Yb4CrS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one S(4), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms to form distorted YbS7 pentagonal bipyramids that share corners with two equivalent Yb(3)S6 octahedra, corners with two equivalent Yb(4)S6 octahedra, corners with four equivalent Cr(1)S6 octahedra,  an edgeedge with one Cr(1)S6 octahedra, edges with three equivalent Yb(3)S6 octahedra, and faces with two equivalent Yb(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 17-82°. In the second Yb site, Yb(2) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(4), and two equivalent S(6) atoms. In the third Yb site, Yb(3) is bonded to one S(5), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(4)S6 octahedra,  a cornercorner with one Cr(1)S6 octahedra, corners with two equivalent Yb(1)S7 pentagonal bipyramids, edges with two equivalent Yb(3)S6 octahedra, and edges with three equivalent Yb(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 51-52°. In the fourth Yb site, Yb(4) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(7) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Yb(1)S7 pentagonal bipyramids, edges with two equivalent Yb(4)S6 octahedra, and edges with three equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 9-51°. Cr(1) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(7) atoms to form CrS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Yb(4)S6 octahedra, corners with four equivalent Yb(1)S7 pentagonal bipyramids, edges with two equivalent Cr(1)S6 octahedra, edges with three equivalent Yb(4)S6 octahedra, and  an edgeedge with one Yb(1)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 9-52°. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Yb(2), two equivalent Yb(4), and one Cr(1) atom to form distorted SYb4Cr trigonal bipyramids that share corners with four equivalent S(6)Yb4 tetrahedra, corners with two equivalent S(3)Yb5 trigonal bipyramids, corners with two equivalent S(4)Yb5 trigonal bipyramids, edges with two equivalent S(2)Yb3Cr2 square pyramids,  an edgeedge with one S(6)Yb4 tetrahedra,  an edgeedge with one S(4)Yb5 trigonal bipyramid, and edges with two equivalent S(1)Yb4Cr trigonal bipyramids. In the second S site, S(2) is bonded to one Yb(4), two equivalent Yb(1), and two equivalent Cr(1) atoms to form SYb3Cr2 square pyramids that share  a cornercorner with one S(6)Yb4 tetrahedra, corners with two equivalent S(3)Yb5 trigonal bipyramids, corners with two equivalent S(4)Yb5 trigonal bipyramids, edges with two equivalent S(2)Yb3Cr2 square pyramids,  an edgeedge with one S(3)Yb5 trigonal bipyramid, and edges with two equivalent S(1)Yb4Cr trigonal bipyramids. In the third S site, S(3) is bonded to one Yb(2), two equivalent Yb(1), and two equivalent Yb(3) atoms to form distorted SYb5 trigonal bipyramids that share corners with two equivalent S(2)Yb3Cr2 square pyramids, corners with two equivalent S(1)Yb4Cr trigonal bipyramids, corners with two equivalent S(4)Yb5 trigonal bipyramids,  an edgeedge with one S(2)Yb3Cr2 square pyramid, edges with two equivalent S(6)Yb4 tetrahedra, edges with two equivalent S(3)Yb5 trigonal bipyramids, and edges with three equivalent S(4)Yb5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Yb(1), two equivalent Yb(2), and two equivalent Yb(3) atoms to form SYb5 trigonal bipyramids that share corners with two equivalent S(2)Yb3Cr2 square pyramids, corners with four equivalent S(6)Yb4 tetrahedra, corners with two equivalent S(1)Yb4Cr trigonal bipyramids, corners with two equivalent S(3)Yb5 trigonal bipyramids,  an edgeedge with one S(6)Yb4 tetrahedra,  an edgeedge with one S(1)Yb4Cr trigonal bipyramid, edges with two equivalent S(4)Yb5 trigonal bipyramids, and edges with three equivalent S(3)Yb5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Yb(3), two equivalent Yb(1), and one Cr(1) atom. In the sixth S site, S(6) is bonded to one Yb(3), one Yb(4), and two equivalent Yb(2) atoms to form distorted SYb4 tetrahedra that share  a cornercorner with one S(2)Yb3Cr2 square pyramid, corners with two equivalent S(6)Yb4 tetrahedra, corners with four equivalent S(1)Yb4Cr trigonal bipyramids, corners with four equivalent S(4)Yb5 trigonal bipyramids,  an edgeedge with one S(1)Yb4Cr trigonal bipyramid,  an edgeedge with one S(4)Yb5 trigonal bipyramid, and edges with two equivalent S(3)Yb5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to two equivalent Yb(4) and two equivalent Cr(1) atoms.
