Tm3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Tm sites. In the first Tm site, Tm(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 Tm site, Tm(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 Tm site, Tm(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 TmS7 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 Tm(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 Tm(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 Tm(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 Tm(2), two equivalent Tm(1), and two equivalent Tm(3) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(3)Tm4Cr square pyramids,  a cornercorner with one S(4)Tm3Cr2 trigonal bipyramid, corners with two equivalent S(2)Tm5 trigonal bipyramids, corners with four equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(3)Tm4Cr square pyramid, edges with two equivalent S(4)Tm3Cr2 trigonal bipyramids, edges with two equivalent S(6)Tm3Cr2 trigonal bipyramids, edges with two equivalent S(5)Tm5 trigonal bipyramids, edges with three equivalent S(2)Tm5 trigonal bipyramids, and  an edgeedge with one S(1)Tm3Cr trigonal pyramid. In the second S site, S(6) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent Cr(2) atoms to form distorted STm3Cr2 trigonal bipyramids that share corners with two equivalent S(3)Tm4Cr square pyramids, corners with two equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with three equivalent S(4)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(2)Tm5 trigonal bipyramids, corners with two equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(3)Tm4Cr square pyramid,  an edgeedge with one S(2)Tm5 trigonal bipyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, edges with three equivalent S(6)Tm3Cr2 trigonal bipyramids, and edges with two equivalent S(1)Tm3Cr trigonal pyramids. In the third S site, S(1) is bonded to one Tm(3), two equivalent Tm(1), and one Cr(2) atom to form distorted STm3Cr trigonal pyramids that share corners with two equivalent S(3)Tm4Cr square pyramids, corners with two equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with two equivalent S(2)Tm5 trigonal bipyramids, corners with three equivalent S(4)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(5)Tm5 trigonal bipyramids, corners with three equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid, edges with two equivalent S(6)Tm3Cr2 trigonal bipyramids, and  a faceface with one S(2)Tm5 trigonal bipyramid. In the fourth S site, S(2) is bonded to one Tm(3), two equivalent Tm(1), and two equivalent Tm(2) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(3)Tm4Cr square pyramids,  a cornercorner with one S(4)Tm3Cr2 trigonal bipyramid, corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with four equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with two equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(3)Tm4Cr square pyramid,  an edgeedge with one S(6)Tm3Cr2 trigonal bipyramid, edges with two equivalent S(4)Tm3Cr2 trigonal bipyramids, edges with two equivalent S(2)Tm5 trigonal bipyramids, edges with three equivalent S(5)Tm5 trigonal bipyramids, and  a faceface with one S(1)Tm3Cr trigonal pyramid. In the fifth S site, S(3) is bonded to two equivalent Tm(2), two equivalent Tm(3), and one Cr(1) atom to form distorted STm4Cr square pyramids that share  a cornercorner with one S(3)Tm4Cr square pyramid, corners with two equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(2)Tm5 trigonal bipyramids, corners with four equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(1)Tm3Cr trigonal pyramids, edges with two equivalent S(3)Tm4Cr square pyramids,  an edgeedge with one S(6)Tm3Cr2 trigonal bipyramid,  an edgeedge with one S(2)Tm5 trigonal bipyramid,  an edgeedge with one S(5)Tm5 trigonal bipyramid, and edges with four equivalent S(4)Tm3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one Tm(1), one Tm(2), one Tm(3), and two equivalent Cr(1) atoms to form distorted STm3Cr2 trigonal bipyramids that share  a cornercorner with one S(2)Tm5 trigonal bipyramid,  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with three equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(4)Tm3Cr2 trigonal bipyramids, corners with three equivalent S(1)Tm3Cr trigonal pyramids, edges with four equivalent S(3)Tm4Cr square pyramids,  an edgeedge with one S(4)Tm3Cr2 trigonal bipyramid, edges with two equivalent S(2)Tm5 trigonal bipyramids, and edges with two equivalent S(5)Tm5 trigonal bipyramids.
