Ce3S2O3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 7-coordinate geometry to three equivalent S(2), one O(1), and three equivalent O(2) atoms. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), one O(1), one O(2), and two equivalent O(3) atoms. In the third Ce site, Ce(3) is bonded in a 3-coordinate geometry to one S(2), four equivalent S(1), one O(3), and two equivalent O(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ce(2) and four equivalent Ce(3) atoms. In the second S site, S(2) is bonded to one Ce(3), two equivalent Ce(2), and three equivalent Ce(1) atoms to form SCe6 octahedra that share corners with three equivalent O(1)Ce4 tetrahedra, corners with five equivalent O(2)Ce4 tetrahedra, edges with four equivalent S(2)Ce6 octahedra, edges with two equivalent O(1)Ce4 tetrahedra, and edges with three equivalent O(2)Ce4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ce(1), one Ce(2), and two equivalent Ce(3) atoms to form OCe4 tetrahedra that share corners with three equivalent S(2)Ce6 octahedra, corners with two equivalent O(1)Ce4 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, edges with two equivalent S(2)Ce6 octahedra, and  an edgeedge with one O(2)Ce4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-51°. In the second O site, O(2) is bonded to one Ce(2) and three equivalent Ce(1) atoms to form OCe4 tetrahedra that share corners with five equivalent S(2)Ce6 octahedra, corners with two equivalent O(1)Ce4 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, edges with three equivalent S(2)Ce6 octahedra,  an edgeedge with one O(1)Ce4 tetrahedra, and edges with two equivalent O(2)Ce4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-50°. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Ce(3) and two equivalent Ce(2) atoms.
Ce3S2O3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 7-coordinate geometry to three equivalent S(2), one O(1), and three equivalent O(2) atoms. There are two shorter (2.95 Å) and one longer (2.97 Å) Ce(1)-S(2) bond length. The Ce(1)-O(1) bond length is 2.26 Å. There are two shorter (2.36 Å) and one longer (2.40 Å) Ce(1)-O(2) bond length. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), one O(1), one O(2), and two equivalent O(3) atoms. The Ce(2)-S(1) bond length is 2.82 Å. Both Ce(2)-S(2) bond lengths are 3.04 Å. The Ce(2)-O(1) bond length is 2.43 Å. The Ce(2)-O(2) bond length is 2.40 Å. Both Ce(2)-O(3) bond lengths are 2.20 Å. In the third Ce site, Ce(3) is bonded in a 3-coordinate geometry to one S(2), four equivalent S(1), one O(3), and two equivalent O(1) atoms. The Ce(3)-S(2) bond length is 3.07 Å. There are two shorter (2.96 Å) and two longer (3.01 Å) Ce(3)-S(1) bond lengths. The Ce(3)-O(3) bond length is 2.30 Å. Both Ce(3)-O(1) bond lengths are 2.42 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ce(2) and four equivalent Ce(3) atoms. In the second S site, S(2) is bonded to one Ce(3), two equivalent Ce(2), and three equivalent Ce(1) atoms to form SCe6 octahedra that share corners with three equivalent O(1)Ce4 tetrahedra, corners with five equivalent O(2)Ce4 tetrahedra, edges with four equivalent S(2)Ce6 octahedra, edges with two equivalent O(1)Ce4 tetrahedra, and edges with three equivalent O(2)Ce4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ce(1), one Ce(2), and two equivalent Ce(3) atoms to form OCe4 tetrahedra that share corners with three equivalent S(2)Ce6 octahedra, corners with two equivalent O(1)Ce4 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, edges with two equivalent S(2)Ce6 octahedra, and  an edgeedge with one O(2)Ce4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-51°. In the second O site, O(2) is bonded to one Ce(2) and three equivalent Ce(1) atoms to form OCe4 tetrahedra that share corners with five equivalent S(2)Ce6 octahedra, corners with two equivalent O(1)Ce4 tetrahedra, corners with two equivalent O(2)Ce4 tetrahedra, edges with three equivalent S(2)Ce6 octahedra,  an edgeedge with one O(1)Ce4 tetrahedra, and edges with two equivalent O(2)Ce4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-50°. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Ce(3) and two equivalent Ce(2) atoms.