La4(TmS2)11 crystallizes in the monoclinic C2/m space group. There are six inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(2), one S(9), two equivalent S(8), and three equivalent S(11) atoms to form distorted TmS7 pentagonal bipyramids that share  a cornercorner with one Tm(4)S6 octahedra, corners with two equivalent Tm(3)S6 octahedra, edges with two equivalent Tm(4)S6 octahedra, and edges with four equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-50°. In the second Tm site, Tm(2) is bonded to one S(4), one S(7), two equivalent S(1), and two equivalent S(10) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. In the third Tm site, Tm(3) is bonded to one S(3), one S(6), two equivalent S(5), and two equivalent S(9) atoms to form TmS6 octahedra that share corners with three equivalent Tm(4)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, edges with two equivalent Tm(3)S6 octahedra, and edges with two equivalent Tm(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-63°. In the fourth Tm site, Tm(4) is bonded to one S(11), two equivalent S(2), 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(4)S6 octahedra, and edges with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 51-63°. In the fifth Tm site, Tm(5) is bonded to one S(10), one S(5), two equivalent S(4), and two equivalent S(6) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. In the sixth Tm site, Tm(6) is bonded to two equivalent S(10) and four equivalent S(7) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(1), one S(9), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(4), one S(8), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. There are eleven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Tm(2), one La(1), and two equivalent La(2) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(6)La2Tm3 square pyramids, corners with two equivalent S(2)La2Tm3 trigonal bipyramids,  a cornercorner with one S(9)LaTm3 trigonal pyramid,  an edgeedge with one S(5)La2Tm3 square pyramid, edges with two equivalent S(7)La2Tm3 square pyramids,  an edgeedge with one S(2)La2Tm3 trigonal bipyramid, edges with two equivalent S(1)La3Tm2 trigonal bipyramids, and edges with two equivalent S(8)La3Tm2 trigonal bipyramids. In the second S site, S(2) is bonded to one Tm(1), two equivalent Tm(4), and two equivalent La(2) atoms to form SLa2Tm3 trigonal bipyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(1)La3Tm2 trigonal bipyramids,  a cornercorner with one S(9)LaTm3 trigonal pyramid,  a cornercorner with one S(11)Tm4 trigonal pyramid,  an edgeedge with one S(5)La2Tm3 square pyramid,  an edgeedge with one S(1)La3Tm2 trigonal bipyramid, edges with two equivalent S(2)La2Tm3 trigonal bipyramids, edges with two equivalent S(8)La3Tm2 trigonal bipyramids, and edges with two equivalent S(11)Tm4 trigonal pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Tm(3) and three equivalent Tm(4) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Tm(2), two equivalent Tm(5), and one La(2) atom. In the fifth S site, S(5) is bonded to one Tm(5), two equivalent Tm(3), and two equivalent La(2) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(2)La2Tm3 trigonal bipyramids, corners with two equivalent S(1)La3Tm2 trigonal bipyramids, corners with two equivalent S(8)La3Tm2 trigonal bipyramids, corners with two equivalent S(9)LaTm3 trigonal pyramids, edges with two equivalent S(5)La2Tm3 square pyramids, edges with two equivalent S(6)La2Tm3 square pyramids,  an edgeedge with one S(2)La2Tm3 trigonal bipyramid,  an edgeedge with one S(1)La3Tm2 trigonal bipyramid, and  an edgeedge with one S(9)LaTm3 trigonal pyramid. In the sixth S site, S(6) is bonded to one Tm(3), two equivalent Tm(5), and two