Ho3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Ho sites. In the first Ho site, Ho(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 Ho site, Ho(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 Ho site, Ho(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 HoS7 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 Ho(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 35°. 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 Ho(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 Ho(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 Ho(2), two equivalent Ho(1), and two equivalent Ho(3) atoms to form distorted SHo5 trigonal bipyramids that share  a cornercorner with one S(4)Ho3Cr2 trigonal bipyramid, corners with two equivalent S(2)Ho5 trigonal bipyramids, corners with four equivalent S(3)Ho4Cr trigonal bipyramids, corners with four equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(3)Ho4Cr trigonal bipyramid, edges with two equivalent S(4)Ho3Cr2 trigonal bipyramids, edges with two equivalent S(6)Ho3Cr2 trigonal bipyramids, edges with two equivalent S(5)Ho5 trigonal bipyramids, edges with three equivalent S(2)Ho5 trigonal bipyramids, and  an edgeedge with one S(1)Ho3Cr trigonal pyramid. In the second S site, S(6) is bonded to one Ho(1), two equivalent Ho(2), and two equivalent Cr(2) atoms to form distorted SHo3Cr2 trigonal bipyramids that share corners with two equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with two equivalent S(3)Ho4Cr trigonal bipyramids, corners with three equivalent S(4)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ho5 trigonal bipyramids, corners with two equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(3)Ho4Cr trigonal bipyramid,  an edgeedge with one S(2)Ho5 trigonal bipyramid, edges with two equivalent S(5)Ho5 trigonal bipyramids, edges with three equivalent S(6)Ho3Cr2 trigonal bipyramids, and edges with two equivalent S(1)Ho3Cr trigonal pyramids. In the third S site, S(1) is bonded to one Ho(3), two equivalent Ho(1), and one Cr(2) atom to form distorted SHo3Cr trigonal pyramids that share corners with two equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with two equivalent S(3)Ho4Cr trigonal bipyramids, corners with two equivalent S(2)Ho5 trigonal bipyramids, corners with three equivalent S(4)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(5)Ho5 trigonal bipyramids, corners with three equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(5)Ho5 trigonal bipyramid, edges with two equivalent S(6)Ho3Cr2 trigonal bipyramids, and  a faceface with one S(2)Ho5 trigonal bipyramid. In the fourth S site, S(2) is bonded to one Ho(3), two equivalent Ho(1), and two equivalent Ho(2) atoms to form distorted SHo5 trigonal bipyramids that share  a cornercorner with one S(4)Ho3Cr2 trigonal bipyramid, corners with two equivalent S(5)Ho5 trigonal bipyramids, corners with four equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(3)Ho4Cr trigonal bipyramids, corners with two equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(6)Ho3Cr2 trigonal bipyramid,  an edgeedge with one S(3)Ho4Cr trigonal bipyramid, edges with two equivalent S(4)Ho3Cr2 trigonal bipyramids, edges with two equivalent S(2)Ho5 trigonal bipyramids, edges with three equivalent S(5)Ho5 trigonal bipyramids, and  a faceface with one S(1)Ho3Cr trigonal pyramid. In the fifth S site, S(3) is bonded to two equivalent Ho(2), two equivalent Ho(3), and one Cr(1) atom to form distorted SHo4Cr trigonal bipyramids that share  a cornercorner with one S(3)Ho4Cr trigonal bipyramid, corners with two equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ho5 trigonal bipyramids, corners with four equivalent S(5)Ho5 trigonal bipyramids, corners with two equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(6)Ho3Cr2 trigonal bipyramid,  an edgeedge with one S(2)Ho5 trigonal bipyramid,  an edgeedge with one S(5)Ho5 trigonal bipyramid, edges with two equivalent S(3)Ho4Cr trigonal bipyramids, and edges with four equivalent S(4)Ho3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one Ho(1), one Ho(2), one Ho(3), and two equivalent Cr(1) atoms to form distorted SHo3Cr2 trigonal bipyramids that share  a cornercorner with one S(2)Ho5 trigonal bipyramid,  a cornercorner with one S(5)Ho5 trigonal bipyramid, corners with three equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(4)Ho3Cr2 trigonal bipyramids, corners with three equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(4)Ho3Cr2 trigonal bipyramid, edges with two equivalent S(2)Ho5 trigonal bipyramids, edges with two equivalent S(5)Ho5 trigonal bipyramids, and edges with four equivalent S(3)Ho4Cr trigonal bipyramids.
