Ce5AgS8 crystallizes in the tetragonal I-4 space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. Ag(1) is bonded in a 8-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ce(2), four equivalent Ce(1), and one Ag(1) atom to form a mixture of distorted face, corner, and edge-sharing SCe5Ag octahedra. The corner-sharing octahedral tilt angles range from 16-47°. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ce(2), four equivalent Ce(1), and one Ag(1) atom.
Ce5AgS8 crystallizes in the tetragonal I-4 space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. There are a spread of Ce(1)-S(1) bond distances ranging from 2.85-3.13 Å. There are a spread of Ce(1)-S(2) bond distances ranging from 2.84-3.07 Å. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. All Ce(2)-S(1) bond lengths are 3.02 Å. All Ce(2)-S(2) bond lengths are 2.85 Å. Ag(1) is bonded in a 8-coordinate geometry to four equivalent S(1) and four equivalent S(2) atoms. All Ag(1)-S(1) bond lengths are 2.85 Å. All Ag(1)-S(2) bond lengths are 3.19 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ce(2), four equivalent Ce(1), and one Ag(1) atom to form a mixture of distorted face, corner, and edge-sharing SCe5Ag octahedra. The corner-sharing octahedral tilt angles range from 16-47°. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ce(2), four equivalent Ce(1), and one Ag(1) atom.