Ce3NS3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 1-coordinate geometry to one N(1), one S(1), two equivalent S(3), and three equivalent S(2) atoms. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one N(1), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. In the third Ce site, Ce(3) is bonded in a 7-coordinate geometry to two equivalent N(1), one S(2), one S(3), and three equivalent S(1) atoms. N(1) is bonded to one Ce(1), one Ce(2), and two equivalent Ce(3) atoms to form NCe4 tetrahedra that share corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with two equivalent N(1)Ce4 tetrahedra, edges with two equivalent S(2)Ce6 octahedra, and edges with three equivalent S(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-51°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent Ce(2), and three equivalent Ce(3) atoms to form distorted SCe6 octahedra that share corners with seven equivalent S(2)Ce6 octahedra, corners with three equivalent N(1)Ce4 tetrahedra, edges with four equivalent S(1)Ce6 octahedra, edges with three equivalent N(1)Ce4 tetrahedra, and  a faceface with one S(2)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. 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 seven equivalent S(1)Ce6 octahedra, corners with three equivalent N(1)Ce4 tetrahedra, edges with four equivalent S(2)Ce6 octahedra, edges with two equivalent N(1)Ce4 tetrahedra, and  a faceface with one S(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Ce(3), two equivalent Ce(1), and two equivalent Ce(2) atoms.
Ce3NS3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 1-coordinate geometry to one N(1), one S(1), two equivalent S(3), and three equivalent S(2) atoms. The Ce(1)-N(1) bond length is 2.29 Å. The Ce(1)-S(1) bond length is 3.58 Å. Both Ce(1)-S(3) bond lengths are 2.85 Å. There are two shorter (2.89 Å) and one longer (3.04 Å) Ce(1)-S(2) bond length. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one N(1), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Ce(2)-N(1) bond length is 2.33 Å. Both Ce(2)-S(1) bond lengths are 2.88 Å. Both Ce(2)-S(2) bond lengths are 3.15 Å. Both Ce(2)-S(3) bond lengths are 2.96 Å. In the third Ce site, Ce(3) is bonded in a 7-coordinate geometry to two equivalent N(1), one S(2), one S(3), and three equivalent S(1) atoms. Both Ce(3)-N(1) bond lengths are 2.39 Å. The Ce(3)-S(2) bond length is 3.18 Å. The Ce(3)-S(3) bond length is 2.89 Å. There is one shorter (2.94 Å) and two longer (3.11 Å) Ce(3)-S(1) bond lengths. N(1) is bonded to one Ce(1), one Ce(2), and two equivalent Ce(3) atoms to form NCe4 tetrahedra that share corners with three equivalent S(1)Ce6 octahedra, corners with three equivalent S(2)Ce6 octahedra, corners with two equivalent N(1)Ce4 tetrahedra, edges with two equivalent S(2)Ce6 octahedra, and edges with three equivalent S(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 17-51°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent Ce(2), and three equivalent Ce(3) atoms to form distorted SCe6 octahedra that share corners with seven equivalent S(2)Ce6 octahedra, corners with three equivalent N(1)Ce4 tetrahedra, edges with four equivalent S(1)Ce6 octahedra, edges with three equivalent N(1)Ce4 tetrahedra, and  a faceface with one S(2)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. 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 seven equivalent S(1)Ce6 octahedra, corners with three equivalent N(1)Ce4 tetrahedra, edges with four equivalent S(2)Ce6 octahedra, edges with two equivalent N(1)Ce4 tetrahedra, and  a faceface with one S(1)Ce6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Ce(3), two equivalent Ce(1), and two equivalent Ce(2) atoms.