Ba3FeS5 crystallizes in the hexagonal P-6 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), two equivalent S(5), and two equivalent S(7) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(4), two equivalent S(6), and two equivalent S(8) atoms. In the third Ba site, Ba(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(3), one S(6), one S(7), one S(9), and three equivalent S(5) atoms. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one S(10), one S(2), one S(4), one S(5), one S(8), one S(9), and three equivalent S(6) atoms. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to three equivalent S(3) and three equivalent S(5) atoms to form face-sharing FeS6 octahedra. In the second Fe site, Fe(2) is bonded to three equivalent S(4) and three equivalent S(6) atoms to form face-sharing FeS6 octahedra. In the third Fe site, Fe(3) is bonded to three equivalent S(5) and three equivalent S(6) atoms to form face-sharing FeS6 octahedra. There are ten inequivalent S sites. In the first S site, S(5) is bonded in a 7-coordinate geometry to one Ba(1), one Ba(4), three equivalent Ba(3), one Fe(1), and one Fe(3) atom. In the second S site, S(6) is bonded in a 7-coordinate geometry to one Ba(2), one Ba(3), three equivalent Ba(4), one Fe(2), and one Fe(3) atom. In the third S site, S(7) is bonded to three equivalent Ba(1), three equivalent Ba(3), and one S(7) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(1)Ba6S pentagonal bipyramids, corners with three equivalent S(10)Ba6S pentagonal bipyramids, edges with three equivalent S(1)Ba6S pentagonal bipyramids,  a faceface with one S(9)Ba6 octahedra, and  a faceface with one S(7)Ba6S pentagonal bipyramid. In the fourth S site, S(8) is bonded to three equivalent Ba(2), three equivalent Ba(4), and one S(8) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(2)Ba6 octahedra, corners with three equivalent S(10)Ba6S pentagonal bipyramids, edges with three equivalent S(2)Ba6 octahedra,  a faceface with one S(9)Ba6 octahedra, and  a faceface with one S(8)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 45°. In the fifth S site, S(9) is bonded to three equivalent Ba(3) and three equivalent Ba(4) atoms to form SBa6 octahedra that share corners with three equivalent S(2)Ba6 octahedra, corners with three equivalent S(1)Ba6S pentagonal bipyramids, edges with three equivalent S(10)Ba6S pentagonal bipyramids,  a faceface with one S(7)Ba6S pentagonal bipyramid, and  a faceface with one S(8)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 43°. In the sixth S site, S(10) is bonded to three equivalent Ba(3), three equivalent Ba(4), and one S(1) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(7)Ba6S pentagonal bipyramids, corners with three equivalent S(8)Ba6S pentagonal bipyramids, edges with three equivalent S(9)Ba6 octahedra,  a faceface with one S(2)Ba6 octahedra, and  a faceface with one S(1)Ba6S pentagonal bipyramid. In the seventh S site, S(1) is bonded to three equivalent Ba(1), three equivalent Ba(3), and one S(10) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(9)Ba6 octahedra, corners with three equivalent S(7)Ba6S pentagonal bipyramids, edges with three equivalent S(7)Ba6S pentagonal bipyramids,  a faceface with one S(1)Ba6S pentagonal bipyramid, and  a faceface with one S(10)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 44°. In the eighth S site, S(2) is bonded to three equivalent Ba(2) and three equivalent Ba(4) atoms to form SBa6 octahedra that share corners with three equivalent S(9)Ba6 octahedra, corners with three equivalent S(8)Ba6S pentagonal bipyramids, edges with three equivalent S(8)Ba6S pentagonal bipyramids,  a faceface with one S(2)Ba6 octahedra, and  a faceface with one S(10)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 43°. In the ninth S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), and two equivalent Fe(1) atoms. In the tenth S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent Ba(4), and two equivalent Fe(2) atoms.
