Yb3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Yb sites. In the first Yb site, Yb(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 Yb site, Yb(2) is bonded in a 9-coordinate geometry to one S(1), one S(4), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms. In the third Yb site, Yb(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 YbS7 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 Yb(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 19°. 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 Yb(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 Yb(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 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)Yb5 square pyramids, corners with four equivalent S(3)Yb4Cr trigonal bipyramids, edges with three equivalent S(2)Yb5 square pyramids,  an edgeedge with one S(3)Yb4Cr trigonal bipyramid, edges with two equivalent S(6)Yb3Cr2 trigonal bipyramids, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the second S site, S(6) is bonded to one Yb(1), two equivalent Yb(2), and two equivalent Cr(2) atoms to form distorted SYb3Cr2 trigonal bipyramids that share corners with four equivalent S(2)Yb5 square pyramids, corners with two equivalent S(6)Yb3Cr2 trigonal bipyramids, corners with two equivalent S(3)Yb4Cr trigonal bipyramids,  an edgeedge with one S(2)Yb5 square pyramid,  an edgeedge with one S(3)Yb4Cr trigonal bipyramid, edges with two equivalent S(5)Yb5 trigonal bipyramids, and edges with three equivalent S(6)Yb3Cr2 trigonal bipyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one Yb(2), one Yb(3), two equivalent Yb(1), and one Cr(2) atom. In the fourth S site, S(2) is bonded to one Yb(3), two equivalent Yb(1), and two equivalent Yb(2) atoms to form SYb5 square pyramids that share corners with two equivalent S(5)Yb5 trigonal bipyramids, corners with four equivalent S(6)Yb3Cr2 trigonal bipyramids, corners with four equivalent S(3)Yb4Cr trigonal bipyramids, edges with two equivalent S(2)Yb5 square pyramids,  an edgeedge with one S(6)Yb3Cr2 trigonal bipyramid,  an edgeedge with one S(3)Yb4Cr trigonal bipyramid, and edges with three equivalent S(5)Yb5 trigonal bipyramids. In the fifth S site, S(3) is bonded to two equivalent Yb(2), two equivalent Yb(3), and one Cr(1) atom to form distorted SYb4Cr trigonal bipyramids that share corners with four equivalent S(2)Yb5 square pyramids,  a cornercorner with one S(3)Yb4Cr trigonal bipyramid, corners with two equivalent S(6)Yb3Cr2 trigonal bipyramids, corners with four equivalent S(5)Yb5 trigonal bipyramids,  an edgeedge with one S(2)Yb5 square pyramid,  an edgeedge with one S(6)Yb3Cr2 trigonal bipyramid,  an edgeedge with one S(5)Yb5 trigonal bipyramid, and edges with two equivalent S(3)Yb4Cr trigonal bipyramids. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to one Yb(1), one Yb(2), one Yb(3), and two equivalent Cr(1) atoms.
Yb3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Yb sites. In the first Yb site, Yb(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 Yb(1)-S(4) bond length is 3.00 Å. The Yb(1)-S(6) bond length is 2.90 Å. Both Yb(1)-S(1) bond lengths are 2.89 Å. Both Yb(1)-S(2) bond lengths are 2.79 Å. Both Yb(1)-S(5) bond lengths are 2.76 Å. In the second Yb site, Yb(2) is bonded in a 9-coordinate geometry to one S(1), one S(4), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms. The Yb(2)-S(1) bond length is 3.40 Å. The Yb(2)-S(4) bond length is 3.22 Å. The Yb(2)-S(5) bond length is 2.97 Å. Both Yb(2)-S(2) bond lengths are 2.76 Å. Both Yb(2)-S(3) bond lengths are 2.87 Å. Both Yb(2)-S(6) bond lengths are 2.95 Å. In the third Yb site, Yb(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 YbS7 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 Yb(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 19°. The Yb(3)-S(1) bond length is 2.79 Å. The Yb(3)-S(2) bond length is 2.87 Å. The Yb(3)-S(4) bond length is 2.89 Å. Both Yb(3)-S(3) bond lengths are 2.79 Å. Both Yb(3)-S(5) bond lengths are 2.74 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 Yb(3)S7 pentagonal bipyramids. Both Cr(1)-S(3) bond lengths are 2.38 Å. All Cr(1)-S(4) bond lengths are 2.39 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 Yb(3)S7 pentagonal bipyramids and edges with two equivalent Cr(2)S6 octahedra. Both Cr(2)-S(1) bond lengths are 2.26 Å. All Cr(2)-S(6) bond lengths are 2.40 Å. There are six inequivalent S sites. In the first S site, S(5) 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)Yb5 square pyramids, corners with four equivalent S(3)Yb4Cr trigonal bipyramids, edges with three equivalent S(2)Yb5 square pyramids,  an edgeedge with one S(3)Yb4Cr trigonal bipyramid, edges with two equivalent S(6)Yb3Cr2 trigonal bipyramids, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the second S site, S(6) is bonded to one Yb(1), two equivalent Yb(2), and two equivalent Cr(2) atoms to form distorted SYb3Cr2 trigonal bipyramids that share corners with four equivalent S(2)Yb5 square pyramids, corners with two equivalent S(6)Yb3Cr2 trigonal bipyramids, corners with two equivalent S(3)Yb4Cr trigonal bipyramids,  an edgeedge with one S(2)Yb5 square pyramid,  an edgeedge with one S(3)Yb4Cr trigonal bipyramid, edges with two equivalent S(5)Yb5 trigonal bipyramids, and edges with three equivalent S(6)Yb3Cr2 trigonal bipyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one Yb(2), one Yb(3), two equivalent Yb(1), and one Cr(2) atom. In the fourth S site, S(2) is bonded to one Yb(3), two equivalent Yb(1), and two equivalent Yb(2) atoms to form SYb5 square pyramids that share corners with two equivalent S(5)Yb5 trigonal bipyramids, corners with four equivalent S(6)Yb3Cr2 trigonal bipyramids, corners with four equivalent S(3)Yb4Cr trigonal bipyramids, edges with two equivalent S(2)Yb5 square pyramids,  an edgeedge with one S(6)Yb3Cr2 trigonal bipyramid,  an edgeedge with one S(3)Yb4Cr trigonal bipyramid, and edges with three equivalent S(5)Yb5 trigonal bipyramids. In the fifth S site, S(3) is bonded to two equivalent Yb(2), two equivalent Yb(3), and one Cr(1) atom to form distorted SYb4Cr trigonal bipyramids that share corners with four equivalent S(2)Yb5 square pyramids,  a cornercorner with one S(3)Yb4Cr trigonal bipyramid, corners with two equivalent S(6)Yb3Cr2 trigonal bipyramids, corners with four equivalent S(5)Yb5 trigonal bipyramids,  an edgeedge with one S(2)Yb5 square pyramid,  an edgeedge with one S(6)Yb3Cr2 trigonal bipyramid,  an edgeedge with one S(5)Yb5 trigonal bipyramid, and edges with two equivalent S(3)Yb4Cr trigonal bipyramids. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to one Yb(1), one Yb(2), one Yb(3), and two equivalent Cr(1) atoms.