Ce4CrS7 crystallizes in the monoclinic P2_1 space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(7), and two equivalent S(5) atoms. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(5), one S(7), and two equivalent S(6) atoms. In the third Ce site, Ce(3) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(6), one S(7), and two equivalent S(4) atoms. In the fourth Ce site, Ce(4) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(5), one S(6), one S(7), and two equivalent S(4) atoms. Cr(1) is bonded to one S(1), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing CrS5 square pyramids. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), one Ce(4), and one Cr(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), and two equivalent Cr(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), one Ce(4), and two equivalent Cr(1) atoms. In the fourth S site, S(4) is bonded to one Ce(1), two equivalent Ce(3), and two equivalent Ce(4) atoms to form distorted SCe5 trigonal bipyramids that share  a cornercorner with one S(7)Ce4 tetrahedra, corners with two equivalent S(5)Ce4 trigonal pyramids, edges with two equivalent S(7)Ce4 tetrahedra, edges with two equivalent S(4)Ce5 trigonal bipyramids, and  an edgeedge with one S(5)Ce4 trigonal pyramid. In the fifth S site, S(5) is bonded to one Ce(2), one Ce(4), and two equivalent Ce(1) atoms to form distorted SCe4 trigonal pyramids that share corners with two equivalent S(7)Ce4 tetrahedra, corners with two equivalent S(4)Ce5 trigonal bipyramids, corners with two equivalent S(5)Ce4 trigonal pyramids,  an edgeedge with one S(7)Ce4 tetrahedra, and  an edgeedge with one S(4)Ce5 trigonal bipyramid. In the sixth S site, S(6) is bonded in a distorted rectangular see-saw-like geometry to one Ce(3), one Ce(4), and two equivalent Ce(2) atoms. In the seventh S site, S(7) is bonded to one Ce(1), one Ce(2), one Ce(3), and one Ce(4) atom to form SCe4 tetrahedra that share  a cornercorner with one S(4)Ce5 trigonal bipyramid, corners with two equivalent S(5)Ce4 trigonal pyramids, edges with two equivalent S(4)Ce5 trigonal bipyramids, and  an edgeedge with one S(5)Ce4 trigonal pyramid.
Ce4CrS7 crystallizes in the monoclinic P2_1 space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(7), and two equivalent S(5) atoms. The Ce(1)-S(1) bond length is 2.89 Å. The Ce(1)-S(2) bond length is 2.83 Å. The Ce(1)-S(3) bond length is 3.05 Å. The Ce(1)-S(4) bond length is 2.93 Å. The Ce(1)-S(7) bond length is 2.78 Å. There is one shorter (2.84 Å) and one longer (3.11 Å) Ce(1)-S(5) bond length. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(5), one S(7), and two equivalent S(6) atoms. The Ce(2)-S(1) bond length is 2.93 Å. The Ce(2)-S(2) bond length is 3.38 Å. The Ce(2)-S(3) bond length is 2.82 Å. The Ce(2)-S(5) bond length is 2.90 Å. The Ce(2)-S(7) bond length is 2.68 Å. There is one shorter (2.84 Å) and one longer (3.32 Å) Ce(2)-S(6) bond length. In the third Ce site, Ce(3) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(6), one S(7), and two equivalent S(4) atoms. The Ce(3)-S(1) bond length is 2.85 Å. The Ce(3)-S(2) bond length is 2.81 Å. The Ce(3)-S(3) bond length is 2.98 Å. The Ce(3)-S(6) bond length is 2.93 Å. The Ce(3)-S(7) bond length is 2.76 Å. There is one shorter (2.89 Å) and one longer (3.22 Å) Ce(3)-S(4) bond length. In the fourth Ce site, Ce(4) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(5), one S(6), one S(7), and two equivalent S(4) atoms. The Ce(4)-S(1) bond length is 3.24 Å. The Ce(4)-S(3) bond length is 3.50 Å. The Ce(4)-S(5) bond length is 2.77 Å. The Ce(4)-S(6) bond length is 2.75 Å. The Ce(4)-S(7) bond length is 2.65 Å. There is one shorter (2.70 Å) and one longer (2.93 Å) Ce(4)-S(4) bond length. Cr(1) is bonded to one S(1), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing CrS5 square pyramids. The Cr(1)-S(1) bond length is 2.57 Å. There is one shorter (2.49 Å) and one longer (2.58 Å) Cr(1)-S(2) bond length. There is one shorter (2.53 Å) and one longer (2.62 Å) Cr(1)-S(3) bond length. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), one Ce(4), and one Cr(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), and two equivalent Cr(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), one Ce(4), and two equivalent Cr(1) atoms. In the fourth S site, S(4) is bonded to one Ce(1), two equivalent Ce(3), and two equivalent Ce(4) atoms to form distorted SCe5 trigonal bipyramids that share  a cornercorner with one S(7)Ce4 tetrahedra, corners with two equivalent S(5)Ce4 trigonal pyramids, edges with two equivalent S(7)Ce4 tetrahedra, edges with two equivalent S(4)Ce5 trigonal bipyramids, and  an edgeedge with one S(5)Ce4 trigonal pyramid. In the fifth S site, S(5) is bonded to one Ce(2), one Ce(4), and two equivalent Ce(1) atoms to form distorted SCe4 trigonal pyramids that share corners with two equivalent S(7)Ce4 tetrahedra, corners with two equivalent S(4)Ce5 trigonal bipyramids, corners with two equivalent S(5)Ce4 trigonal pyramids,  an edgeedge with one S(7)Ce4 tetrahedra, and  an edgeedge with one S(4)Ce5 trigonal bipyramid. In the sixth S site, S(6) is bonded in a distorted rectangular see-saw-like geometry to one Ce(3), one Ce(4), and two equivalent Ce(2) atoms. In the seventh S site, S(7) is bonded to one Ce(1), one Ce(2), one Ce(3), and one Ce(4) atom to form SCe4 tetrahedra that share  a cornercorner with one S(4)Ce5 trigonal bipyramid, corners with two equivalent S(5)Ce4 trigonal pyramids, edges with two equivalent S(4)Ce5 trigonal bipyramids, and  an edgeedge with one S(5)Ce4 trigonal pyramid.