La(TmS2)3 crystallizes in the monoclinic P2_1/m space group. There are three 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(2)S6 octahedra, corners with two equivalent Tm(3)S6 octahedra, edges with two equivalent Tm(2)S6 octahedra, and edges with four equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-51°. In the second Tm site, Tm(2) 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(3)S6 octahedra,  a cornercorner with one Tm(1)S7 pentagonal bipyramid, edges with four equivalent Tm(2)S6 octahedra, and edges with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 52-63°. In the third Tm site, Tm(3) 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(2)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, and edges with four equivalent Tm(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. La(1) 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. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Tm(2) and three equivalent Tm(1) atoms to form distorted STm4 tetrahedra that share corners with two equivalent S(1)Tm4 tetrahedra,  a cornercorner with one S(5)La2Tm3 trigonal bipyramid, corners with four equivalent S(6)La3Tm2 trigonal bipyramids, corners with three equivalent S(2)LaTm3 trigonal pyramids, edges with two equivalent S(1)Tm4 tetrahedra,  an edgeedge with one S(6)La3Tm2 trigonal bipyramid, and edges with two equivalent S(5)La2Tm3 trigonal bipyramids. In the second S site, S(2) is bonded to one Tm(1), two equivalent Tm(3), and one La(1) atom to form distorted SLaTm3 trigonal pyramids that share corners with two equivalent S(4)La2Tm3 square pyramids, corners with three equivalent S(1)Tm4 tetrahedra,  a cornercorner with one S(6)La3Tm2 trigonal bipyramid, corners with three equivalent S(5)La2Tm3 trigonal bipyramids, corners with two equivalent S(2)LaTm3 trigonal pyramids, edges with three equivalent S(4)La2Tm3 square pyramids, and edges with two equivalent S(6)La3Tm2 trigonal bipyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Tm(3) and three equivalent Tm(2) atoms. In the fourth S site, S(4) is bonded to three equivalent Tm(3) and two equivalent La(1) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(5)La2Tm3 trigonal bipyramids, corners with four equivalent S(6)La3Tm2 trigonal bipyramids, corners with two equivalent S(2)LaTm3 trigonal pyramids, edges with four equivalent S(4)La2Tm3 square pyramids,  an edgeedge with one S(5)La2Tm3 trigonal bipyramid,  an edgeedge with one S(6)La3Tm2 trigonal bipyramid, and edges with three equivalent S(2)LaTm3 trigonal pyramids. In the fifth S site, S(5) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent La(1) atoms to form distorted SLa2Tm3 trigonal bipyramids that share corners with two equivalent S(4)La2Tm3 square pyramids,  a cornercorner with one S(1)Tm4 tetrahedra, corners with two equivalent S(6)La3Tm2 trigonal bipyramids, corners with three equivalent S(2)LaTm3 trigonal pyramids,  an edgeedge with one S(4)La2Tm3 square pyramid, edges with two equivalent S(1)Tm4 tetrahedra, edges with two equivalent S(5)La2Tm3 trigonal bipyramids, and edges with three equivalent S(6)La3Tm2 trigonal bipyramids. In the sixth S site, S(6) is bonded to two equivalent Tm(1) and three equivalent La(1) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with four equivalent S(4)La2Tm3 square pyramids, corners with four equivalent S(1)Tm4 tetrahedra, corners with two equivalent S(5)La2Tm3 trigonal bipyramids,  a cornercorner with one S(2)LaTm3 trigonal pyramid,  an edgeedge with one S(4)La2Tm3 square pyramid,  an edgeedge with one S(1)Tm4 tetrahedra, edges with three equivalent S(5)La2Tm3 trigonal bipyramids, edges with four equivalent S(6)La3Tm2 trigonal bipyramids, and edges with two equivalent S(2)LaTm3 trigonal pyramids.
