Ce3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to one S(4), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms. In the third Ce site, Ce(3) is bonded to one S(1), one S(2), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form distorted CeS7 pentagonal bipyramids that share  a cornercorner with one Cr(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Ce(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 29°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form CrS6 octahedra that share edges with two equivalent Cr(1)S6 octahedra and edges with four equivalent Ce(3)S7 pentagonal bipyramids. In the second Cr site, Cr(2) is bonded to two equivalent S(1) and four equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent Ce(3)S7 pentagonal bipyramids and edges with two equivalent Cr(2)S6 octahedra. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Ce(2), two equivalent Ce(1), and two equivalent Ce(3) atoms to form distorted SCe5 trigonal bipyramids that share  a cornercorner with one S(4)Ce3Cr2 trigonal bipyramid, corners with two equivalent S(2)Ce5 trigonal bipyramids, corners with four equivalent S(3)Ce4Cr trigonal bipyramids,  an edgeedge with one S(3)Ce4Cr trigonal bipyramid, edges with two equivalent S(4)Ce3Cr2 trigonal bipyramids, edges with two equivalent S(6)Ce3Cr2 trigonal bipyramids, edges with two equivalent S(5)Ce5 trigonal bipyramids, and edges with three equivalent S(2)Ce5 trigonal bipyramids. In the second S site, S(6) is bonded to one Ce(1), two equivalent Ce(2), and two equivalent Cr(2) atoms to form distorted SCe3Cr2 trigonal bipyramids that share corners with two equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with two equivalent S(3)Ce4Cr trigonal bipyramids, corners with three equivalent S(4)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ce5 trigonal bipyramids,  an edgeedge with one S(3)Ce4Cr trigonal bipyramid,  an edgeedge with one S(2)Ce5 trigonal bipyramid, edges with two equivalent S(5)Ce5 trigonal bipyramids, and edges with three equivalent S(6)Ce3Cr2 trigonal bipyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one Ce(3), two equivalent Ce(1), and one Cr(2) atom. In the fourth S site, S(2) is bonded to one Ce(3), two equivalent Ce(1), and two equivalent Ce(2) atoms to form SCe5 trigonal bipyramids that share  a cornercorner with one S(4)Ce3Cr2 trigonal bipyramid, corners with two equivalent S(5)Ce5 trigonal bipyramids, corners with four equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(3)Ce4Cr trigonal bipyramids,  an edgeedge with one S(6)Ce3Cr2 trigonal bipyramid,  an edgeedge with one S(3)Ce4Cr trigonal bipyramid, edges with two equivalent S(4)Ce3Cr2 trigonal bipyramids, edges with two equivalent S(2)Ce5 trigonal bipyramids, and edges with three equivalent S(5)Ce5 trigonal bipyramids. In the fifth S site, S(3) is bonded to two equivalent Ce(2), two equivalent Ce(3), and one Cr(1) atom to form distorted SCe4Cr trigonal bipyramids that share  a cornercorner with one S(3)Ce4Cr trigonal bipyramid, corners with two equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ce5 trigonal bipyramids, corners with four equivalent S(5)Ce5 trigonal bipyramids,  an edgeedge with one S(6)Ce3Cr2 trigonal bipyramid,  an edgeedge with one S(2)Ce5 trigonal bipyramid,  an edgeedge with one S(5)Ce5 trigonal bipyramid, edges with two equivalent S(3)Ce4Cr trigonal bipyramids, and edges with four equivalent S(4)Ce3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one Ce(1), one Ce(2), one Ce(3), and two equivalent Cr(1) atoms to form distorted SCe3Cr2 trigonal bipyramids that share  a cornercorner with one S(2)Ce5 trigonal bipyramid,  a cornercorner with one S(5)Ce5 trigonal bipyramid, corners with three equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(4)Ce3Cr2 trigonal bipyramids,  an edgeedge with one S(4)Ce3Cr2 trigonal bipyramid, edges with two equivalent S(2)Ce5 trigonal bipyramids, edges with two equivalent S(5)Ce5 trigonal bipyramids, and edges with four equivalent S(3)Ce4Cr trigonal bipyramids.
