CeLaSbS5Br crystallizes in the orthorhombic P2_12_12_1 space group. Ce(1) is bonded in a 10-coordinate geometry to one S(1), one S(2), one S(4), one S(5), three equivalent S(3), and three equivalent Br(1) atoms. La(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(4), two equivalent S(5), and one Br(1) atom. Sb(1) is bonded in a 3-coordinate geometry to one S(2), one S(3), and two equivalent S(5) atoms. There are five inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent La(1), and one S(4) atom to form SLa2CeS tetrahedra that share corners with two equivalent S(1)La2CeS tetrahedra, corners with two equivalent S(4)La2CeS tetrahedra, corners with three equivalent S(3)Ce3Sb tetrahedra, corners with three equivalent Br(1)LaCe3 tetrahedra,  a cornercorner with one S(5)La2CeSb2 trigonal bipyramid, corners with five equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one Br(1)LaCe3 tetrahedra, edges with two equivalent S(5)La2CeSb2 trigonal bipyramids, and  a faceface with one S(4)La2CeS tetrahedra. In the second S site, S(2) is bonded to one Ce(1), two equivalent La(1), and one Sb(1) atom to form SLa2CeSb trigonal pyramids that share  a cornercorner with one Br(1)LaCe3 tetrahedra, corners with two equivalent S(3)Ce3Sb tetrahedra, corners with five equivalent S(1)La2CeS tetrahedra, corners with five equivalent S(4)La2CeS tetrahedra, corners with three equivalent S(5)La2CeSb2 trigonal bipyramids, corners with two equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one S(3)Ce3Sb tetrahedra, edges with two equivalent Br(1)LaCe3 tetrahedra, and edges with two equivalent S(5)La2CeSb2 trigonal bipyramids. In the third S site, S(3) is bonded to three equivalent Ce(1) and one Sb(1) atom to form distorted SCe3Sb tetrahedra that share corners with two equivalent S(3)Ce3Sb tetrahedra, corners with three equivalent S(1)La2CeS tetrahedra, corners with three equivalent S(4)La2CeS tetrahedra, corners with seven equivalent Br(1)LaCe3 tetrahedra,  a cornercorner with one S(5)La2CeSb2 trigonal bipyramid, corners with two equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one Br(1)LaCe3 tetrahedra, edges with two equivalent S(3)Ce3Sb tetrahedra, edges with two equivalent S(5)La2CeSb2 trigonal bipyramids, and  an edgeedge with one S(2)La2CeSb trigonal pyramid. In the fourth S site, S(4) is bonded to one Ce(1), two equivalent La(1), and one S(1) atom to form SLa2CeS tetrahedra that share corners with two equivalent S(1)La2CeS tetrahedra, corners with two equivalent S(4)La2CeS tetrahedra, corners with three equivalent S(3)Ce3Sb tetrahedra, corners with three equivalent Br(1)LaCe3 tetrahedra,  a cornercorner with one S(5)La2CeSb2 trigonal bipyramid, corners with five equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one Br(1)LaCe3 tetrahedra, edges with two equivalent S(5)La2CeSb2 trigonal bipyramids, and  a faceface with one S(1)La2CeS tetrahedra. In the fifth S site, S(5) is bonded to one Ce(1), two equivalent La(1), and two equivalent Sb(1) atoms to form distorted SLa2CeSb2 trigonal bipyramids that share  a cornercorner with one S(3)Ce3Sb tetrahedra,  a cornercorner with one S(1)La2CeS tetrahedra,  a cornercorner with one S(4)La2CeS tetrahedra, corners with five equivalent Br(1)LaCe3 tetrahedra, corners with four equivalent S(5)La2CeSb2 trigonal bipyramids, corners with three equivalent S(2)La2CeSb trigonal pyramids, edges with two equivalent S(3)Ce3Sb tetrahedra, edges with two equivalent S(1)La2CeS tetrahedra, edges with two equivalent S(4)La2CeS tetrahedra, and edges with two equivalent S(2)La2CeSb trigonal pyramids. Br(1) is bonded to three equivalent Ce(1) and one La(1) atom to form distorted BrLaCe3 tetrahedra that share corners with two equivalent Br(1)LaCe3 tetrahedra, corners with three equivalent S(1)La2CeS tetrahedra, corners with three equivalent S(4)La2CeS tetrahedra, corners with seven equivalent S(3)Ce3Sb tetrahedra, corners with five equivalent S(5)La2CeSb2 trigonal bipyramids,  a cornercorner with one S(2)La2CeSb trigonal pyramid,  an edgeedge with one S(3)Ce3Sb tetrahedra,  an edgeedge with one S(1)La2CeS tetrahedra,  an edgeedge with one S(4)La2CeS tetrahedra, edges with two equivalent Br(1)LaCe3 tetrahedra, and edges with two equivalent S(2)La2CeSb trigonal pyramids.
