La2S2O crystallizes in the monoclinic P2_1/c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to two equivalent S(2), four equivalent S(1), and one O(1) atom. In the second La site, La(2) is bonded in a 7-coordinate geometry to one S(1), three equivalent S(2), and three equivalent O(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to one La(2) and four equivalent La(1) atoms to form distorted SLa5 trigonal bipyramids that share corners with three equivalent O(1)La4 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, corners with nine equivalent S(2)La5 trigonal bipyramids, edges with two equivalent O(1)La4 tetrahedra,  an edgeedge with one S(2)La5 trigonal bipyramid, and edges with four equivalent S(1)La5 trigonal bipyramids. In the second S site, S(2) is bonded to two equivalent La(1) and three equivalent La(2) atoms to form distorted SLa5 trigonal bipyramids that share corners with three equivalent O(1)La4 tetrahedra, corners with two equivalent S(2)La5 trigonal bipyramids, corners with nine equivalent S(1)La5 trigonal bipyramids, edges with four equivalent O(1)La4 tetrahedra,  an edgeedge with one S(1)La5 trigonal bipyramid, and edges with three equivalent S(2)La5 trigonal bipyramids. O(1) is bonded to one La(1) and three equivalent La(2) atoms to form OLa4 tetrahedra that share corners with four equivalent O(1)La4 tetrahedra, corners with three equivalent S(1)La5 trigonal bipyramids, corners with three equivalent S(2)La5 trigonal bipyramids,  an edgeedge with one O(1)La4 tetrahedra, edges with two equivalent S(1)La5 trigonal bipyramids, and edges with four equivalent S(2)La5 trigonal bipyramids.
La2S2O crystallizes in the monoclinic P2_1/c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to two equivalent S(2), four equivalent S(1), and one O(1) atom. There is one shorter (2.93 Å) and one longer (3.01 Å) La(1)-S(2) bond length. There are a spread of La(1)-S(1) bond distances ranging from 2.91-3.02 Å. The La(1)-O(1) bond length is 2.38 Å. In the second La site, La(2) is bonded in a 7-coordinate geometry to one S(1), three equivalent S(2), and three equivalent O(1) atoms. The La(2)-S(1) bond length is 3.09 Å. There are a spread of La(2)-S(2) bond distances ranging from 2.95-3.18 Å. There are a spread of La(2)-O(1) bond distances ranging from 2.40-2.44 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one La(2) and four equivalent La(1) atoms to form distorted SLa5 trigonal bipyramids that share corners with three equivalent O(1)La4 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, corners with nine equivalent S(2)La5 trigonal bipyramids, edges with two equivalent O(1)La4 tetrahedra,  an edgeedge with one S(2)La5 trigonal bipyramid, and edges with four equivalent S(1)La5 trigonal bipyramids. In the second S site, S(2) is bonded to two equivalent La(1) and three equivalent La(2) atoms to form distorted SLa5 trigonal bipyramids that share corners with three equivalent O(1)La4 tetrahedra, corners with two equivalent S(2)La5 trigonal bipyramids, corners with nine equivalent S(1)La5 trigonal bipyramids, edges with four equivalent O(1)La4 tetrahedra,  an edgeedge with one S(1)La5 trigonal bipyramid, and edges with three equivalent S(2)La5 trigonal bipyramids. O(1) is bonded to one La(1) and three equivalent La(2) atoms to form OLa4 tetrahedra that share corners with four equivalent O(1)La4 tetrahedra, corners with three equivalent S(1)La5 trigonal bipyramids, corners with three equivalent S(2)La5 trigonal bipyramids,  an edgeedge with one O(1)La4 tetrahedra, edges with two equivalent S(1)La5 trigonal bipyramids, and edges with four equivalent S(2)La5 trigonal bipyramids.