Tm4CeS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(7), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms to form distorted TmS7 pentagonal bipyramids that share corners with two equivalent Tm(3)S6 octahedra, corners with two equivalent Tm(4)S6 octahedra, corners with four equivalent Ce(1)S6 octahedra,  an edgeedge with one Ce(1)S6 octahedra, edges with three equivalent Tm(4)S6 octahedra, edges with two equivalent Tm(2)S7 pentagonal bipyramids, and faces with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-64°. In the second Tm site, Tm(2) is bonded to one S(6), two equivalent S(1), two equivalent S(4), and two equivalent S(7) atoms to form distorted TmS7 pentagonal bipyramids that share corners with two equivalent Tm(4)S6 octahedra, corners with two equivalent Ce(1)S6 octahedra, corners with four equivalent Tm(3)S6 octahedra,  an edgeedge with one Tm(3)S6 octahedra, edges with three equivalent Tm(4)S6 octahedra, edges with two equivalent Tm(1)S7 pentagonal bipyramids, and faces with two equivalent Tm(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-69°. In the third Tm site, Tm(3) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(5) atoms to form TmS6 octahedra that share  a cornercorner with one Tm(4)S6 octahedra, corners with two equivalent Ce(1)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, corners with four equivalent Tm(2)S7 pentagonal bipyramids, edges with two equivalent Tm(3)S6 octahedra, edges with three equivalent Ce(1)S6 octahedra, and  an edgeedge with one Tm(2)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-58°. In the fourth Tm site, Tm(4) is bonded to one S(3), one S(4), two equivalent S(6), and two equivalent S(7) atoms to form TmS6 octahedra that share  a cornercorner with one Tm(3)S6 octahedra,  a cornercorner with one Ce(1)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, corners with two equivalent Tm(2)S7 pentagonal bipyramids, edges with two equivalent Tm(4)S6 octahedra, edges with three equivalent Tm(1)S7 pentagonal bipyramids, and edges with three equivalent Tm(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 57-58°. Ce(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(5) atoms to form CeS6 octahedra that share  a cornercorner with one Tm(4)S6 octahedra, corners with two equivalent Tm(3)S6 octahedra, corners with two equivalent Tm(2)S7 pentagonal bipyramids, corners with four equivalent Tm(1)S7 pentagonal bipyramids, edges with two equivalent Ce(1)S6 octahedra, edges with three equivalent Tm(3)S6 octahedra, and  an edgeedge with one Tm(1)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-57°. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Tm(2), two equivalent Tm(3), and one Ce(1) atom to form SCeTm4 trigonal bipyramids that share  a cornercorner with one S(3)CeTm3 tetrahedra, corners with four equivalent S(4)Tm4 tetrahedra, corners with two equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(4)Tm4 tetrahedra,  an edgeedge with one S(7)Tm5 trigonal bipyramid, edges with two equivalent S(2)Ce2Tm3 trigonal bipyramids, and edges with two equivalent S(1)CeTm4 trigonal bipyramids. In the second S site, S(2) is bonded to one Tm(3), two equivalent Tm(1), and two equivalent Ce(1) atoms to form SCe2Tm3 trigonal bipyramids that share  a cornercorner with one S(4)Tm4 tetrahedra, corners with four equivalent S(3)CeTm3 tetrahedra, corners with two equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(3)CeTm3 tetrahedra,  an edgeedge with one S(6)Tm5 trigonal bipyramid, edges with two equivalent S(2)Ce2Tm3 trigonal bipyramids, and edges with two equivalent S(1)CeTm4 trigonal bipyramids. In the third S site, S(3) is bonded to one Tm(4), two equivalent Tm(1), and one Ce(1) atom to form SCeTm3 tetrahedra that share  a cornercorner with one S(4)Tm4 tetrahedra, corners with two equivalent S(3)CeTm3 tetrahedra,  a cornercorner with one S(1)CeTm4 trigonal bipyramid, corners with four equivalent S(2)Ce2Tm3 trigonal bipyramids, corners with four equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(2)Ce2Tm3 trigonal bipyramid,  an edgeedge with one S(6)Tm5 trigonal bipyramid, and edges with two equivalent S(7)Tm5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Tm(3), one Tm(4), and two equivalent Tm(2) atoms to form distorted STm4 tetrahedra that share  a cornercorner