FeSb2S4 crystallizes in the orthorhombic Pnma space group. Fe(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form edge-sharing FeS6 octahedra. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 5-coordinate geometry to two equivalent S(3) and three equivalent S(4) atoms. In the second Sb site, Sb(2) is bonded in a distorted trigonal non-coplanar geometry to one S(1) and two equivalent S(2) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to two equivalent Fe(1) and one Sb(2) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Fe(1) and two equivalent Sb(2) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Fe(1) and two equivalent Sb(1) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Fe(1) and three equivalent Sb(1) atoms.
FeSb2S4 crystallizes in the orthorhombic Pnma space group. Fe(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form edge-sharing FeS6 octahedra. The Fe(1)-S(2) bond length is 2.23 Å. The Fe(1)-S(3) bond length is 2.27 Å. Both Fe(1)-S(1) bond lengths are 2.36 Å. Both Fe(1)-S(4) bond lengths are 2.34 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 5-coordinate geometry to two equivalent S(3) and three equivalent S(4) atoms. Both Sb(1)-S(3) bond lengths are 2.59 Å. There is one shorter (2.62 Å) and two longer (3.01 Å) Sb(1)-S(4) bond lengths. In the second Sb site, Sb(2) is bonded in a distorted trigonal non-coplanar geometry to one S(1) and two equivalent S(2) atoms. The Sb(2)-S(1) bond length is 2.53 Å. Both Sb(2)-S(2) bond lengths are 2.56 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to two equivalent Fe(1) and one Sb(2) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Fe(1) and two equivalent Sb(2) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Fe(1) and two equivalent Sb(1) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Fe(1) and three equivalent Sb(1) atoms.