Ba3FeS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(2), and four equivalent S(1) atoms. Fe(1) is bonded in a tetrahedral geometry to one S(3), one S(4), and two equivalent S(1) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), and one Fe(1) atom. In the second S site, S(2) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form distorted corner-sharing SBa6 octahedra. The corner-sharing octahedral tilt angles range from 31-46°. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), four equivalent Ba(1), and one Fe(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(2), four equivalent Ba(1), and one Fe(1) atom.
Ba3FeS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. There is one shorter (3.30 Å) and one longer (3.38 Å) Ba(1)-S(2) bond length. There is one shorter (3.27 Å) and one longer (3.38 Å) Ba(1)-S(3) bond length. There is one shorter (3.29 Å) and one longer (3.43 Å) Ba(1)-S(4) bond length. There are a spread of Ba(1)-S(1) bond distances ranging from 3.30-3.72 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(2), and four equivalent S(1) atoms. The Ba(2)-S(3) bond length is 3.24 Å. The Ba(2)-S(4) bond length is 3.15 Å. There is one shorter (3.13 Å) and one longer (3.58 Å) Ba(2)-S(2) bond length. There are two shorter (3.10 Å) and two longer (3.24 Å) Ba(2)-S(1) bond lengths. Fe(1) is bonded in a tetrahedral geometry to one S(3), one S(4), and two equivalent S(1) atoms. The Fe(1)-S(3) bond length is 2.17 Å. The Fe(1)-S(4) bond length is 2.20 Å. Both Fe(1)-S(1) bond lengths are 2.18 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), and one Fe(1) atom. In the second S site, S(2) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form distorted corner-sharing SBa6 octahedra. The corner-sharing octahedral tilt angles range from 31-46°. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), four equivalent Ba(1), and one Fe(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(2), four equivalent Ba(1), and one Fe(1) atom.