La3Si2S8Br crystallizes in the monoclinic C2/c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), three equivalent S(2), and one Br(1) atom. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(3), four equivalent S(4), and one Br(1) atom. Si(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded to one La(2), two equivalent La(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing SLa3Si tetrahedra. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent La(1) and one Si(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one La(2), two equivalent La(1), and one Si(1) atom. In the fourth S site, S(4) is bonded to one La(1), two equivalent La(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing SLa3Si trigonal pyramids. Br(1) is bonded in a 3-coordinate geometry to one La(2) and two equivalent La(1) atoms.
La3Si2S8Br crystallizes in the monoclinic C2/c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), three equivalent S(2), and one Br(1) atom. The La(1)-S(4) bond length is 2.96 Å. There is one shorter (2.99 Å) and one longer (3.06 Å) La(1)-S(1) bond length. There is one shorter (3.07 Å) and one longer (3.14 Å) La(1)-S(3) bond length. There are a spread of La(1)-S(2) bond distances ranging from 2.96-3.08 Å. The La(1)-Br(1) bond length is 3.40 Å. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(3), four equivalent S(4), and one Br(1) atom. Both La(2)-S(1) bond lengths are 2.93 Å. Both La(2)-S(3) bond lengths are 2.94 Å. There are two shorter (3.31 Å) and two longer (3.35 Å) La(2)-S(4) bond lengths. The La(2)-Br(1) bond length is 3.14 Å. Si(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Si(1)-S(1) bond length is 2.13 Å. The Si(1)-S(2) bond length is 2.14 Å. The Si(1)-S(3) bond length is 2.12 Å. The Si(1)-S(4) bond length is 2.12 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one La(2), two equivalent La(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing SLa3Si tetrahedra. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent La(1) and one Si(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one La(2), two equivalent La(1), and one Si(1) atom. In the fourth S site, S(4) is bonded to one La(1), two equivalent La(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing SLa3Si trigonal pyramids. Br(1) is bonded in a 3-coordinate geometry to one La(2) and two equivalent La(1) atoms.