Ce3AsS3 crystallizes in the cubic P2_13 space group. Ce(1) is bonded to two equivalent As(1), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of distorted edge, face, and corner-sharing CeAs2S6 hexagonal bipyramids. As(1) is bonded to six equivalent Ce(1) atoms to form distorted AsCe6 octahedra that share corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with three equivalent S(3)Ce6 octahedra, corners with six equivalent As(1)Ce6 octahedra, edges with three equivalent S(1)Ce6 octahedra, edges with three equivalent S(3)Ce6 octahedra,  a faceface with one S(1)Ce6 octahedra,  a faceface with one S(3)Ce6 octahedra, and faces with three equivalent S(2)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°. There are three inequivalent S sites. In the first S site, S(1) is bonded to six equivalent Ce(1) atoms to form distorted SCe6 octahedra that share corners with three equivalent As(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with three equivalent S(3)Ce6 octahedra, corners with six equivalent S(1)Ce6 octahedra, edges with three equivalent As(1)Ce6 octahedra, edges with three equivalent S(2)Ce6 octahedra,  a faceface with one As(1)Ce6 octahedra,  a faceface with one S(2)Ce6 octahedra, and faces with three equivalent S(3)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°. In the second S site, S(2) is bonded to six equivalent Ce(1) atoms to form distorted SCe6 octahedra that share corners with three equivalent As(1)Ce6 octahedra, corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(3)Ce6 octahedra, corners with six equivalent S(2)Ce6 octahedra, edges with three equivalent S(1)Ce6 octahedra, edges with three equivalent S(3)Ce6 octahedra,  a faceface with one S(1)Ce6 octahedra,  a faceface with one S(3)Ce6 octahedra, and faces with three equivalent As(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-49°. In the third S site, S(3) is bonded to six equivalent Ce(1) atoms to form distorted SCe6 octahedra that share corners with three equivalent As(1)Ce6 octahedra, corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with six equivalent S(3)Ce6 octahedra, edges with three equivalent As(1)Ce6 octahedra, edges with three equivalent S(2)Ce6 octahedra,  a faceface with one As(1)Ce6 octahedra,  a faceface with one S(2)Ce6 octahedra, and faces with three equivalent S(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°.
Ce3AsS3 crystallizes in the cubic P2_13 space group. Ce(1) is bonded to two equivalent As(1), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of distorted edge, face, and corner-sharing CeAs2S6 hexagonal bipyramids. There is one shorter (2.94 Å) and one longer (3.04 Å) Ce(1)-As(1) bond length. There is one shorter (2.90 Å) and one longer (3.08 Å) Ce(1)-S(1) bond length. There is one shorter (2.90 Å) and one longer (3.07 Å) Ce(1)-S(2) bond length. There is one shorter (2.91 Å) and one longer (3.07 Å) Ce(1)-S(3) bond length. As(1) is bonded to six equivalent Ce(1) atoms to form distorted AsCe6 octahedra that share corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with three equivalent S(3)Ce6 octahedra, corners with six equivalent As(1)Ce6 octahedra, edges with three equivalent S(1)Ce6 octahedra, edges with three equivalent S(3)Ce6 octahedra,  a faceface with one S(1)Ce6 octahedra,  a faceface with one S(3)Ce6 octahedra, and faces with three equivalent S(2)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°. There are three inequivalent S sites. In the first S site, S(1) is bonded to six equivalent Ce(1) atoms to form distorted SCe6 octahedra that share corners with three equivalent As(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with three equivalent S(3)Ce6 octahedra, corners with six equivalent S(1)Ce6 octahedra, edges with three equivalent As(1)Ce6 octahedra, edges with three equivalent S(2)Ce6 octahedra,  a faceface with one As(1)Ce6 octahedra,  a faceface with one S(2)Ce6 octahedra, and faces with three equivalent S(3)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°. In the second S site, S(2) is bonded to six equivalent Ce(1) atoms to form distorted SCe6 octahedra that share corners with three equivalent As(1)Ce6 octahedra, corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(3)Ce6 octahedra, corners with six equivalent S(2)Ce6 octahedra, edges with three equivalent S(1)Ce6 octahedra, edges with three equivalent S(3)Ce6 octahedra,  a faceface with one S(1)Ce6 octahedra,  a faceface with one S(3)Ce6 octahedra, and faces with three equivalent As(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-49°. In the third S site, S(3) is bonded to six equivalent Ce(1) atoms to form distorted SCe6 octahedra that share corners with three equivalent As(1)Ce6 octahedra, corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with six equivalent S(3)Ce6 octahedra, edges with three equivalent As(1)Ce6 octahedra, edges with three equivalent S(2)Ce6 octahedra,  a faceface with one As(1)Ce6 octahedra,  a faceface with one S(2)Ce6 octahedra, and faces with three equivalent S(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-50°.