CeLaSbS5Br crystallizes in the orthorhombic P2_12_12_1 space group. Ce(1) is bonded in a 10-coordinate geometry to one S(1), one S(2), one S(4), one S(5), three equivalent S(3), and three equivalent Br(1) atoms. The Ce(1)-S(1) bond length is 2.96 Å. The Ce(1)-S(2) bond length is 3.08 Å. The Ce(1)-S(4) bond length is 2.96 Å. The Ce(1)-S(5) bond length is 3.10 Å. There are a spread of Ce(1)-S(3) bond distances ranging from 2.93-3.11 Å. There are two shorter (3.39 Å) and one longer (3.40 Å) Ce(1)-Br(1) bond length. La(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(4), two equivalent S(5), and one Br(1) atom. There is one shorter (3.04 Å) and one longer (3.05 Å) La(1)-S(1) bond length. There is one shorter (3.01 Å) and one longer (3.04 Å) La(1)-S(2) bond length. Both La(1)-S(4) bond lengths are 3.04 Å. There is one shorter (3.04 Å) and one longer (3.05 Å) La(1)-S(5) bond length. The La(1)-Br(1) bond length is 3.10 Å. Sb(1) is bonded in a 3-coordinate geometry to one S(2), one S(3), and two equivalent S(5) atoms. The Sb(1)-S(2) bond length is 2.48 Å. The Sb(1)-S(3) bond length is 2.44 Å. There is one shorter (2.51 Å) and one longer (3.10 Å) Sb(1)-S(5) bond length. There are five inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent La(1), and one S(4) atom to form SLa2CeS tetrahedra that share corners with two equivalent S(1)La2CeS tetrahedra, corners with two equivalent S(4)La2CeS tetrahedra, corners with three equivalent S(3)Ce3Sb tetrahedra, corners with three equivalent Br(1)LaCe3 tetrahedra,  a cornercorner with one S(5)La2CeSb2 trigonal bipyramid, corners with five equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one Br(1)LaCe3 tetrahedra, edges with two equivalent S(5)La2CeSb2 trigonal bipyramids, and  a faceface with one S(4)La2CeS tetrahedra. The S(1)-S(4) bond length is 2.09 Å. In the second S site, S(2) is bonded to one Ce(1), two equivalent La(1), and one Sb(1) atom to form SLa2CeSb trigonal pyramids that share  a cornercorner with one Br(1)LaCe3 tetrahedra, corners with two equivalent S(3)Ce3Sb tetrahedra, corners with five equivalent S(1)La2CeS tetrahedra, corners with five equivalent S(4)La2CeS tetrahedra, corners with three equivalent S(5)La2CeSb2 trigonal bipyramids, corners with two equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one S(3)Ce3Sb tetrahedra, edges with two equivalent Br(1)LaCe3 tetrahedra, and edges with two equivalent S(5)La2CeSb2 trigonal bipyramids. In the third S site, S(3) is bonded to three equivalent Ce(1) and one Sb(1) atom to form distorted SCe3Sb tetrahedra that share corners with two equivalent S(3)Ce3Sb tetrahedra, corners with three equivalent S(1)La2CeS tetrahedra, corners with three equivalent S(4)La2CeS tetrahedra, corners with seven equivalent Br(1)LaCe3 tetrahedra,  a cornercorner with one S(5)La2CeSb2 trigonal bipyramid, corners with two equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one Br(1)LaCe3 tetrahedra, edges with two equivalent S(3)Ce3Sb tetrahedra, edges with two equivalent S(5)La2CeSb2 trigonal bipyramids, and  an edgeedge with one S(2)La2CeSb trigonal pyramid. In the fourth S site, S(4) is bonded to one Ce(1), two equivalent La(1), and one S(1) atom to form SLa2CeS tetrahedra that share corners with two equivalent S(1)La2CeS tetrahedra, corners with two equivalent S(4)La2CeS tetrahedra, corners with three equivalent S(3)Ce3Sb tetrahedra, corners with three equivalent Br(1)LaCe3 tetrahedra,  a cornercorner with one S(5)La2CeSb2 trigonal bipyramid, corners with five equivalent S(2)La2CeSb trigonal pyramids,  an edgeedge with one Br(1)LaCe3 tetrahedra, edges with two equivalent S(5)La2CeSb2 trigonal bipyramids, and  a faceface with one S(1)La2CeS tetrahedra. In the fifth S site, S(5) is bonded to one Ce(1), two equivalent La(1), and two equivalent Sb(1) atoms to form distorted SLa2CeSb2 trigonal bipyramids that share  a cornercorner with one S(3)Ce3Sb tetrahedra,  a cornercorner with one S(1)La2CeS tetrahedra,  a cornercorner with one S(4)La2CeS tetrahedra, corners with five equivalent Br(1)LaCe3 tetrahedra, corners with four equivalent S(5)La2CeSb2 trigonal bipyramids, corners with three equivalent S(2)La2CeSb trigonal pyramids, edges with two equivalent S(3)Ce3Sb tetrahedra, edges with two equivalent S(1)La2CeS tetrahedra, edges with two equivalent S(4)La2CeS tetrahedra, and edges with two equivalent S(2)La2CeSb trigonal pyramids. Br(1) is bonded to three equivalent Ce(1) and one La(1) atom to form distorted BrLaCe3 tetrahedra that share corners with two equivalent Br(1)LaCe3 tetrahedra, corners with three equivalent S(1)La2CeS tetrahedra, corners with three equivalent S(4)La2CeS tetrahedra, corners with seven equivalent S(3)Ce3Sb tetrahedra, corners with five equivalent S(5)La2CeSb2 trigonal bipyramids,  a cornercorner with one S(2)La2CeSb trigonal pyramid,  an edgeedge with one S(3)Ce3Sb tetrahedra,  an edgeedge with one S(1)La2CeS tetrahedra,  an edgeedge with one S(4)La2CeS tetrahedra, edges with two equivalent Br(1)LaCe3 tetrahedra, and edges with two equivalent S(2)La2CeSb trigonal pyramids.