with one S(3)CeTm3 tetrahedra, corners with two equivalent S(4)Tm4 tetrahedra,  a cornercorner with one S(2)Ce2Tm3 trigonal bipyramid, corners with four equivalent S(1)CeTm4 trigonal bipyramids, corners with four equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(1)CeTm4 trigonal bipyramid,  an edgeedge with one S(7)Tm5 trigonal bipyramid, and edges with two equivalent S(6)Tm5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to two equivalent Tm(3) and two equivalent Ce(1) atoms. In the sixth S site, S(6) is bonded to one Tm(2), two equivalent Tm(1), and two equivalent Tm(4) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(3)CeTm3 tetrahedra, corners with two equivalent S(2)Ce2Tm3 trigonal bipyramids, corners with two equivalent S(1)CeTm4 trigonal bipyramids, corners with two equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(3)CeTm3 tetrahedra, edges with two equivalent S(4)Tm4 tetrahedra,  an edgeedge with one S(2)Ce2Tm3 trigonal bipyramid, edges with two equivalent S(6)Tm5 trigonal bipyramids, and edges with three equivalent S(7)Tm5 trigonal bipyramids. In the seventh S site, S(7) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent Tm(4) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(4)Tm4 tetrahedra, corners with two equivalent S(2)Ce2Tm3 trigonal bipyramids, corners with two equivalent S(1)CeTm4 trigonal bipyramids, corners with two equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(4)Tm4 tetrahedra, edges with two equivalent S(3)CeTm3 tetrahedra,  an edgeedge with one S(1)CeTm4 trigonal bipyramid, edges with two equivalent S(7)Tm5 trigonal bipyramids, and edges with three equivalent S(6)Tm5 trigonal bipyramids.
Tm4CeS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(7), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms to form distorted TmS7 pentagonal bipyramids that share corners with two equivalent Tm(3)S6 octahedra, corners with two equivalent Tm(4)S6 octahedra, corners with four equivalent Ce(1)S6 octahedra,  an edgeedge with one Ce(1)S6 octahedra, edges with three equivalent Tm(4)S6 octahedra, edges with two equivalent Tm(2)S7 pentagonal bipyramids, and faces with two equivalent Tm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-64°. The Tm(1)-S(7) bond length is 2.93 Å. Both Tm(1)-S(2) bond lengths are 2.87 Å. Both Tm(1)-S(3) bond lengths are 2.71 Å. Both Tm(1)-S(6) bond lengths are 2.83 Å. In the second Tm site, Tm(2) is bonded to one S(6), two equivalent S(1), two equivalent S(4), and two equivalent S(7) atoms to form distorted TmS7 pentagonal bipyramids that share corners with two equivalent Tm(4)S6 octahedra, corners with two equivalent Ce(1)S6 octahedra, corners with four equivalent Tm(3)S6 octahedra,  an edgeedge with one Tm(3)S6 octahedra, edges with three equivalent Tm(4)S6 octahedra, edges with two equivalent Tm(1)S7 pentagonal bipyramids, and faces with two equivalent Tm(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-69°. The Tm(2)-S(6) bond length is 2.93 Å. Both Tm(2)-S(1) bond lengths are 2.91 Å. Both Tm(2)-S(4) bond lengths are 2.73 Å. Both Tm(2)-S(7) bond lengths are 2.83 Å. In the third Tm site, Tm(3) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(5) atoms to form TmS6 octahedra that share  a cornercorner with one Tm(4)S6 octahedra, corners with two equivalent Ce(1)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, corners with four equivalent Tm(2)S7 pentagonal bipyramids, edges with two equivalent Tm(3)S6 octahedra, edges with three equivalent Ce(1)S6 octahedra, and  an edgeedge with one Tm(2)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-58°. The Tm(3)-S(2) bond length is 2.83 Å. The Tm(3)-S(4) bond length is 2.70 Å. Both Tm(3)-S(1) bond lengths are 2.74 Å. Both Tm(3)-S(5) bond lengths are 2.64 Å. In the fourth Tm site, Tm(4) is bonded to one S(3), one S(4), two equivalent S(6), and two equivalent S(7) atoms to form TmS6 octahedra that share  a cornercorner with one Tm(3)S6 octahedra,  a cornercorner with one Ce(1)S6 octahedra, corners with two equivalent Tm(1)S7 pentagonal bipyramids, corners with two equivalent Tm(2)S7 pentagonal bipyramids, edges with two equivalent Tm(4)S6 octahedra, edges with three equivalent Tm(1)S7 pentagonal bipyramids, and edges with three equivalent Tm(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 