TmLaS3 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(3), two equivalent S(11), and three equivalent S(8) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 58°. In the second Tm site, Tm(2) is bonded to one S(2), one S(3), two equivalent S(10), and two equivalent S(9) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 58°. In the third Tm site, Tm(3) is bonded to one S(4), one S(7), two equivalent S(12), and three equivalent S(1) atoms to form a mixture of distorted corner, face, and edge-sharing TmS7 pentagonal bipyramids. In the fourth Tm site, Tm(4) is bonded to one S(5), one S(6), two equivalent S(12), and three equivalent S(4) atoms to form a mixture of distorted corner, face, and edge-sharing TmS7 pentagonal bipyramids. There are four inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(11), one S(12), two equivalent S(3), two equivalent S(5), and two equivalent S(7) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(10), one S(4), two equivalent S(1), two equivalent S(6), and two equivalent S(7) atoms. In the third La site, La(3) is bonded in a 8-coordinate geometry to one S(10), one S(11), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. In the fourth La site, La(4) is bonded in a 8-coordinate geometry to one S(11), two equivalent S(2), two equivalent S(8), and three equivalent S(9) atoms. There are twelve inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Tm(3) and two equivalent La(2) atoms to form distorted SLa2Tm3 trigonal bipyramids that share corners with four equivalent S(7)La4Tm square pyramids, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with four equivalent S(12)LaTm4 trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(6)La4Tm trigonal bipyramid,  an edgeedge with one S(12)LaTm4 trigonal bipyramid, edges with four equivalent S(1)La2Tm3 trigonal bipyramids, and  a faceface with one S(7)La4Tm square pyramid. In the second S site, S(2) is bonded to one Tm(2), two equivalent La(3), and two equivalent La(4) atoms to form distorted SLa4Tm square pyramids that share corners with two equivalent S(8)La2Tm3 square pyramids,  a cornercorner with one S(3)La2Tm2 tetrahedra, corners with two equivalent S(9)La3Tm2 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(6)La4Tm trigonal bipyramids,  an edgeedge with one S(8)La2Tm3 square pyramid, edges with two equivalent S(2)La4Tm square pyramids,  an edgeedge with one S(5)La4Tm trigonal bipyramid,  an edgeedge with one S(6)La4Tm trigonal bipyramid, edges with three equivalent S(9)La3Tm2 trigonal bipyramids, and edges with two equivalent S(10)La2Tm2 trigonal pyramids. In the third S site, S(3) is bonded to one Tm(1), one Tm(2), and two equivalent La(1) atoms to form distorted SLa2Tm2 tetrahedra that share  a cornercorner with one S(2)La4Tm square pyramid, corners with two equivalent S(7)La4Tm square pyramids, corners with three equivalent S(8)La2Tm3 square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(9)La3Tm2 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(12)LaTm4 trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(7)La4Tm square pyramid, and  an edgeedge with one S(5)La4Tm trigonal bipyramid. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Tm(3), three equivalent Tm(4), and one La(2) atom. In the fifth S site, S(5) is bonded to one Tm(4), two equivalent La(1), and two equivalent La(3) atoms to form SLa4Tm trigonal bipyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with two equivalent S(7)La4Tm square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(2)La4Tm square pyramid,  an edgeedge with one S(7)La4Tm square pyramid,  an edgeedge with one S(3)La2Tm2 tetrahedra, edges with two equivalent S(5)La4Tm trigonal bipyramids, edges with two equivalent S(12)LaTm4 trigonal bipyramids, and  a faceface with one S(6)La4Tm trigonal bipyramid. In the sixth S site, S(6) is bonded to one Tm(4), two equivalent La(2), and two equivalent La(3) atoms to form distorted SLa4Tm trigonal bipyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with