S(1) atom to form a mixture of distorted edge and corner-sharing OLi3S tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one S(1) atom.
Li2SO4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent S(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Li(1)-O(2) bond lengths are 2.08 Å. All Li(1)-O(1) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 73-81°. Both Li(2)-O(1) bond lengths are 2.13 Å. Both Li(2)-O(2) bond lengths are 2.00 Å. S(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-50°. Both S(1)-O(1) bond lengths are 1.50 Å. Both S(1)-O(2) bond lengths are 1.48 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one S(1) atom to form a mixture of distorted edge and corner-sharing OLi3S tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one S(1) atom.