Ce2S3 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to one S(1), three equivalent S(4), and three equivalent S(5) atoms to form distorted edge-sharing CeS7 pentagonal bipyramids. In the second Ce site, Ce(2) is bonded to one S(2), three equivalent S(3), and three equivalent S(6) atoms to form distorted edge-sharing CeS7 pentagonal bipyramids. In the third Ce site, Ce(3) is bonded in a 8-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. In the fourth Ce site, Ce(4) is bonded in a 8-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent Ce(3), and two equivalent Ce(4) atoms to form a mixture of corner, edge, and face-sharing SCe5 square pyramids. In the second S site, S(2) is bonded to one Ce(2), two equivalent Ce(3), and two equivalent Ce(4) atoms to form a mixture of corner, edge, and face-sharing SCe5 square pyramids. In the third S site, S(3) is bonded to two equivalent Ce(4) and three equivalent Ce(2) atoms to form a mixture of distorted corner, edge, and face-sharing SCe5 trigonal bipyramids. In the fourth S site, S(4) is bonded to two equivalent Ce(3) and three equivalent Ce(1) atoms to form a mixture of distorted corner, edge, and face-sharing SCe5 trigonal bipyramids. In the fifth S site, S(5) is bonded to one Ce(3), one Ce(4), and three equivalent Ce(1) atoms to form a mixture of distorted corner and edge-sharing SCe5 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ce(3), one Ce(4), and three equivalent Ce(2) atoms to form a mixture of distorted corner and edge-sharing SCe5 trigonal bipyramids.
Ce2S3 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to one S(1), three equivalent S(4), and three equivalent S(5) atoms to form distorted edge-sharing CeS7 pentagonal bipyramids. The Ce(1)-S(1) bond length is 2.91 Å. There are two shorter (2.87 Å) and one longer (2.99 Å) Ce(1)-S(4) bond length. There are two shorter (2.85 Å) and one longer (3.01 Å) Ce(1)-S(5) bond length. In the second Ce site, Ce(2) is bonded to one S(2), three equivalent S(3), and three equivalent S(6) atoms to form distorted edge-sharing CeS7 pentagonal bipyramids. The Ce(2)-S(2) bond length is 2.91 Å. There are two shorter (2.87 Å) and one longer (2.98 Å) Ce(2)-S(3) bond length. There are two shorter (2.85 Å) and one longer (3.02 Å) Ce(2)-S(6) bond length. In the third Ce site, Ce(3) is bonded in a 8-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. The Ce(3)-S(5) bond length is 3.23 Å. The Ce(3)-S(6) bond length is 3.05 Å. Both Ce(3)-S(1) bond lengths are 2.99 Å. Both Ce(3)-S(2) bond lengths are 2.84 Å. Both Ce(3)-S(4) bond lengths are 2.98 Å. In the fourth Ce site, Ce(4) is bonded in a 8-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Ce(4)-S(5) bond length is 3.03 Å. The Ce(4)-S(6) bond length is 3.24 Å. Both Ce(4)-S(1) bond lengths are 2.85 Å. Both Ce(4)-S(2) bond lengths are 2.99 Å. Both Ce(4)-S(3) bond lengths are 2.99 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent Ce(3), and two equivalent Ce(4) atoms to form a mixture of corner, edge, and face-sharing SCe5 square pyramids. In the second S site, S(2) is bonded to one Ce(2), two equivalent Ce(3), and two equivalent Ce(4) atoms to form a mixture of corner, edge, and face-sharing SCe5 square pyramids. In the third S site, S(3) is bonded to two equivalent Ce(4) and three equivalent Ce(2) atoms to form a mixture of distorted corner, edge, and face-sharing SCe5 trigonal bipyramids. In the fourth S site, S(4) is bonded to two equivalent Ce(3) and three equivalent Ce(1) atoms to form a mixture of distorted corner, edge, and face-sharing SCe5 trigonal bipyramids. In the fifth S site, S(5) is bonded to one Ce(3), one Ce(4), and three equivalent Ce(1) atoms to form a mixture of distorted corner and edge-sharing SCe5 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ce(3), one Ce(4), and three equivalent Ce(2) atoms to form a mixture of distorted corner and edge-sharing SCe5 trigonal bipyramids.