Ce4S3O4 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 3-coordinate geometry to one S(2), four equivalent S(1), one O(1), and two 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), two equivalent O(1), and two equivalent O(2) 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(1) atoms. In the second S site, S(2) is bonded to two equivalent Ce(1) and four equivalent Ce(2) atoms to form SCe6 octahedra that share corners with four equivalent O(2)Ce4 tetrahedra, edges with two equivalent S(2)Ce6 octahedra, and edges with four equivalent O(2)Ce4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ce(1) and two equivalent Ce(2) atoms. In the second O site, O(2) is bonded to two equivalent Ce(1) and two equivalent Ce(2) atoms to form distorted OCe4 tetrahedra that share corners with two equivalent S(2)Ce6 octahedra, 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 are 51°.
Ce4S3O4 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 3-coordinate geometry to one S(2), four equivalent S(1), one O(1), and two equivalent O(2) atoms. The Ce(1)-S(2) bond length is 3.08 Å. There are two shorter (2.99 Å) and two longer (3.01 Å) Ce(1)-S(1) bond lengths. The Ce(1)-O(1) bond length is 2.30 Å. Both Ce(1)-O(2) bond lengths are 2.40 Å. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent O(1), and two equivalent O(2) atoms. The Ce(2)-S(1) bond length is 2.83 Å. Both Ce(2)-S(2) bond lengths are 2.99 Å. Both Ce(2)-O(1) bond lengths are 2.19 Å. There is one shorter (2.26 Å) and one longer (2.44 Å) Ce(2)-O(2) bond length. 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(1) atoms. In the second S site, S(2) is bonded to two equivalent Ce(1) and four equivalent Ce(2) atoms to form SCe6 octahedra that share corners with four equivalent O(2)Ce4 tetrahedra, edges with two equivalent S(2)Ce6 octahedra, and edges with four equivalent O(2)Ce4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ce(1) and two equivalent Ce(2) atoms. In the second O site, O(2) is bonded to two equivalent Ce(1) and two equivalent Ce(2) atoms to form distorted OCe4 tetrahedra that share corners with two equivalent S(2)Ce6 octahedra, 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 are 51°.