FeBiS2Br crystallizes in the monoclinic C2/m space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form FeS6 octahedra that share corners with two equivalent Fe(2)S2Br4 octahedra and edges with two equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 37°. In the second Fe site, Fe(2) is bonded to two equivalent S(2) and four equivalent Br(1) atoms to form FeS2Br4 octahedra that share corners with two equivalent Fe(1)S6 octahedra and edges with two equivalent Fe(2)S2Br4 octahedra. The corner-sharing octahedral tilt angles are 37°. Bi(1) is bonded in a 6-coordinate geometry to two equivalent S(2), three equivalent S(1), and one Br(1) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Fe(1) and three equivalent Bi(1) atoms. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Fe(1), one Fe(2), and two equivalent Bi(1) atoms. Br(1) is bonded in a distorted water-like geometry to two equivalent Fe(2) and one Bi(1) atom.
FeBiS2Br crystallizes in the monoclinic C2/m space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form FeS6 octahedra that share corners with two equivalent Fe(2)S2Br4 octahedra and edges with two equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 37°. Both Fe(1)-S(2) bond lengths are 2.36 Å. All Fe(1)-S(1) bond lengths are 2.37 Å. In the second Fe site, Fe(2) is bonded to two equivalent S(2) and four equivalent Br(1) atoms to form FeS2Br4 octahedra that share corners with two equivalent Fe(1)S6 octahedra and edges with two equivalent Fe(2)S2Br4 octahedra. The corner-sharing octahedral tilt angles are 37°. Both Fe(2)-S(2) bond lengths are 2.32 Å. All Fe(2)-Br(1) bond lengths are 2.46 Å. Bi(1) is bonded in a 6-coordinate geometry to two equivalent S(2), three equivalent S(1), and one Br(1) atom. Both Bi(1)-S(2) bond lengths are 2.70 Å. There is one shorter (2.64 Å) and two longer (3.11 Å) Bi(1)-S(1) bond lengths. The Bi(1)-Br(1) bond length is 3.16 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Fe(1) and three equivalent Bi(1) atoms. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Fe(1), one Fe(2), and two equivalent Bi(1) atoms. Br(1) is bonded in a distorted water-like geometry to two equivalent Fe(2) and one Bi(1) atom.