Tm2S3 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(2), one S(5), two equivalent S(6), and three equivalent S(1) atoms to form distorted TmS7 pentagonal bipyramids that share  a cornercorner with one Tm(3)S6 octahedra, corners with two equivalent Tm(4)S6 octahedra, edges with two equivalent Tm(3)S6 octahedra, and edges with four equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 37-50°. In the second Tm site, Tm(2) is bonded in a 8-coordinate geometry to one S(2), two equivalent S(4), two equivalent S(5), and three equivalent S(6) atoms. In the third Tm site, Tm(3) is bonded to one S(1), two equivalent S(5), and three equivalent S(3) atoms to form TmS6 octahedra that share corners with three equivalent Tm(4)S6 octahedra,  a cornercorner with one Tm(1)S7 pentagonal bipyramid, edges with four equivalent Tm(3)S6 octahedra, and edges with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 59°. In the fourth Tm site, Tm(4) is bonded to one S(3), two equivalent S(2), and three equivalent S(4) atoms to form TmS6 octahedra that share corners with three equivalent Tm(3)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, and edges with four equivalent Tm(4)S6 octahedra. The corner-sharing octahedral tilt angles are 59°. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Tm(3) and three equivalent Tm(1) atoms to form distorted STm4 trigonal pyramids that share  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with four equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(1)Tm4 trigonal pyramids, corners with three equivalent S(2)Tm4 trigonal pyramids, corners with three equivalent S(3)Tm4 trigonal pyramids,  an edgeedge with one S(6)Tm5 trigonal bipyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, and edges with two equivalent S(1)Tm4 trigonal pyramids. In the second S site, S(2) is bonded to one Tm(1), one Tm(2), and two equivalent Tm(4) atoms to form distorted STm4 trigonal pyramids that share corners with two equivalent S(4)Tm5 square pyramids,  a cornercorner with one S(6)Tm5 trigonal bipyramid, corners with three equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(2)Tm4 trigonal pyramids, corners with two equivalent S(3)Tm4 trigonal pyramids, corners with three equivalent S(1)Tm4 trigonal pyramids, edges with three equivalent S(4)Tm5 square pyramids, and edges with two equivalent S(6)Tm5 trigonal bipyramids. In the third S site, S(3) is bonded to one Tm(4) and three equivalent Tm(3) atoms to form distorted STm4 trigonal pyramids that share corners with three equivalent S(4)Tm5 square pyramids, corners with four equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(2)Tm4 trigonal pyramids, corners with two equivalent S(3)Tm4 trigonal pyramids, corners with three equivalent S(1)Tm4 trigonal pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid, and edges with two equivalent S(3)Tm4 trigonal pyramids. In the fourth S site, S(4) is bonded to two equivalent Tm(2) and three equivalent Tm(4) atoms to form STm5 square pyramids that share corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with four equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(2)Tm4 trigonal pyramids, corners with three equivalent S(3)Tm4 trigonal pyramids, edges with four equivalent S(4)Tm5 square pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid,  an edgeedge with one S(6)Tm5 trigonal bipyramid, and edges with three equivalent S(2)Tm4 trigonal pyramids. In the fifth S site, S(5) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent Tm(3) atoms to form STm5 trigonal bipyramids that share corners with two equivalent S(4)Tm5 square pyramids, corners with two equivalent S(6)Tm5 trigonal bipyramids,  a cornercorner with one S(1)Tm4 trigonal pyramid, corners with three equivalent S(2)Tm4 trigonal pyramids, corners with four equivalent S(3)Tm4 trigonal pyramids,  an edgeedge with one S(4)Tm5 square pyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, edges with three equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(3)Tm4 trigonal pyramid, and edges with two equivalent S(1)Tm4 trigonal pyramids. In the sixth S site, S(6) is bonded to two equivalent Tm(1) and three equivalent Tm(2) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(4)Tm5 square pyramids, corners with two equivalent S(5)Tm5 trigonal bipyramids,  a cornercorner with one S(2)Tm4 trigonal pyramid, corners with four equivalent S(1)Tm4 trigonal pyramids,  an edgeedge with one S(4)Tm5 square pyramid, edges with three equivalent S(5)Tm5 trigonal bipyramids, edges with four equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(1)Tm4 trigonal pyramid, and edges with two equivalent S(2)Tm4 trigonal pyramids.