Tm3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Tm sites. In the first Tm site, Tm(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 Tm(1)-S(4) bond length is 2.89 Å. The Tm(1)-S(6) bond length is 2.88 Å. Both Tm(1)-S(1) bond lengths are 2.73 Å. Both Tm(1)-S(2) bond lengths are 2.83 Å. Both Tm(1)-S(5) bond lengths are 2.78 Å. In the second Tm site, Tm(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 Tm(2)-S(4) bond length is 3.05 Å. The Tm(2)-S(5) bond length is 2.98 Å. Both Tm(2)-S(2) bond lengths are 2.72 Å. Both Tm(2)-S(3) bond lengths are 2.83 Å. Both Tm(2)-S(6) bond lengths are 2.85 Å. In the third Tm site, Tm(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 TmS7 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 Tm(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 35°. The Tm(3)-S(1) bond length is 2.69 Å. The Tm(3)-S(2) bond length is 2.83 Å. The Tm(3)-S(4) bond length is 2.79 Å. Both Tm(3)-S(3) bond lengths are 2.74 Å. Both Tm(3)-S(5) bond lengths are 2.70 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 Tm(3)S7 pentagonal bipyramids. Both Cr(1)-S(3) bond lengths are 2.41 Å. All Cr(1)-S(4) bond lengths are 2.44 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 Tm(3)S7 pentagonal bipyramids and edges with two equivalent Cr(2)S6 octahedra. Both Cr(2)-S(1) bond lengths are 2.34 Å. All Cr(2)-S(6) bond lengths are 2.47 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Tm(2), two equivalent Tm(1), and two equivalent Tm(3) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(3)Tm4Cr square pyramids,  a cornercorner with one S(4)Tm3Cr2 trigonal bipyramid, corners with two equivalent S(2)Tm5 trigonal bipyramids, corners with four equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(3)Tm4Cr square pyramid, edges with two equivalent S(4)Tm3Cr2 trigonal bipyramids, edges with two equivalent S(6)Tm3Cr2 trigonal bipyramids, edges with two equivalent S(5)Tm5 trigonal bipyramids, edges with three equivalent S(2)Tm5 trigonal bipyramids, and  an edgeedge with one S(1)Tm3Cr trigonal pyramid. In the second S site, S(6) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent Cr(2) atoms to form distorted STm3Cr2 trigonal bipyramids that share corners with two equivalent S(3)Tm4Cr square pyramids, corners with two equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with three equivalent S(4)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(2)Tm5 trigonal bipyramids, corners with two equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(3)Tm4Cr square pyramid,  an edgeedge with one S(2)Tm5 trigonal bipyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, edges with three equivalent S(6)Tm3Cr2 trigonal bipyramids, and edges with two equivalent S(1)Tm3Cr trigonal pyramids. In the third S site, S(1) is bonded to one Tm(3), two equivalent Tm(1), and one Cr(2) atom to form distorted STm3Cr trigonal pyramids that share corners with two equivalent S(3)Tm4Cr square pyramids, corners with two equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with two equivalent S(2)Tm5 trigonal bipyramids, corners with three equivalent S(4)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(5)Tm5 trigonal bipyramids, corners with three equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid, edges with two equivalent S(6)Tm3Cr2 trigonal bipyramids, and  a faceface with one S(2)Tm5 trigonal bipyramid. In the fourth S site, S(2) is bonded to one Tm(3), two equivalent Tm(1), and two equivalent Tm(2) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(3)Tm4Cr square pyramids,  a cornercorner with one S(4)Tm3Cr2 trigonal bipyramid, corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with four equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with two equivalent S(1)Tm3Cr trigonal pyramids,  an edgeedge with one S(3)Tm4Cr square pyramid,  an edgeedge with one S(6)Tm3Cr2 trigonal bipyramid, edges with two equivalent S(4)Tm3Cr2 trigonal bipyramids, edges with two equivalent S(2)Tm5 trigonal bipyramids, edges with three equivalent S(5)Tm5 trigonal bipyramids, and  a faceface with one S(1)Tm3Cr trigonal pyramid. In the fifth S site, S(3) is bonded to two equivalent Tm(2), two equivalent Tm(3), and one Cr(1) atom to form distorted STm4Cr square pyramids that share  a cornercorner with one S(3)Tm4Cr square pyramid, corners with two equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(2)Tm5 trigonal bipyramids, corners with four equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(1)Tm3Cr trigonal pyramids, edges with two equivalent S(3)Tm4Cr square pyramids,  an edgeedge with one S(6)Tm3Cr2 trigonal bipyramid,  an edgeedge with one S(2)Tm5 trigonal bipyramid,  an edgeedge with one S(5)Tm5 trigonal bipyramid, and edges with four equivalent S(4)Tm3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one Tm(1), one Tm(2), one Tm(3), and two equivalent Cr(1) atoms to form distorted STm3Cr2 trigonal bipyramids that share  a cornercorner with one S(2)Tm5 trigonal bipyramid,  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with three equivalent S(6)Tm3Cr2 trigonal bipyramids, corners with four equivalent S(4)Tm3Cr2 trigonal bipyramids, corners with three equivalent S(1)Tm3Cr trigonal pyramids, edges with four equivalent S(3)Tm4Cr square pyramids,  an edgeedge with one S(4)Tm3Cr2 trigonal bipyramid, edges with two equivalent S(2)Tm5 trigonal bipyramids, and edges with two equivalent S(5)Tm5 trigonal bipyramids.