Ce3Si2S8Cl crystallizes in the monoclinic C2/c space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(4), three equivalent S(2), and one Cl(1) atom. In the second Ce site, Ce(2) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(4), four equivalent S(3), and one Cl(1) atom. Si(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Ce(2), two equivalent Ce(1), and one Si(1) atom to form distorted corner-sharing SCe3Si trigonal pyramids. In the second S site, S(1) is bonded in a 4-coordinate geometry to one Ce(2), two equivalent Ce(1), and one Si(1) atom. In the third S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ce(1) and one Si(1) atom. In the fourth S site, S(3) is bonded in a 4-coordinate geometry to one Ce(1), two equivalent Ce(2), and one Si(1) atom. Cl(1) is bonded in a 3-coordinate geometry to one Ce(2) and two equivalent Ce(1) atoms.
Ce3Si2S8Cl crystallizes in the monoclinic C2/c space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(4), three equivalent S(2), and one Cl(1) atom. The Ce(1)-S(3) bond length is 2.91 Å. There is one shorter (2.99 Å) and one longer (3.11 Å) Ce(1)-S(1) bond length. There is one shorter (2.95 Å) and one longer (3.01 Å) Ce(1)-S(4) bond length. There are a spread of Ce(1)-S(2) bond distances ranging from 2.92-3.08 Å. The Ce(1)-Cl(1) bond length is 3.38 Å. In the second Ce site, Ce(2) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(4), four equivalent S(3), and one Cl(1) atom. Both Ce(2)-S(1) bond lengths are 2.90 Å. Both Ce(2)-S(4) bond lengths are 2.91 Å. There are two shorter (3.33 Å) and two longer (3.37 Å) Ce(2)-S(3) bond lengths. The Ce(2)-Cl(1) bond length is 2.88 Å. Si(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Si(1)-S(1) bond length is 2.12 Å. The Si(1)-S(2) bond length is 2.14 Å. The Si(1)-S(3) bond length is 2.12 Å. The Si(1)-S(4) bond length is 2.13 Å. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Ce(2), two equivalent Ce(1), and one Si(1) atom to form distorted corner-sharing SCe3Si trigonal pyramids. In the second S site, S(1) is bonded in a 4-coordinate geometry to one Ce(2), two equivalent Ce(1), and one Si(1) atom. In the third S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ce(1) and one Si(1) atom. In the fourth S site, S(3) is bonded in a 4-coordinate geometry to one Ce(1), two equivalent Ce(2), and one Si(1) atom. Cl(1) is bonded in a 3-coordinate geometry to one Ce(2) and two equivalent Ce(1) atoms.