La2SbS5Br crystallizes in the orthorhombic Pnma space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 10-coordinate geometry to one S(3), one S(4), two equivalent S(1), three equivalent S(2), and three equivalent Br(1) atoms. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent S(3), two equivalent S(4), four equivalent S(1), and one Br(1) atom. Sb(1) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(4), and two equivalent S(3) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded to one La(1), two equivalent La(2), and one S(1) atom to form SLa3S tetrahedra that share corners with three equivalent S(2)La3Sb tetrahedra, corners with three equivalent Br(1)La4 tetrahedra, corners with four equivalent S(1)La3S tetrahedra,  a cornercorner with one S(3)La3Sb2 trigonal bipyramid, corners with five equivalent S(4)La3Sb trigonal pyramids,  an edgeedge with one Br(1)La4 tetrahedra, edges with two equivalent S(3)La3Sb2 trigonal bipyramids, and  a faceface with one S(1)La3S tetrahedra. In the second S site, S(2) is bonded to three equivalent La(1) and one Sb(1) atom to form distorted SLa3Sb tetrahedra that share corners with two equivalent S(2)La3Sb tetrahedra, corners with six equivalent S(1)La3S tetrahedra, corners with seven equivalent Br(1)La4 tetrahedra,  a cornercorner with one S(3)La3Sb2 trigonal bipyramid, corners with two equivalent S(4)La3Sb trigonal pyramids,  an edgeedge with one Br(1)La4 tetrahedra, edges with two equivalent S(2)La3Sb tetrahedra, edges with two equivalent S(3)La3Sb2 trigonal bipyramids, and  an edgeedge with one S(4)La3Sb trigonal pyramid. In the third S site, S(3) is bonded to one La(1), two equivalent La(2), and two equivalent Sb(1) atoms to form SLa3Sb2 trigonal bipyramids that share  a cornercorner with one S(2)La3Sb tetrahedra, corners with two equivalent S(1)La3S tetrahedra, corners with five equivalent Br(1)La4 tetrahedra, corners with four equivalent S(3)La3Sb2 trigonal bipyramids, corners with three equivalent S(4)La3Sb trigonal pyramids, edges with two equivalent S(2)La3Sb tetrahedra, edges with four equivalent S(1)La3S tetrahedra, and edges with two equivalent S(4)La3Sb trigonal pyramids. In the fourth S site, S(4) is bonded to one La(1), two equivalent La(2), and one Sb(1) atom to form SLa3Sb trigonal pyramids that share  a cornercorner with one Br(1)La4 tetrahedra, corners with two equivalent S(2)La3Sb tetrahedra, corners with ten equivalent S(1)La3S tetrahedra, corners with three equivalent S(3)La3Sb2 trigonal bipyramids, corners with two equivalent S(4)La3Sb trigonal pyramids,  an edgeedge with one S(2)La3Sb tetrahedra, edges with two equivalent Br(1)La4 tetrahedra, and edges with two equivalent S(3)La3Sb2 trigonal bipyramids. Br(1) is bonded to one La(2) and three equivalent La(1) atoms to form BrLa4 tetrahedra that share corners with two equivalent Br(1)La4 tetrahedra, corners with six equivalent S(1)La3S tetrahedra, corners with seven equivalent S(2)La3Sb tetrahedra, corners with five equivalent S(3)La3Sb2 trigonal bipyramids,  a cornercorner with one S(4)La3Sb trigonal pyramid,  an edgeedge with one S(2)La3Sb tetrahedra, edges with two equivalent S(1)La3S tetrahedra, edges with two equivalent Br(1)La4 tetrahedra, and edges with two equivalent S(4)La3Sb trigonal pyramids.