equivalent La(1) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(7)La2Tm3 square pyramids, corners with two equivalent S(1)La3Tm2 trigonal bipyramids, corners with two equivalent S(8)La3Tm2 trigonal bipyramids,  an edgeedge with one S(7)La2Tm3 square pyramid, edges with two equivalent S(5)La2Tm3 square pyramids, edges with two equivalent S(6)La2Tm3 square pyramids,  an edgeedge with one S(8)La3Tm2 trigonal bipyramid, and edges with two equivalent S(9)LaTm3 trigonal pyramids. In the seventh S site, S(7) is bonded to one Tm(2), two equivalent Tm(6), and two equivalent La(1) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(6)La2Tm3 square pyramids, corners with two equivalent S(7)La2Tm3 square pyramids, corners with two equivalent S(8)La3Tm2 trigonal bipyramids, corners with two equivalent S(9)LaTm3 trigonal pyramids,  an edgeedge with one S(6)La2Tm3 square pyramid, edges with three equivalent S(7)La2Tm3 square pyramids,  an edgeedge with one S(8)La3Tm2 trigonal bipyramid, and edges with two equivalent S(1)La3Tm2 trigonal bipyramids. In the eighth S site, S(8) is bonded to two equivalent Tm(1), one La(2), and two equivalent La(1) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(6)La2Tm3 square pyramids, corners with two equivalent S(7)La2Tm3 square pyramids, corners with four equivalent S(11)Tm4 trigonal pyramids,  an edgeedge with one S(6)La2Tm3 square pyramid,  an edgeedge with one S(7)La2Tm3 square pyramid, edges with two equivalent S(2)La2Tm3 trigonal bipyramids, edges with two equivalent S(1)La3Tm2 trigonal bipyramids, edges with two equivalent S(8)La3Tm2 trigonal bipyramids,  an edgeedge with one S(11)Tm4 trigonal pyramid, and edges with two equivalent S(9)LaTm3 trigonal pyramids. In the ninth S site, S(9) is bonded to one Tm(1), two equivalent Tm(3), and one La(1) atom to form SLaTm3 trigonal pyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(7)La2Tm3 square pyramids,  a cornercorner with one S(2)La2Tm3 trigonal bipyramid,  a cornercorner with one S(1)La3Tm2 trigonal bipyramid, corners with two equivalent S(9)LaTm3 trigonal pyramids, corners with three equivalent S(11)Tm4 trigonal pyramids,  an edgeedge with one S(5)La2Tm3 square pyramid, edges with two equivalent S(6)La2Tm3 square pyramids, and edges with two equivalent S(8)La3Tm2 trigonal bipyramids. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Tm(5), one Tm(6), and two equivalent Tm(2) atoms. In the eleventh S site, S(11) is bonded to one Tm(4) and three equivalent Tm(1) atoms to form distorted STm4 trigonal pyramids that share  a cornercorner with one S(2)La2Tm3 trigonal bipyramid, corners with four equivalent S(8)La3Tm2 trigonal bipyramids, corners with two equivalent S(11)Tm4 trigonal pyramids, corners with three equivalent S(9)LaTm3 trigonal pyramids,  an edgeedge with one S(8)La3Tm2 trigonal bipyramid, edges with two equivalent S(2)La2Tm3 trigonal bipyramids, and edges with two equivalent S(11)Tm4 trigonal pyramids.
La4(TmS2)11 crystallizes in the monoclinic C2/m space group. There are six inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(2), one S(9), two equivalent S(8), and three equivalent S(11) atoms to form distorted TmS7 pentagonal bipyramids that share  a cornercorner with one Tm(4)S6 octahedra, corners with two equivalent Tm(3)S6 octahedra, edges with two equivalent Tm(4)S6 octahedra, and edges with four equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-50°. The Tm(1)-S(2) bond length is 2.86 Å. The Tm(1)-S(9) bond length is 2.75 Å. Both Tm(1)-S(8) bond lengths are 2.87 Å. There are two shorter (2.68 Å) and one longer (2.86 Å) Tm(1)-S(11) bond length. In the second Tm site, Tm(2) is bonded to one S(4), one S(7), two equivalent S(1), and two equivalent