La(TmS2)3 crystallizes in the monoclinic P2_1/m space group. There are three 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(2)S6 octahedra, corners with two equivalent Tm(3)S6 octahedra, edges with two equivalent Tm(2)S6 octahedra, and edges with four equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-51°. The Tm(1)-S(2) bond length is 2.70 Å. The Tm(1)-S(5) bond length is 2.83 Å. Both Tm(1)-S(6) bond lengths are 2.88 Å. There are two shorter (2.66 Å) and one longer (2.86 Å) Tm(1)-S(1) bond length. In the second Tm site, Tm(2) 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(3)S6 octahedra,  a cornercorner with one Tm(1)S7 pentagonal bipyramid, edges with four equivalent Tm(2)S6 octahedra, and edges with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 52-63°. The Tm(2)-S(1) bond length is 2.64 Å. Both Tm(2)-S(5) bond lengths are 2.74 Å. There are two shorter (2.68 Å) and one longer (2.75 Å) Tm(2)-S(3) bond length. In the third Tm site, Tm(3) 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(2)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, and edges with four equivalent Tm(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. The Tm(3)-S(3) bond length is 2.68 Å. Both Tm(3)-S(2) bond lengths are 2.62 Å. There is one shorter (2.68 Å) and two longer (2.76 Å) Tm(3)-S(4) bond lengths. La(1) 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 La(1)-S(2) bond length is 3.02 Å. Both La(1)-S(4) bond lengths are 3.05 Å. Both La(1)-S(5) bond lengths are 3.06 Å. There are two shorter (2.93 Å) and one longer (2.97 Å) La(1)-S(6) bond length. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Tm(2) and three equivalent Tm(1) atoms to form distorted STm4 tetrahedra that share corners with two equivalent S(1)Tm4 tetrahedra,  a cornercorner with one S(5)La2Tm3 trigonal bipyramid, corners with four equivalent S(6)La3Tm2 trigonal bipyramids, corners with three equivalent S(2)LaTm3 trigonal pyramids, edges with two equivalent S(1)Tm4 tetrahedra,  an edgeedge with one S(6)La3Tm2 trigonal bipyramid, and edges with two equivalent S(5)La2Tm3 trigonal bipyramids. In the second S site, S(2) is bonded to one Tm(1), two equivalent Tm(3), and one La(1) atom to form distorted SLaTm3 trigonal pyramids that share corners with two equivalent S(4)La2Tm3 square pyramids, corners with three equivalent S(1)Tm4 tetrahedra,  a cornercorner with one S(6)La3Tm2 trigonal bipyramid, corners with three equivalent S(5)La2Tm3 trigonal bipyramids, corners with two equivalent S(2)LaTm3 trigonal pyramids, edges with three equivalent S(4)La2Tm3 square pyramids, and edges with two equivalent S(6)La3Tm2 trigonal bipyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Tm(3) and three equivalent Tm(2) atoms. In the fourth S site, S(4) is bonded to three equivalent Tm(3) and two equivalent La(1) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(5)La2Tm3 trigonal bipyramids, corners with four equivalent S(6)La3Tm2 trigonal bipyramids, corners with two equivalent S(2)LaTm3 trigonal pyramids, edges with four equivalent S(4)La2Tm3 square pyramids,  an edgeedge with one S(5)La2Tm3 trigonal bipyramid,  an edgeedge with one S(6)La3Tm2 trigonal bipyramid, and edges with three equivalent S(2)LaTm3 trigonal pyramids. In the fifth S site, S(5) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent La(1) atoms to form distorted SLa2Tm3 trigonal bipyramids that share corners with two equivalent S(4)La2Tm3 square pyramids,  a cornercorner with one S(1)Tm4 tetrahedra, corners with two equivalent S(6)La3Tm2 trigonal bipyramids, corners with three equivalent S(2)LaTm3 trigonal pyramids,  an edgeedge with one S(4)La2Tm3 square pyramid, edges with two equivalent S(1)Tm4 tetrahedra, edges with two equivalent S(5)La2Tm3 trigonal bipyramids, and edges with three equivalent S(6)La3Tm2 trigonal bipyramids. In the sixth S site, S(6) is bonded to two equivalent Tm(1) and three equivalent La(1) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with four equivalent S(4)La2Tm3 square pyramids, corners with four equivalent S(1)Tm4 tetrahedra, corners with two equivalent S(5)La2Tm3 trigonal bipyramids,  a cornercorner with one S(2)LaTm3 trigonal pyramid,  an edgeedge with one S(4)La2Tm3 square pyramid,  an edgeedge with one S(1)Tm4 tetrahedra, edges with three equivalent S(5)La2Tm3 trigonal bipyramids, edges with four equivalent S(6)La3Tm2 trigonal bipyramids, and edges with two equivalent S(2)LaTm3 trigonal pyramids.