La2SbS5Br crystallizes in the orthorhombic Pnma space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 10-coordinate geometry to one S(3), one S(4), two equivalent S(1), three equivalent S(2), and three equivalent Br(1) atoms. The La(1)-S(3) bond length is 3.15 Å. The La(1)-S(4) bond length is 3.15 Å. Both La(1)-S(1) bond lengths are 3.00 Å. There is one shorter (2.99 Å) and two longer (3.09 Å) La(1)-S(2) bond lengths. There is one shorter (3.33 Å) and two longer (3.36 Å) La(1)-Br(1) bond lengths. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent S(3), two equivalent S(4), four equivalent S(1), and one Br(1) atom. There is one shorter (3.03 Å) and one longer (3.08 Å) La(2)-S(3) bond length. Both La(2)-S(4) bond lengths are 3.00 Å. There are two shorter (3.02 Å) and two longer (3.04 Å) La(2)-S(1) bond lengths. The La(2)-Br(1) bond length is 3.15 Å. Sb(1) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(4), and two equivalent S(3) atoms. The Sb(1)-S(2) bond length is 2.41 Å. The Sb(1)-S(4) bond length is 2.46 Å. Both Sb(1)-S(3) bond lengths are 2.77 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one La(1), two equivalent La(2), and one S(1) atom to form SLa3S tetrahedra that share corners with three equivalent S(2)La3Sb tetrahedra, corners with three equivalent Br(1)La4 tetrahedra, corners with four equivalent S(1)La3S tetrahedra,  a cornercorner with one S(3)La3Sb2 trigonal bipyramid, corners with five equivalent S(4)La3Sb trigonal pyramids,  an edgeedge with one Br(1)La4 tetrahedra, edges with two equivalent S(3)La3Sb2 trigonal bipyramids, and  a faceface with one S(1)La3S tetrahedra. The S(1)-S(1) bond length is 2.08 Å. In the second S site, S(2) is bonded to three equivalent La(1) and one Sb(1) atom to form distorted SLa3Sb tetrahedra that share corners with two equivalent S(2)La3Sb tetrahedra, corners with six equivalent S(1)La3S tetrahedra, corners with seven equivalent Br(1)La4 tetrahedra,  a cornercorner with one S(3)La3Sb2 trigonal bipyramid, corners with two equivalent S(4)La3Sb trigonal pyramids,  an edgeedge with one Br(1)La4 tetrahedra, edges with two equivalent S(2)La3Sb tetrahedra, edges with two equivalent S(3)La3Sb2 trigonal bipyramids, and  an edgeedge with one S(4)La3Sb trigonal pyramid. In the third S site, S(3) is bonded to one La(1), two equivalent La(2), and two equivalent Sb(1) atoms to form SLa3Sb2 trigonal bipyramids that share  a cornercorner with one S(2)La3Sb tetrahedra, corners with two equivalent S(1)La3S tetrahedra, corners with five equivalent Br(1)La4 tetrahedra, corners with four equivalent S(3)La3Sb2 trigonal bipyramids, corners with three equivalent S(4)La3Sb trigonal pyramids, edges with two equivalent S(2)La3Sb tetrahedra, edges with four equivalent S(1)La3S tetrahedra, and edges with two equivalent S(4)La3Sb trigonal pyramids. In the fourth S site, S(4) is bonded to one La(1), two equivalent La(2), and one Sb(1) atom to form SLa3Sb trigonal pyramids that share  a cornercorner with one Br(1)La4 tetrahedra, corners with two equivalent S(2)La3Sb tetrahedra, corners with ten equivalent S(1)La3S tetrahedra, corners with three equivalent S(3)La3Sb2 trigonal bipyramids, corners with two equivalent S(4)La3Sb trigonal pyramids,  an edgeedge with one S(2)La3Sb tetrahedra, edges with two equivalent Br(1)La4 tetrahedra, and edges with two equivalent S(3)La3Sb2 trigonal bipyramids. Br(1) is bonded to one La(2) and three equivalent La(1) atoms to form BrLa4 tetrahedra that share corners with two equivalent Br(1)La4 tetrahedra, corners with six equivalent S(1)La3S tetrahedra, corners with seven equivalent S(2)La3Sb tetrahedra, corners with five equivalent S(3)La3Sb2 trigonal bipyramids,  a cornercorner with one S(4)La3Sb trigonal pyramid,  an edgeedge with one S(2)La3Sb tetrahedra, edges with two equivalent S(1)La3S tetrahedra, edges with two equivalent Br(1)La4 tetrahedra, and edges with two equivalent S(4)La3Sb trigonal pyramids.