NaCe5S8 crystallizes in the tetragonal I-4 space group. Na(1) is bonded to four equivalent S(1) and four equivalent S(2) atoms to form distorted NaS8 hexagonal bipyramids that share corners with eight equivalent Ce(1)S8 hexagonal bipyramids, edges with four equivalent Ce(2)S8 hexagonal bipyramids, and faces with eight equivalent Ce(1)S8 hexagonal bipyramids. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to four equivalent S(1) and four equivalent S(2) atoms to form distorted CeS8 hexagonal bipyramids that share corners with two equivalent Na(1)S8 hexagonal bipyramids, corners with two equivalent Ce(2)S8 hexagonal bipyramids, corners with four equivalent Ce(1)S8 hexagonal bipyramids, edges with four equivalent Ce(1)S8 hexagonal bipyramids, faces with two equivalent Na(1)S8 hexagonal bipyramids, faces with two equivalent Ce(2)S8 hexagonal bipyramids, and faces with four equivalent Ce(1)S8 hexagonal bipyramids. In the second Ce site, Ce(2) is bonded to four equivalent S(1) and four equivalent S(2) atoms to form distorted CeS8 hexagonal bipyramids that share corners with eight equivalent Ce(1)S8 hexagonal bipyramids, edges with four equivalent Na(1)S8 hexagonal bipyramids, and faces with eight equivalent Ce(1)S8 hexagonal bipyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Ce(2), and four equivalent Ce(1) atoms to form a mixture of distorted face, corner, and edge-sharing SNaCe5 octahedra. The corner-sharing octahedral tilt angles range from 16-52°. In the second S site, S(2) is bonded to one Na(1), one Ce(2), and four equivalent Ce(1) atoms to form a mixture of distorted face, corner, and edge-sharing SNaCe5 octahedra. The corner-sharing octahedral tilt angles range from 17-52°.
NaCe5S8 crystallizes in the tetragonal I-4 space group. Na(1) is bonded to four equivalent S(1) and four equivalent S(2) atoms to form distorted NaS8 hexagonal bipyramids that share corners with eight equivalent Ce(1)S8 hexagonal bipyramids, edges with four equivalent Ce(2)S8 hexagonal bipyramids, and faces with eight equivalent Ce(1)S8 hexagonal bipyramids. All Na(1)-S(1) bond lengths are 2.90 Å. All Na(1)-S(2) bond lengths are 3.14 Å. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to four equivalent S(1) and four equivalent S(2) atoms to form distorted CeS8 hexagonal bipyramids that share corners with two equivalent Na(1)S8 hexagonal bipyramids, corners with two equivalent Ce(2)S8 hexagonal bipyramids, corners with four equivalent Ce(1)S8 hexagonal bipyramids, edges with four equivalent Ce(1)S8 hexagonal bipyramids, faces with two equivalent Na(1)S8 hexagonal bipyramids, faces with two equivalent Ce(2)S8 hexagonal bipyramids, and faces with four equivalent Ce(1)S8 hexagonal bipyramids. There are a spread of Ce(1)-S(1) bond distances ranging from 2.87-3.06 Å. There are a spread of Ce(1)-S(2) bond distances ranging from 2.84-3.08 Å. In the second Ce site, Ce(2) is bonded to four equivalent S(1) and four equivalent S(2) atoms to form distorted CeS8 hexagonal bipyramids that share corners with eight equivalent Ce(1)S8 hexagonal bipyramids, edges with four equivalent Na(1)S8 hexagonal bipyramids, and faces with eight equivalent Ce(1)S8 hexagonal bipyramids. All Ce(2)-S(1) bond lengths are 3.01 Å. All Ce(2)-S(2) bond lengths are 2.86 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Ce(2), and four equivalent Ce(1) atoms to form a mixture of distorted face, corner, and edge-sharing SNaCe5 octahedra. The corner-sharing octahedral tilt angles range from 16-52°. In the second S site, S(2) is bonded to one Na(1), one Ce(2), and four equivalent Ce(1) atoms to form a mixture of distorted face, corner, and edge-sharing SNaCe5 octahedra. The corner-sharing octahedral tilt angles range from 17-52°.