57-58°. The Tm(4)-S(3) bond length is 2.65 Å. The Tm(4)-S(4) bond length is 2.66 Å. Both Tm(4)-S(6) bond lengths are 2.74 Å. Both Tm(4)-S(7) bond lengths are 2.75 Å. Ce(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(5) atoms to form CeS6 octahedra that share  a cornercorner with one Tm(4)S6 octahedra, corners with two equivalent Tm(3)S6 octahedra, corners with two equivalent Tm(2)S7 pentagonal bipyramids, corners with four equivalent Tm(1)S7 pentagonal bipyramids, edges with two equivalent Ce(1)S6 octahedra, edges with three equivalent Tm(3)S6 octahedra, and  an edgeedge with one Tm(1)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-57°. The Ce(1)-S(1) bond length is 2.91 Å. The Ce(1)-S(3) bond length is 2.78 Å. Both Ce(1)-S(2) bond lengths are 2.86 Å. Both Ce(1)-S(5) bond lengths are 2.76 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Tm(2), two equivalent Tm(3), and one Ce(1) atom to form SCeTm4 trigonal bipyramids that share  a cornercorner with one S(3)CeTm3 tetrahedra, corners with four equivalent S(4)Tm4 tetrahedra, corners with two equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(4)Tm4 tetrahedra,  an edgeedge with one S(7)Tm5 trigonal bipyramid, edges with two equivalent S(2)Ce2Tm3 trigonal bipyramids, and edges with two equivalent S(1)CeTm4 trigonal bipyramids. In the second S site, S(2) is bonded to one Tm(3), two equivalent Tm(1), and two equivalent Ce(1) atoms to form SCe2Tm3 trigonal bipyramids that share  a cornercorner with one S(4)Tm4 tetrahedra, corners with four equivalent S(3)CeTm3 tetrahedra, corners with two equivalent S(6)Tm5 trigonal bipyramids, corners with two equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(3)CeTm3 tetrahedra,  an edgeedge with one S(6)Tm5 trigonal bipyramid, edges with two equivalent S(2)Ce2Tm3 trigonal bipyramids, and edges with two equivalent S(1)CeTm4 trigonal bipyramids. In the third S site, S(3) is bonded to one Tm(4), two equivalent Tm(1), and one Ce(1) atom to form SCeTm3 tetrahedra that share  a cornercorner with one S(4)Tm4 tetrahedra, corners with two equivalent S(3)CeTm3 tetrahedra,  a cornercorner with one S(1)CeTm4 trigonal bipyramid, corners with four equivalent S(2)Ce2Tm3 trigonal bipyramids, corners with four equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(2)Ce2Tm3 trigonal bipyramid,  an edgeedge with one S(6)Tm5 trigonal bipyramid, and edges with two equivalent S(7)Tm5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Tm(3), one Tm(4), and two equivalent Tm(2) atoms to form distorted STm4 tetrahedra that share  a cornercorner with one S(3)CeTm3 tetrahedra, corners with two equivalent S(4)Tm4 tetrahedra,  a cornercorner with one S(2)Ce2Tm3 trigonal bipyramid, corners with four equivalent S(1)CeTm4 trigonal bipyramids, corners with four equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(1)CeTm4 trigonal bipyramid,  an edgeedge with one S(7)Tm5 trigonal bipyramid, and edges with two equivalent S(6)Tm5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to two equivalent Tm(3) and two equivalent Ce(1) atoms. In the sixth S site, S(6) is bonded to one Tm(2), two equivalent Tm(1), and two equivalent Tm(4) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(3)CeTm3 tetrahedra, corners with two equivalent S(2)Ce2Tm3 trigonal bipyramids, corners with two equivalent S(1)CeTm4 trigonal bipyramids, corners with two equivalent S(7)Tm5 trigonal bipyramids,  an edgeedge with one S(3)CeTm3 tetrahedra, edges with two equivalent S(4)Tm4 tetrahedra,  an edgeedge with one S(2)Ce2Tm3 trigonal bipyramid, edges with two equivalent S(6)Tm5 trigonal bipyramids, and edges with three equivalent S(7)Tm5 trigonal bipyramids. In the seventh S site, S(7) is bonded to one Tm(1), two equivalent Tm(2), and two equivalent Tm(4) atoms to form distorted STm5 trigonal bipyramids that share corners with four equivalent S(4)Tm4 tetrahedra, corners with two equivalent S(2)Ce2Tm3 trigonal bipyramids, corners with two equivalent S(1)CeTm4 trigonal bipyramids, corners with two equivalent S(6)Tm5 trigonal bipyramids,  an edgeedge with one S(4)Tm4 tetrahedra, edges with two equivalent S(3)CeTm3 tetrahedra,  an edgeedge with one S(1)CeTm4 trigonal bipyramid, edges with two equivalent S(7)Tm5 trigonal bipyramids, and edges with three equivalent S(6)Tm5 trigonal bipyramids.