Ba3FeS5 crystallizes in the hexagonal P-6 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), two equivalent S(5), and two equivalent S(7) atoms. Both Ba(1)-S(1) bond lengths are 3.43 Å. There is one shorter (2.97 Å) and one longer (3.03 Å) Ba(1)-S(3) bond length. Both Ba(1)-S(5) bond lengths are 3.32 Å. Both Ba(1)-S(7) bond lengths are 3.30 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(4), two equivalent S(6), and two equivalent S(8) atoms. Both Ba(2)-S(2) bond lengths are 3.29 Å. There is one shorter (2.99 Å) and one longer (3.11 Å) Ba(2)-S(4) bond length. Both Ba(2)-S(6) bond lengths are 3.41 Å. Both Ba(2)-S(8) bond lengths are 3.38 Å. In the third Ba site, Ba(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(3), one S(6), one S(7), one S(9), and three equivalent S(5) atoms. The Ba(3)-S(1) bond length is 3.29 Å. The Ba(3)-S(10) bond length is 3.29 Å. The Ba(3)-S(3) bond length is 3.34 Å. The Ba(3)-S(6) bond length is 3.36 Å. The Ba(3)-S(7) bond length is 3.43 Å. The Ba(3)-S(9) bond length is 3.20 Å. There are a spread of Ba(3)-S(5) bond distances ranging from 3.02-3.83 Å. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one S(10), one S(2), one S(4), one S(5), one S(8), one S(9), and three equivalent S(6) atoms. The Ba(4)-S(10) bond length is 3.59 Å. The Ba(4)-S(2) bond length is 3.20 Å. The Ba(4)-S(4) bond length is 3.37 Å. The Ba(4)-S(5) bond length is 3.41 Å. The Ba(4)-S(8) bond length is 3.50 Å. The Ba(4)-S(9) bond length is 3.29 Å. There are a spread of Ba(4)-S(6) bond distances ranging from 3.06-3.81 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to three equivalent S(3) and three equivalent S(5) atoms to form face-sharing FeS6 octahedra. All Fe(1)-S(3) bond lengths are 2.70 Å. All Fe(1)-S(5) bond lengths are 2.44 Å. In the second Fe site, Fe(2) is bonded to three equivalent S(4) and three equivalent S(6) atoms to form face-sharing FeS6 octahedra. All Fe(2)-S(4) bond lengths are 2.62 Å. All Fe(2)-S(6) bond lengths are 2.49 Å. In the third Fe site, Fe(3) is bonded to three equivalent S(5) and three equivalent S(6) atoms to form face-sharing FeS6 octahedra. All Fe(3)-S(5) bond lengths are 2.59 Å. All Fe(3)-S(6) bond lengths are 2.51 Å. There are ten inequivalent S sites. In the first S site, S(5) is bonded in a 7-coordinate geometry to one Ba(1), one Ba(4), three equivalent Ba(3), one Fe(1), and one Fe(3) atom. In the second S site, S(6) is bonded in a 7-coordinate geometry to one Ba(2), one Ba(3), three equivalent Ba(4), one Fe(2), and one Fe(3) atom. In the third S site, S(7) is bonded to three equivalent Ba(1), three equivalent Ba(3), and one S(7) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(1)Ba6S pentagonal bipyramids, corners with three equivalent S(10)Ba6S pentagonal bipyramids, edges with three equivalent S(1)Ba6S pentagonal bipyramids,  a faceface with one S(9)Ba6 octahedra, and  a faceface with one S(7)Ba6S pentagonal bipyramid. The S(7)-S(7) bond length is 2.13 Å. In the fourth S site, S(8) is bonded to three equivalent Ba(2), three equivalent Ba(4), and one S(8) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(2)Ba6 octahedra, corners with three equivalent S(10)Ba6S pentagonal bipyramids, edges with three equivalent S(2)Ba6 octahedra,  a faceface with one S(9)Ba6 octahedra, and  a faceface with one S(8)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 45°. The S(8)-S(8) bond length is 2.12 Å. In the fifth S site, S(9) is bonded to three equivalent Ba(3) and three equivalent Ba(4) atoms to form SBa6 octahedra that share corners with three equivalent S(2)Ba6 octahedra, corners with three equivalent S(1)Ba6S pentagonal bipyramids, edges with three equivalent S(10)Ba6S pentagonal bipyramids,  a faceface with one S(7)Ba6S pentagonal bipyramid, and  a faceface with one S(8)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 43°. In the sixth S site, S(10) is bonded to three equivalent Ba(3), three equivalent Ba(4), and one S(1) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(7)Ba6S pentagonal bipyramids, corners with three equivalent S(8)Ba6S pentagonal bipyramids, edges with three equivalent S(9)Ba6 octahedra,  a faceface with one S(2)Ba6 octahedra, and  a faceface with one S(1)Ba6S pentagonal bipyramid. The S(10)-S(1) bond length is 2.20 Å. In the seventh S site, S(1) is bonded to three equivalent Ba(1), three equivalent Ba(3), and one S(10) atom to form distorted SBa6S pentagonal bipyramids that share corners with three equivalent S(9)Ba6 octahedra, corners with three equivalent S(7)Ba6S pentagonal bipyramids, edges with three equivalent S(7)Ba6S pentagonal bipyramids,  a faceface with one S(1)Ba6S pentagonal bipyramid, and  a faceface with one S(10)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 44°. In the eighth S site, S(2) is bonded to three equivalent Ba(2) and three equivalent Ba(4) atoms to form SBa6 octahedra that share corners with three equivalent S(9)Ba6 octahedra, corners with three equivalent S(8)Ba6S pentagonal bipyramids, edges with three equivalent S(8)Ba6S pentagonal bipyramids,  a faceface with one S(2)Ba6 octahedra, and  a faceface with one S(10)Ba6S pentagonal bipyramid. The corner-sharing octahedral tilt angles are 43°. In the ninth S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), and two equivalent Fe(1) atoms. In the tenth S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent Ba(4), and two equivalent Fe(2) atoms.