Ce2SiS5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to two equivalent S(3), two equivalent S(4), two equivalent S(5), and three equivalent S(1) atoms. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one S(3), one S(4), one S(5), two equivalent S(1), and two equivalent S(2) atoms. Si(1) is bonded in a trigonal non-coplanar geometry to one S(2), one S(3), and one S(4) atom. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ce(2) and three equivalent Ce(1) atoms. In the second S site, S(2) is bonded in a trigonal planar geometry to two equivalent Ce(2) and one Si(1) atom. In the third S site, S(3) is bonded to one Ce(2), two equivalent Ce(1), and one Si(1) atom to form corner-sharing SCe3Si trigonal pyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ce(2), two equivalent Ce(1), and one Si(1) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Ce(2) and two equivalent Ce(1) atoms.
Ce2SiS5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to two equivalent S(3), two equivalent S(4), two equivalent S(5), and three equivalent S(1) atoms. There is one shorter (2.86 Å) and one longer (2.98 Å) Ce(1)-S(3) bond length. There is one shorter (2.87 Å) and one longer (2.94 Å) Ce(1)-S(4) bond length. There is one shorter (2.71 Å) and one longer (2.83 Å) Ce(1)-S(5) bond length. There are a spread of Ce(1)-S(1) bond distances ranging from 2.88-3.63 Å. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one S(3), one S(4), one S(5), two equivalent S(1), and two equivalent S(2) atoms. The Ce(2)-S(3) bond length is 2.84 Å. The Ce(2)-S(4) bond length is 2.90 Å. The Ce(2)-S(5) bond length is 2.76 Å. There is one shorter (2.70 Å) and one longer (2.86 Å) Ce(2)-S(1) bond length. There is one shorter (2.78 Å) and one longer (2.79 Å) Ce(2)-S(2) bond length. Si(1) is bonded in a trigonal non-coplanar geometry to one S(2), one S(3), and one S(4) atom. The Si(1)-S(2) bond length is 2.20 Å. The Si(1)-S(3) bond length is 2.26 Å. The Si(1)-S(4) bond length is 2.28 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ce(2) and three equivalent Ce(1) atoms. In the second S site, S(2) is bonded in a trigonal planar geometry to two equivalent Ce(2) and one Si(1) atom. In the third S site, S(3) is bonded to one Ce(2), two equivalent Ce(1), and one Si(1) atom to form corner-sharing SCe3Si trigonal pyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ce(2), two equivalent Ce(1), and one Si(1) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Ce(2) and two equivalent Ce(1) atoms.