Yb4CrS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one S(4), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms to form distorted YbS7 pentagonal bipyramids that share corners with two equivalent Yb(3)S6 octahedra, corners with two equivalent Yb(4)S6 octahedra, corners with four equivalent Cr(1)S6 octahedra,  an edgeedge with one Cr(1)S6 octahedra, edges with three equivalent Yb(3)S6 octahedra, and faces with two equivalent Yb(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 17-82°. The Yb(1)-S(4) bond length is 2.89 Å. Both Yb(1)-S(2) bond lengths are 3.04 Å. Both Yb(1)-S(3) bond lengths are 2.74 Å. Both Yb(1)-S(5) bond lengths are 2.83 Å. In the second Yb site, Yb(2) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(4), and two equivalent S(6) atoms. The Yb(2)-S(3) bond length is 3.20 Å. Both Yb(2)-S(1) bond lengths are 2.92 Å. Both Yb(2)-S(4) bond lengths are 2.84 Å. Both Yb(2)-S(6) bond lengths are 2.78 Å. In the third Yb site, Yb(3) is bonded to one S(5), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(4)S6 octahedra,  a cornercorner with one Cr(1)S6 octahedra, corners with two equivalent Yb(1)S7 pentagonal bipyramids, edges with two equivalent Yb(3)S6 octahedra, and edges with three equivalent Yb(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 51-52°. The Yb(3)-S(5) bond length is 2.79 Å. The Yb(3)-S(6) bond length is 2.68 Å. Both Yb(3)-S(3) bond lengths are 2.78 Å. Both Yb(3)-S(4) bond lengths are 2.77 Å. In the fourth Yb site, Yb(4) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(7) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Yb(1)S7 pentagonal bipyramids, edges with two equivalent Yb(4)S6 octahedra, and edges with three equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 9-51°. The Yb(4)-S(2) bond length is 2.81 Å. The Yb(4)-S(6) bond length is 2.67 Å. Both Yb(4)-S(1) bond lengths are 2.76 Å. Both Yb(4)-S(7) bond lengths are 2.84 Å. Cr(1) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(7) atoms to form CrS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Yb(4)S6 octahedra, corners with four equivalent Yb(1)S7 pentagonal bipyramids, edges with two equivalent Cr(1)S6 octahedra, edges with three equivalent Yb(4)S6 octahedra, and  an edgeedge with one Yb(1)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 9-52°. The Cr(1)-S(1) bond length is 2.40 Å. The Cr(1)-S(5) bond length is 2.32 Å. Both Cr(1)-S(2) bond lengths are 2.43 Å. Both Cr(1)-S(7) bond lengths are 2.44 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Yb(2), two equivalent Yb(4), and one Cr(1) atom to form distorted SYb4Cr trigonal bipyramids that share corners with four equivalent S(6)Yb4 tetrahedra, corners with two equivalent S(3)Yb5 trigonal bipyramids, corners with two equivalent S(4)Yb5 trigonal bipyramids, edges with two equivalent S(2)Yb3Cr2 square pyramids,  an edgeedge with one S(6)Yb4 tetrahedra,  an edgeedge with one S(4)Yb5 trigonal bipyramid, and edges with two equivalent S(1)Yb4Cr trigonal bipyramids. In the second S site, S(2) is bonded to one Yb(4), two equivalent Yb(1), and two equivalent Cr(1) atoms to form SYb3Cr2 square pyramids that share  a cornercorner with one S(6)Yb4 tetrahedra, corners with two equivalent S(3)Yb5 trigonal bipyramids, corners with two equivalent S(4)Yb5 trigonal bipyramids, edges with two equivalent S(2)Yb3Cr2 square pyramids,  an edgeedge with one S(3)Yb5 trigonal bipyramid, and edges with two equivalent S(1)Yb4Cr trigonal bipyramids. In the third S site, S(3) is bonded to one Yb(2), two equivalent Yb(1), and two equivalent Yb(3) atoms to form distorted SYb5 trigonal bipyramids that share corners with two equivalent S(2)Yb3Cr2 square pyramids, corners with two equivalent S(1)Yb4Cr trigonal bipyramids, corners with two equivalent S(4)Yb5 trigonal bipyramids,  an edgeedge with one S(2)Yb3Cr2 square pyramid, edges with two equivalent S(6)Yb4 tetrahedra, edges with two equivalent S(3)Yb5 trigonal bipyramids, and edges with three equivalent S(4)Yb5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Yb(1), two equivalent Yb(2), and two equivalent Yb(3) atoms to form SYb5 trigonal bipyramids that share corners with two equivalent S(2)Yb3Cr2 square pyramids, corners with four equivalent S(6)Yb4 tetrahedra, corners with two equivalent S(1)Yb4Cr trigonal bipyramids, corners with two equivalent S(3)Yb5 trigonal bipyramids,  an edgeedge with one S(6)Yb4 tetrahedra,  an edgeedge with one S(1)Yb4Cr trigonal bipyramid, edges with two equivalent S(4)Yb5 trigonal bipyramids, and edges with three equivalent S(3)Yb5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Yb(3), two equivalent Yb(1), and one Cr(1) atom. In the sixth S site, S(6) is bonded to one Yb(3), one Yb(4), and two equivalent Yb(2) atoms to form distorted SYb4 tetrahedra that share  a cornercorner with one S(2)Yb3Cr2 square pyramid, corners with two equivalent S(6)Yb4 tetrahedra, corners with four equivalent S(1)Yb4Cr trigonal bipyramids, corners with four equivalent S(4)Yb5 trigonal bipyramids,  an edgeedge with one S(1)Yb4Cr trigonal bipyramid,  an edgeedge with one S(4)Yb5 trigonal bipyramid, and edges with two equivalent S(3)Yb5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to two equivalent Yb(4) and two equivalent Cr(1) atoms.