two equivalent S(7)La4Tm square pyramids, corners with two equivalent S(1)La2Tm3 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(12)LaTm4 trigonal bipyramids,  an edgeedge with one S(2)La4Tm square pyramid,  an edgeedge with one S(7)La4Tm square pyramid,  an edgeedge with one S(1)La2Tm3 trigonal bipyramid, edges with two equivalent S(6)La4Tm trigonal bipyramids, edges with two equivalent S(10)La2Tm2 trigonal pyramids, and  a faceface with one S(5)La4Tm trigonal bipyramid. In the seventh S site, S(7) is bonded to one Tm(3), two equivalent La(1), and two equivalent La(2) atoms to form distorted SLa4Tm square pyramids that share corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with four equivalent S(1)La2Tm3 trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids, edges with two equivalent S(7)La4Tm square pyramids,  an edgeedge with one S(3)La2Tm2 tetrahedra,  an edgeedge with one S(5)La4Tm trigonal bipyramid,  an edgeedge with one S(6)La4Tm trigonal bipyramid, edges with two equivalent S(12)LaTm4 trigonal bipyramids, and  a faceface with one S(1)La2Tm3 trigonal bipyramid. In the eighth S site, S(8) is bonded to three equivalent Tm(1) and two equivalent La(4) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with three equivalent S(3)La2Tm2 tetrahedra, corners with four equivalent S(9)La3Tm2 trigonal bipyramids,  an edgeedge with one S(2)La4Tm square pyramid, edges with four equivalent S(8)La2Tm3 square pyramids, and  an edgeedge with one S(9)La3Tm2 trigonal bipyramid. In the ninth S site, S(9) is bonded to two equivalent Tm(2) and three equivalent La(4) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with four equivalent S(8)La2Tm3 square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(8)La2Tm3 square pyramid, edges with three equivalent S(2)La4Tm square pyramids, edges with four equivalent S(9)La3Tm2 trigonal bipyramids, and  an edgeedge with one S(10)La2Tm2 trigonal pyramid. In the tenth S site, S(10) is bonded to two equivalent Tm(2), one La(2), and one La(3) atom to form distorted SLa2Tm2 trigonal pyramids that share corners with two equivalent S(7)La4Tm square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(1)La2Tm3 trigonal bipyramids, corners with two equivalent S(9)La3Tm2 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids, edges with two equivalent S(2)La4Tm square pyramids,  an edgeedge with one S(9)La3Tm2 trigonal bipyramid, and edges with two equivalent S(6)La4Tm trigonal bipyramids. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to two equivalent Tm(1), one La(1), one La(3), and one La(4) atom. In the twelfth S site, S(12) is bonded to two equivalent Tm(3), two equivalent Tm(4), and one La(1) atom to form distorted SLaTm4 trigonal bipyramids that share corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with four equivalent S(1)La2Tm3 trigonal bipyramids, edges with two equivalent S(7)La4Tm square pyramids,  an edgeedge with one S(1)La2Tm3 trigonal bipyramid, edges with two equivalent S(5)La4Tm trigonal bipyramids, and edges with two equivalent S(12)LaTm4 trigonal bipyramids.
TmLaS3 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(3), two equivalent S(11), and three equivalent S(8) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Tm(1)-S(3) bond length is 2.60 Å. Both Tm(1)-S(11) bond lengths are 2.61 Å. There is one shorter (2.69 Å) and two longer (2.79 Å) Tm(1)-S(8) bond lengths. In the second Tm site, Tm(2) is bonded to one S(2), one S(3), two equivalent S(10), and two equivalent S(9) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Tm(2)-S(2) bond length is 2.66 Å. The Tm(2)-S(3) bond length is 2.64 Å. Both Tm(2)-S(10) bond lengths are 2.63 Å. Both Tm(2)-S(9) bond lengths are 2.80 Å. In the third Tm site, Tm(3) is bonded to one S(4), one S(7), two equivalent S(12), and three equivalent S(1) atoms to form a mixture of distorted corner, face, and edge-sharing TmS7 pentagonal bipyramids. The Tm(3)-S(4) bond length is 2.95 Å. The