Ce3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. The Ce(1)-S(4) bond length is 3.07 Å. The Ce(1)-S(6) bond length is 2.92 Å. Both Ce(1)-S(1) bond lengths are 2.83 Å. Both Ce(1)-S(2) bond lengths are 2.93 Å. Both Ce(1)-S(5) bond lengths are 2.85 Å. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to one S(4), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms. The Ce(2)-S(4) bond length is 3.16 Å. The Ce(2)-S(5) bond length is 3.07 Å. Both Ce(2)-S(2) bond lengths are 2.83 Å. Both Ce(2)-S(3) bond lengths are 2.92 Å. Both Ce(2)-S(6) bond lengths are 2.90 Å. In the third Ce site, Ce(3) is bonded to one S(1), one S(2), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form distorted CeS7 pentagonal bipyramids that share  a cornercorner with one Cr(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Ce(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 29°. The Ce(3)-S(1) bond length is 2.77 Å. The Ce(3)-S(2) bond length is 2.91 Å. The Ce(3)-S(4) bond length is 2.88 Å. Both Ce(3)-S(3) bond lengths are 2.83 Å. Both Ce(3)-S(5) bond lengths are 2.80 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form CrS6 octahedra that share edges with two equivalent Cr(1)S6 octahedra and edges with four equivalent Ce(3)S7 pentagonal bipyramids. Both Cr(1)-S(3) bond lengths are 2.43 Å. All Cr(1)-S(4) bond lengths are 2.50 Å. In the second Cr site, Cr(2) is bonded to two equivalent S(1) and four equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent Ce(3)S7 pentagonal bipyramids and edges with two equivalent Cr(2)S6 octahedra. Both Cr(2)-S(1) bond lengths are 2.33 Å. All Cr(2)-S(6) bond lengths are 2.54 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Ce(2), two equivalent Ce(1), and two equivalent Ce(3) atoms to form distorted SCe5 trigonal bipyramids that share  a cornercorner with one S(4)Ce3Cr2 trigonal bipyramid, corners with two equivalent S(2)Ce5 trigonal bipyramids, corners with four equivalent S(3)Ce4Cr trigonal bipyramids,  an edgeedge with one S(3)Ce4Cr trigonal bipyramid, edges with two equivalent S(4)Ce3Cr2 trigonal bipyramids, edges with two equivalent S(6)Ce3Cr2 trigonal bipyramids, edges with two equivalent S(5)Ce5 trigonal bipyramids, and edges with three equivalent S(2)Ce5 trigonal bipyramids. In the second S site, S(6) is bonded to one Ce(1), two equivalent Ce(2), and two equivalent Cr(2) atoms to form distorted SCe3Cr2 trigonal bipyramids that share corners with two equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with two equivalent S(3)Ce4Cr trigonal bipyramids, corners with three equivalent S(4)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ce5 trigonal bipyramids,  an edgeedge with one S(3)Ce4Cr trigonal bipyramid,  an edgeedge with one S(2)Ce5 trigonal bipyramid, edges with two equivalent S(5)Ce5 trigonal bipyramids, and edges with three equivalent S(6)Ce3Cr2 trigonal bipyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one Ce(3), two equivalent Ce(1), and one Cr(2) atom. In the fourth S site, S(2) is bonded to one Ce(3), two equivalent Ce(1), and two equivalent Ce(2) atoms to form SCe5 trigonal bipyramids that share  a cornercorner with one S(4)Ce3Cr2 trigonal bipyramid, corners with two equivalent S(5)Ce5 trigonal bipyramids, corners with four equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(3)Ce4Cr trigonal bipyramids,  an edgeedge with one S(6)Ce3Cr2 trigonal bipyramid,  an edgeedge with one S(3)Ce4Cr trigonal bipyramid, edges with two equivalent S(4)Ce3Cr2 trigonal bipyramids, edges with two equivalent S(2)Ce5 trigonal bipyramids, and edges with three equivalent S(5)Ce5 trigonal bipyramids. In the fifth S site, S(3) is bonded to two equivalent Ce(2), two equivalent Ce(3), and one Cr(1) atom to form distorted SCe4Cr trigonal bipyramids that share  a cornercorner with one S(3)Ce4Cr trigonal bipyramid, corners with two equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ce5 trigonal bipyramids, corners with four equivalent S(5)Ce5 trigonal bipyramids,  an edgeedge with one S(6)Ce3Cr2 trigonal bipyramid,  an edgeedge with one S(2)Ce5 trigonal bipyramid,  an edgeedge with one S(5)Ce5 trigonal bipyramid, edges with two equivalent S(3)Ce4Cr trigonal bipyramids, and edges with four equivalent S(4)Ce3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one Ce(1), one Ce(2), one Ce(3), and two equivalent Cr(1) atoms to form distorted SCe3Cr2 trigonal bipyramids that share  a cornercorner with one S(2)Ce5 trigonal bipyramid,  a cornercorner with one S(5)Ce5 trigonal bipyramid, corners with three equivalent S(6)Ce3Cr2 trigonal bipyramids, corners with four equivalent S(4)Ce3Cr2 trigonal bipyramids,  an edgeedge with one S(4)Ce3Cr2 trigonal bipyramid, edges with two equivalent S(2)Ce5 trigonal bipyramids, edges with two equivalent S(5)Ce5 trigonal bipyramids, and edges with four equivalent S(3)Ce4Cr trigonal bipyramids.