S(10) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. The Tm(2)-S(4) bond length is 2.64 Å. The Tm(2)-S(7) bond length is 2.72 Å. Both Tm(2)-S(1) bond lengths are 2.76 Å. Both Tm(2)-S(10) bond lengths are 2.70 Å. In the third Tm site, Tm(3) is bonded to one S(3), one S(6), two equivalent S(5), and two equivalent S(9) atoms to form TmS6 octahedra that share corners with three equivalent Tm(4)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, edges with two equivalent Tm(3)S6 octahedra, and edges with two equivalent Tm(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-63°. The Tm(3)-S(3) bond length is 2.71 Å. The Tm(3)-S(6) bond length is 2.70 Å. Both Tm(3)-S(5) bond lengths are 2.78 Å. Both Tm(3)-S(9) bond lengths are 2.64 Å. In the fourth Tm site, Tm(4) is bonded to one S(11), two equivalent S(2), 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(4)S6 octahedra, and edges with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 51-63°. The Tm(4)-S(11) bond length is 2.65 Å. Both Tm(4)-S(2) bond lengths are 2.75 Å. There are two shorter (2.71 Å) and one longer (2.76 Å) Tm(4)-S(3) bond length. In the fifth Tm site, Tm(5) is bonded to one S(10), one S(5), two equivalent S(4), and two equivalent S(6) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. The Tm(5)-S(10) bond length is 2.75 Å. The Tm(5)-S(5) bond length is 2.73 Å. Both Tm(5)-S(4) bond lengths are 2.64 Å. Both Tm(5)-S(6) bond lengths are 2.76 Å. In the sixth Tm site, Tm(6) is bonded to two equivalent S(10) and four equivalent S(7) atoms to form a mixture of corner and edge-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 55°. Both Tm(6)-S(10) bond lengths are 2.72 Å. All Tm(6)-S(7) bond lengths are 2.71 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(1), one S(9), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms. The La(1)-S(1) bond length is 3.02 Å. The La(1)-S(9) bond length is 2.96 Å. Both La(1)-S(6) bond lengths are 3.06 Å. Both La(1)-S(7) bond lengths are 3.04 Å. Both La(1)-S(8) bond lengths are 2.94 Å. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(4), one S(8), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. The La(2)-S(4) bond length is 3.47 Å. The La(2)-S(8) bond length is 2.97 Å. Both La(2)-S(1) bond lengths are 2.92 Å. Both La(2)-S(2) bond lengths are 3.00 Å. Both La(2)-S(5) bond lengths are 3.02 Å. There are eleven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Tm(2), one La(1), and two equivalent La(2) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(6)La2Tm3 square pyramids, corners with two equivalent S(2)La2Tm3 trigonal bipyramids,  a cornercorner with one S(9)LaTm3 trigonal pyramid,  an edgeedge with one S(5)La2Tm3 square pyramid, edges with two equivalent S(7)La2Tm3 square pyramids,  an edgeedge with one S(2)La2Tm3 trigonal bipyramid, edges with two equivalent S(1)La3Tm2 trigonal bipyramids, and edges with two equivalent S(8)La3Tm2 trigonal bipyramids. In the second S site, S(2) is bonded to one Tm(1), two equivalent Tm(4), and two equivalent La(2) atoms to form SLa2Tm3 trigonal bipyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(1)La3Tm2 trigonal bipyramids,  a cornercorner with one S(9)LaTm3 trigonal pyramid,  a cornercorner with one S(11)Tm4 trigonal pyramid,  an edgeedge with one S(5)La2Tm3 square pyramid,  an edgeedge with one S(1)La3Tm2 trigonal bipyramid, edges with two equivalent S(2)La2Tm3 trigonal bipyramids, edges with two equivalent S(8)La3Tm2 trigonal bipyramids, and edges with two equivalent S(11)Tm4 trigonal pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Tm(3) and three equivalent Tm(4) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Tm(2), two equivalent Tm(5), and one La(2) atom. In the fifth