Tm(3)-S(7) bond length is 2.68 Å. Both Tm(3)-S(12) bond lengths are 2.76 Å. There are two shorter (2.72 Å) and one longer (2.94 Å) Tm(3)-S(1) bond length. In the fourth Tm site, Tm(4) is bonded to one S(5), one S(6), two equivalent S(12), and three equivalent S(4) atoms to form a mixture of distorted corner, face, and edge-sharing TmS7 pentagonal bipyramids. The Tm(4)-S(5) bond length is 2.95 Å. The Tm(4)-S(6) bond length is 2.78 Å. Both Tm(4)-S(12) bond lengths are 2.85 Å. There are two shorter (2.70 Å) and one longer (2.85 Å) Tm(4)-S(4) bond length. There are four inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(11), one S(12), two equivalent S(3), two equivalent S(5), and two equivalent S(7) atoms. The La(1)-S(11) bond length is 3.49 Å. The La(1)-S(12) bond length is 3.08 Å. Both La(1)-S(3) bond lengths are 2.93 Å. Both La(1)-S(5) bond lengths are 2.97 Å. Both La(1)-S(7) bond lengths are 3.01 Å. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(10), one S(4), two equivalent S(1), two equivalent S(6), and two equivalent S(7) atoms. The La(2)-S(10) bond length is 2.88 Å. The La(2)-S(4) bond length is 3.35 Å. Both La(2)-S(1) bond lengths are 2.95 Å. Both La(2)-S(6) bond lengths are 2.90 Å. Both La(2)-S(7) bond lengths are 3.09 Å. In the third La site, La(3) is bonded in a 8-coordinate geometry to one S(10), one S(11), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. The La(3)-S(10) bond length is 3.02 Å. The La(3)-S(11) bond length is 2.93 Å. Both La(3)-S(2) bond lengths are 2.98 Å. Both La(3)-S(5) bond lengths are 2.99 Å. Both La(3)-S(6) bond lengths are 3.00 Å. In the fourth La site, La(4) is bonded in a 8-coordinate geometry to one S(11), two equivalent S(2), two equivalent S(8), and three equivalent S(9) atoms. The La(4)-S(11) bond length is 3.19 Å. Both La(4)-S(2) bond lengths are 2.92 Å. Both La(4)-S(8) bond lengths are 2.99 Å. There is one shorter (2.98 Å) and two longer (3.05 Å) La(4)-S(9) bond lengths. There are twelve inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Tm(3) and two equivalent La(2) atoms to form distorted SLa2Tm3 trigonal bipyramids that share corners with four equivalent S(7)La4Tm square pyramids, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with four equivalent S(12)LaTm4 trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(6)La4Tm trigonal bipyramid,  an edgeedge with one S(12)LaTm4 trigonal bipyramid, edges with four equivalent S(1)La2Tm3 trigonal bipyramids, and  a faceface with one S(7)La4Tm square pyramid. In the second S site, S(2) is bonded to one Tm(2), two equivalent La(3), and two equivalent La(4) atoms to form distorted SLa4Tm square pyramids that share corners with two equivalent S(8)La2Tm3 square pyramids,  a cornercorner with one S(3)La2Tm2 tetrahedra, corners with two equivalent S(9)La3Tm2 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(6)La4Tm trigonal bipyramids,  an edgeedge with one S(8)La2Tm3 square pyramid, edges with two equivalent S(2)La4Tm square pyramids,  an edgeedge with one S(5)La4Tm trigonal bipyramid,  an edgeedge with one S(6)La4Tm trigonal bipyramid, edges with three equivalent S(9)La3Tm2 trigonal bipyramids, and edges with two equivalent S(10)La2Tm2 trigonal pyramids. In the third S site, S(3) is bonded to one Tm(1), one Tm(2), and two equivalent La(1) atoms to form distorted SLa2Tm2 tetrahedra that share  a cornercorner with one S(2)La4Tm square pyramid, corners with two equivalent S(7)La4Tm square pyramids, corners with three equivalent S(8)La2Tm3 square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(9)La3Tm2 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(12)LaTm4 trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(7)La4Tm square pyramid, and  an edgeedge with one S(5)La4Tm trigonal bipyramid. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Tm(3), three equivalent Tm(4), and one La(2) atom. In the fifth S site, S(5) is bonded to one Tm(4), two equivalent La(1), and two equivalent La(3) atoms to form SLa4Tm trigonal bipyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with two equivalent S(7)La4Tm square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(2)La4Tm square pyramid,  an edgeedge with one S(7)La4Tm square pyramid,  an edgeedge with one S(3)La2Tm2 tetrahedra, edges with two equivalent S(5)La4Tm trigonal bipyramids, edges with two equivalent S(12)LaTm4 trigonal bipyramids, and  a faceface with one S(6)La4Tm trigonal bipyramid. In the sixth S site, S(6) is bonded to one Tm(4), two equivalent La(2), and two equivalent La(3) atoms to form distorted SLa4Tm trigonal bipyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with two equivalent S(7)La4Tm square pyramids, corners with two equivalent S(1)La2Tm3 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(12)LaTm4 trigonal bipyramids,  an edgeedge with one S(2)La4Tm square pyramid,  an edgeedge with one S(7)La4Tm square pyramid,  an edgeedge with one S(1)La2Tm3 trigonal bipyramid, edges with two equivalent S(6)La4Tm trigonal bipyramids, edges with two equivalent S(10)La2Tm2 trigonal pyramids, and  a faceface with one S(5)La4Tm trigonal bipyramid. In the seventh S site, S(7) is bonded to one Tm(3), two equivalent La(1), and two equivalent La(2) atoms to form distorted SLa4Tm square pyramids that share corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with four equivalent S(1)La2Tm3 trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids, edges with two equivalent S(7)La4Tm square pyramids,  an edgeedge with one S(3)La2Tm2 tetrahedra,  an edgeedge with one S(5)La4Tm trigonal bipyramid,  an edgeedge with one S(6)La4Tm trigonal bipyramid, edges with two equivalent S(12)LaTm4 trigonal bipyramids, and  a faceface with one S(1)La2Tm3 trigonal bipyramid. In the eighth S site, S(8) is bonded to three equivalent Tm(1) and two equivalent La(4) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with three equivalent S(3)La2Tm2 tetrahedra, corners with four equivalent S(9)La3Tm2 trigonal bipyramids,  an edgeedge with one S(2)La4Tm square pyramid, edges with four equivalent S(8)La2Tm3 square pyramids, and  an edgeedge with one S(9)La3Tm2 trigonal bipyramid. In the ninth S site, S(9) is bonded to two equivalent Tm(2) and three equivalent La(4) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with two equivalent S(2)La4Tm square pyramids, corners with four equivalent S(8)La2Tm3 square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(10)La2Tm2 trigonal pyramids,  an edgeedge with one S(8)La2Tm3 square pyramid, edges with three equivalent S(2)La4Tm square pyramids, edges with four equivalent S(9)La3Tm2 trigonal bipyramids, and  an edgeedge with one S(10)La2Tm2 trigonal pyramid. In the tenth S site, S(10) is bonded to two equivalent Tm(2), one La(2), and one La(3) atom to form distorted SLa2Tm2 trigonal pyramids that share corners with two equivalent S(7)La4Tm square pyramids, corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(1)La2Tm3 trigonal bipyramids, corners with two equivalent S(9)La3Tm2 trigonal bipyramids, corners with two equivalent S(5)La4Tm trigonal bipyramids, corners with two equivalent S(10)La2Tm2 trigonal pyramids, edges with two equivalent S(2)La4Tm square pyramids,  an edgeedge with one S(9)La3Tm2 trigonal bipyramid, and edges with two equivalent S(6)La4Tm trigonal bipyramids. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to two equivalent Tm(1), one La(1), one La(3), and one La(4) atom. In the twelfth S site, S(12) is bonded to two equivalent Tm(3), two equivalent Tm(4), and one La(1) atom to form distorted SLaTm4 trigonal bipyramids that share corners with two equivalent S(3)La2Tm2 tetrahedra, corners with two equivalent S(6)La4Tm trigonal bipyramids, corners with four equivalent S(1)La2Tm3 trigonal bipyramids, edges with two equivalent S(7)La4Tm square pyramids,  an edgeedge with one S(1)La2Tm3 trigonal bipyramid, edges with two equivalent S(5)La4Tm trigonal bipyramids, and edges with two equivalent S(12)LaTm4 trigonal bipyramids.