Tm2S3 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(2), one S(5), two equivalent S(6), and three equivalent S(1) atoms to form distorted TmS7 pentagonal bipyramids that share  a cornercorner with one Tm(3)S6 octahedra, corners with two equivalent Tm(4)S6 octahedra, edges with two equivalent Tm(3)S6 octahedra, and edges with four equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 37-50°. The Tm(1)-S(2) bond length is 2.64 Å. The Tm(1)-S(5) bond length is 2.81 Å. Both Tm(1)-S(6) bond lengths are 2.90 Å. There are two shorter (2.64 Å) and one longer (2.87 Å) Tm(1)-S(1) bond length. In the second Tm site, Tm(2) is bonded in a 8-coordinate geometry to one S(2), two equivalent S(4), two equivalent S(5), and three equivalent S(6) atoms. The Tm(2)-S(2) bond length is 2.84 Å. Both Tm(2)-S(4) bond lengths are 2.97 Å. Both Tm(2)-S(5) bond lengths are 2.93 Å. There are two shorter (2.75 Å) and one longer (2.85 Å) Tm(2)-S(6) bond length. In the third Tm site, Tm(3) is bonded to one S(1), two equivalent S(5), and three equivalent S(3) atoms to form TmS6 octahedra that share corners with three equivalent Tm(4)S6 octahedra,  a cornercorner with one Tm(1)S7 pentagonal bipyramid, edges with four equivalent Tm(3)S6 octahedra, and edges with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 59°. The Tm(3)-S(1) bond length is 2.62 Å. Both Tm(3)-S(5) bond lengths are 2.73 Å. There are two shorter (2.67 Å) and one longer (2.72 Å) Tm(3)-S(3) bond length. In the fourth Tm site, Tm(4) is bonded to one S(3), two equivalent S(2), and three equivalent S(4) atoms to form TmS6 octahedra that share corners with three equivalent Tm(3)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, and edges with four equivalent Tm(4)S6 octahedra. The corner-sharing octahedral tilt angles are 59°. The Tm(4)-S(3) bond length is 2.65 Å. Both Tm(4)-S(2) bond lengths are 2.62 Å. There is one shorter (2.69 Å) and two longer (2.73 Å) Tm(4)-S(4) bond lengths. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Tm(3) and three equivalent Tm(1) atoms to form distorted STm4 trigonal pyramids that share  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with four equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(1)Tm4 trigonal pyramids, corners with three equivalent S(2)Tm4 trigonal pyramids, corners with three equivalent S(3)Tm4 trigonal pyramids,  an edgeedge with one S(6)Tm5 trigonal bipyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, and edges with two equivalent S(1)Tm4 trigonal pyramids. In the second S site, S(2) is bonded to one Tm(1), one Tm(2), and two equivalent Tm(4) atoms to form distorted STm4 trigonal pyramids that share corners with two equivalent S(4)Tm5 square pyramids,  a cornercorner with one S(6)Tm5 trigonal bipyramid, corners with three equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(2)Tm4 trigonal pyramids, corners with two equivalent S(3)Tm4 trigonal pyramids, corners with three equivalent S(1)Tm4 trigonal pyramids, edges with three equivalent S(4)Tm5 square pyramids, and edges with two equivalent S(6)Tm5 trigonal bipyramids. In the third S site, S(3) is bonded to one Tm(4) and three equivalent Tm(3) atoms to form distorted STm4 trigonal pyramids that share corners with three equivalent S(4)Tm5 square pyramids, corners with four equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(2)Tm4 trigonal pyramids, corners with two equivalent S(3)Tm4 trigonal pyramids, corners with three equivalent S(1)Tm4 trigonal pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid, and edges with two equivalent S(3)Tm4 trigonal pyramids. In the fourth S site, S(4) is bonded to two equivalent Tm(2) and three equivalent Tm(4) atoms to form STm5 square pyramids that share corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with four equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(2)Tm4 trigonal pyramids, corners with three equivalent S(3)Tm4 trigonal pyramids, edges with four equivalent S(4)Tm5 square pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid,  an edgeedge with one S(6)Tm5 trigonal bipyramid, and edges with three equivalent S(2)Tm4 trigonal pyramids. In the fifth S site, S(5) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent Tm(3) atoms to form STm5 trigonal bipyramids that share corners with two equivalent S(4)Tm5 square pyramids, corners with two equivalent S(6)Tm5 trigonal bipyramids,  a cornercorner with one S(1)Tm4 trigonal pyramid, corners with three equivalent S(2)Tm4 trigonal pyramids, corners with four equivalent S(3)Tm4 trigonal pyramids,  an edgeedge with one S(4)Tm5 square pyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, edges with three equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(3)Tm4 trigonal pyramid, and edges with two equivalent S(1)Tm4 trigonal pyramids. In the sixth S site, S(6) is bonded to two equivalent Tm(1) and three equivalent Tm(2) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(4)Tm5 square pyramids, corners with two equivalent S(5)Tm5 trigonal bipyramids,  a cornercorner with one S(2)Tm4 trigonal pyramid, corners with four equivalent S(1)Tm4 trigonal pyramids,  an edgeedge with one S(4)Tm5 square pyramid, edges with three equivalent S(5)Tm5 trigonal bipyramids, edges with four equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(1)Tm4 trigonal pyramid, and edges with two equivalent S(2)Tm4 trigonal pyramids.