S site, S(5) is bonded to one Tm(5), two equivalent Tm(3), and two equivalent La(2) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(2)La2Tm3 trigonal bipyramids, corners with two equivalent S(1)La3Tm2 trigonal bipyramids, corners with two equivalent S(8)La3Tm2 trigonal bipyramids, corners with two equivalent S(9)LaTm3 trigonal pyramids, edges with two equivalent S(5)La2Tm3 square pyramids, edges with two equivalent S(6)La2Tm3 square pyramids,  an edgeedge with one S(2)La2Tm3 trigonal bipyramid,  an edgeedge with one S(1)La3Tm2 trigonal bipyramid, and  an edgeedge with one S(9)LaTm3 trigonal pyramid. In the sixth S site, S(6) is bonded to one Tm(3), two equivalent Tm(5), and two equivalent La(1) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(7)La2Tm3 square pyramids, corners with two equivalent S(1)La3Tm2 trigonal bipyramids, corners with two equivalent S(8)La3Tm2 trigonal bipyramids,  an edgeedge with one S(7)La2Tm3 square pyramid, edges with two equivalent S(5)La2Tm3 square pyramids, edges with two equivalent S(6)La2Tm3 square pyramids,  an edgeedge with one S(8)La3Tm2 trigonal bipyramid, and edges with two equivalent S(9)LaTm3 trigonal pyramids. In the seventh S site, S(7) is bonded to one Tm(2), two equivalent Tm(6), and two equivalent La(1) atoms to form SLa2Tm3 square pyramids that share corners with two equivalent S(6)La2Tm3 square pyramids, corners with two equivalent S(7)La2Tm3 square pyramids, corners with two equivalent S(8)La3Tm2 trigonal bipyramids, corners with two equivalent S(9)LaTm3 trigonal pyramids,  an edgeedge with one S(6)La2Tm3 square pyramid, edges with three equivalent S(7)La2Tm3 square pyramids,  an edgeedge with one S(8)La3Tm2 trigonal bipyramid, and edges with two equivalent S(1)La3Tm2 trigonal bipyramids. In the eighth S site, S(8) is bonded to two equivalent Tm(1), one La(2), and two equivalent La(1) atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(6)La2Tm3 square pyramids, corners with two equivalent S(7)La2Tm3 square pyramids, corners with four equivalent S(11)Tm4 trigonal pyramids,  an edgeedge with one S(6)La2Tm3 square pyramid,  an edgeedge with one S(7)La2Tm3 square pyramid, edges with two equivalent S(2)La2Tm3 trigonal bipyramids, edges with two equivalent S(1)La3Tm2 trigonal bipyramids, edges with two equivalent S(8)La3Tm2 trigonal bipyramids,  an edgeedge with one S(11)Tm4 trigonal pyramid, and edges with two equivalent S(9)LaTm3 trigonal pyramids. In the ninth S site, S(9) is bonded to one Tm(1), two equivalent Tm(3), and one La(1) atom to form SLaTm3 trigonal pyramids that share corners with two equivalent S(5)La2Tm3 square pyramids, corners with two equivalent S(7)La2Tm3 square pyramids,  a cornercorner with one S(2)La2Tm3 trigonal bipyramid,  a cornercorner with one S(1)La3Tm2 trigonal bipyramid, corners with two equivalent S(9)LaTm3 trigonal pyramids, corners with three equivalent S(11)Tm4 trigonal pyramids,  an edgeedge with one S(5)La2Tm3 square pyramid, edges with two equivalent S(6)La2Tm3 square pyramids, and edges with two equivalent S(8)La3Tm2 trigonal bipyramids. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Tm(5), one Tm(6), and two equivalent Tm(2) atoms. In the eleventh S site, S(11) is bonded to one Tm(4) and three equivalent Tm(1) atoms to form distorted STm4 trigonal pyramids that share  a cornercorner with one S(2)La2Tm3 trigonal bipyramid, corners with four equivalent S(8)La3Tm2 trigonal bipyramids, corners with two equivalent S(11)Tm4 trigonal pyramids, corners with three equivalent S(9)LaTm3 trigonal pyramids,  an edgeedge with one S(8)La3Tm2 trigonal bipyramid, edges with two equivalent S(2)La2Tm3 trigonal bipyramids, and edges with two equivalent S(11)Tm4 trigonal pyramids.