Ho3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Ho sites. In the first Ho site, Ho(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 Ho(1)-S(4) bond length is 2.89 Å. The Ho(1)-S(6) bond length is 2.90 Å. Both Ho(1)-S(1) bond lengths are 2.75 Å. Both Ho(1)-S(2) bond lengths are 2.85 Å. Both Ho(1)-S(5) bond lengths are 2.79 Å. In the second Ho site, Ho(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 Ho(2)-S(4) bond length is 3.12 Å. The Ho(2)-S(5) bond length is 3.00 Å. Both Ho(2)-S(2) bond lengths are 2.73 Å. Both Ho(2)-S(3) bond lengths are 2.84 Å. Both Ho(2)-S(6) bond lengths are 2.86 Å. In the third Ho site, Ho(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 HoS7 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 Ho(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 35°. The Ho(3)-S(1) bond length is 2.70 Å. The Ho(3)-S(2) bond length is 2.84 Å. The Ho(3)-S(4) bond length is 2.80 Å. Both Ho(3)-S(3) bond lengths are 2.76 Å. Both Ho(3)-S(5) bond lengths are 2.71 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 Ho(3)S7 pentagonal bipyramids. Both Cr(1)-S(3) bond lengths are 2.42 Å. All Cr(1)-S(4) bond lengths are 2.45 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 Ho(3)S7 pentagonal bipyramids and edges with two equivalent Cr(2)S6 octahedra. Both Cr(2)-S(1) bond lengths are 2.35 Å. All Cr(2)-S(6) bond lengths are 2.48 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Ho(2), two equivalent Ho(1), and two equivalent Ho(3) atoms to form distorted SHo5 trigonal bipyramids that share  a cornercorner with one S(4)Ho3Cr2 trigonal bipyramid, corners with two equivalent S(2)Ho5 trigonal bipyramids, corners with four equivalent S(3)Ho4Cr trigonal bipyramids, corners with four equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(3)Ho4Cr trigonal bipyramid, edges with two equivalent S(4)Ho3Cr2 trigonal bipyramids, edges with two equivalent S(6)Ho3Cr2 trigonal bipyramids, edges with two equivalent S(5)Ho5 trigonal bipyramids, edges with three equivalent S(2)Ho5 trigonal bipyramids, and  an edgeedge with one S(1)Ho3Cr trigonal pyramid. In the second S site, S(6) is bonded to one Ho(1), two equivalent Ho(2), and two equivalent Cr(2) atoms to form distorted SHo3Cr2 trigonal bipyramids that share corners with two equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with two equivalent S(3)Ho4Cr trigonal bipyramids, corners with three equivalent S(4)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ho5 trigonal bipyramids, corners with two equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(3)Ho4Cr trigonal bipyramid,  an edgeedge with one S(2)Ho5 trigonal bipyramid, edges with two equivalent S(5)Ho5 trigonal bipyramids, edges with three equivalent S(6)Ho3Cr2 trigonal bipyramids, and edges with two equivalent S(1)Ho3Cr trigonal pyramids. In the third S site, S(1) is bonded to one Ho(3), two equivalent Ho(1), and one Cr(2) atom to form distorted SHo3Cr trigonal pyramids that share corners with two equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with two equivalent S(3)Ho4Cr trigonal bipyramids, corners with two equivalent S(2)Ho5 trigonal bipyramids, corners with three equivalent S(4)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(5)Ho5 trigonal bipyramids, corners with three equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(5)Ho5 trigonal bipyramid, edges with two equivalent S(6)Ho3Cr2 trigonal bipyramids, and  a faceface with one S(2)Ho5 trigonal bipyramid. In the fourth S site, S(2) is bonded to one Ho(3), two equivalent Ho(1), and two equivalent Ho(2) atoms to form distorted SHo5 trigonal bipyramids that share  a cornercorner with one S(4)Ho3Cr2 trigonal bipyramid, corners with two equivalent S(5)Ho5 trigonal bipyramids, corners with four equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(3)Ho4Cr trigonal bipyramids, corners with two equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(6)Ho3Cr2 trigonal bipyramid,  an edgeedge with one S(3)Ho4Cr trigonal bipyramid, edges with two equivalent S(4)Ho3Cr2 trigonal bipyramids, edges with two equivalent S(2)Ho5 trigonal bipyramids, edges with three equivalent S(5)Ho5 trigonal bipyramids, and  a faceface with one S(1)Ho3Cr trigonal pyramid. In the fifth S site, S(3) is bonded to two equivalent Ho(2), two equivalent Ho(3), and one Cr(1) atom to form distorted SHo4Cr trigonal bipyramids that share  a cornercorner with one S(3)Ho4Cr trigonal bipyramid, corners with two equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(2)Ho5 trigonal bipyramids, corners with four equivalent S(5)Ho5 trigonal bipyramids, corners with two equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(6)Ho3Cr2 trigonal bipyramid,  an edgeedge with one S(2)Ho5 trigonal bipyramid,  an edgeedge with one S(5)Ho5 trigonal bipyramid, edges with two equivalent S(3)Ho4Cr trigonal bipyramids, and edges with four equivalent S(4)Ho3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one Ho(1), one Ho(2), one Ho(3), and two equivalent Cr(1) atoms to form distorted SHo3Cr2 trigonal bipyramids that share  a cornercorner with one S(2)Ho5 trigonal bipyramid,  a cornercorner with one S(5)Ho5 trigonal bipyramid, corners with three equivalent S(6)Ho3Cr2 trigonal bipyramids, corners with four equivalent S(4)Ho3Cr2 trigonal bipyramids, corners with three equivalent S(1)Ho3Cr trigonal pyramids,  an edgeedge with one S(4)Ho3Cr2 trigonal bipyramid, edges with two equivalent S(2)Ho5 trigonal bipyramids, edges with two equivalent S(5)Ho5 trigonal bipyramids, and edges with four equivalent S(3)Ho4Cr trigonal bipyramids.