Ba6Ti5S15O crystallizes in the orthorhombic C222_1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one S(2), one S(3), one S(4), one S(5), one S(6), one S(7), three equivalent S(8), and one O(1) atom. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one S(2), one S(3), one S(5), one S(6), one S(7), one S(8), and three equivalent S(4) atoms. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one S(3), two equivalent S(2), two equivalent S(5), two equivalent S(6), and three equivalent S(1) atoms. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), one S(3), one S(5), one S(6), and one S(8) atom to form face-sharing TiS6 octahedra. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one S(2), one S(3), one S(4), one S(7), one S(8), and one O(1) atom. In the third Ti site, Ti(3) is bonded to two equivalent S(1), two equivalent S(5), and two equivalent S(6) atoms to form face-sharing TiS6 octahedra. There are eight inequivalent S sites. In the first S site, S(8) is bonded in a 6-coordinate geometry to one Ba(2), three equivalent Ba(1), one Ti(1), and one Ti(2) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to three equivalent Ba(3), one Ti(1), and one Ti(3) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), two equivalent Ba(3), one Ti(1), and one Ti(2) atom. In the fourth S site, S(3) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ti(1), and one Ti(2) atom. In the fifth S site, S(4) is bonded in a 5-coordinate geometry to one Ba(1), three equivalent Ba(2), and one Ti(2) atom. In the sixth S site, S(5) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), one Ti(1), and one Ti(3) atom to form a mixture of distorted face, corner, and edge-sharing SBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. In the seventh S site, S(6) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), one Ti(1), and one Ti(3) atom to form a mixture of distorted face, corner, and edge-sharing SBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 7-64°. In the eighth S site, S(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Ti(2) atoms to form distorted corner-sharing SBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 8-64°. O(1) is bonded in a linear geometry to two equivalent Ba(1) and two equivalent Ti(2) atoms.
Ba6Ti5S15O crystallizes in the orthorhombic C222_1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one S(2), one S(3), one S(4), one S(5), one S(6), one S(7), three equivalent S(8), and one O(1) atom. The Ba(1)-S(2) bond length is 3.26 Å. The Ba(1)-S(3) bond length is 3.18 Å. The Ba(1)-S(4) bond length is 3.17 Å. The Ba(1)-S(5) bond length is 3.23 Å. The Ba(1)-S(6) bond length is 3.38 Å. The Ba(1)-S(7) bond length is 3.24 Å. There are a spread of Ba(1)-S(8) bond distances ranging from 3.19-3.44 Å. The Ba(1)-O(1) bond length is 3.44 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one S(2), one S(3), one S(5), one S(6), one S(7), one S(8), and three equivalent S(4) atoms. The Ba(2)-S(2) bond length is 3.25 Å. The Ba(2)-S(3) bond length is 3.25 Å. The Ba(2)-S(5) bond length is 3.40 Å. The Ba(2)-S(6) bond length is 3.37 Å. The Ba(2)-S(7) bond length is 3.41 Å. The Ba(2)-S(8) bond length is 3.18 Å. There are a spread of Ba(2)-S(4) bond distances ranging from 3.41-3.49 Å. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one S(3), two equivalent S(2), two equivalent S(5), two equivalent S(6), and three equivalent S(1) atoms. The Ba(3)-S(3) bond length is 3.36 Å. There is one shorter (3.38 Å) and one longer (3.77 Å) Ba(3)-S(2) bond length. There is one shorter (3.37 Å) and one longer (3.43 Å) Ba(3)-S(5) bond length. There is one shorter (3.30 Å) and one longer (3.42 Å) Ba(3)-S(6) bond length. There are a spread of Ba(3)-S(1) bond distances ranging from 3.26-3.42 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), one S(3), one S(5), one S(6), and one S(8) atom to form face-sharing TiS6 octahedra. The Ti(1)-S(1) bond length is 2.47 Å. The Ti(1)-S(2) bond length is 2.29 Å. The Ti(1)-S(3) bond length is 2.53 Å. The Ti(1)-S(5) bond length is 2.66 Å. The Ti(1)-S(6) bond length is 2.38 Å. The Ti(1)-S(8) bond length is 2.40 Å. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one S(2), one S(3), one S(4), one S(7), one S(8), and one O(1) atom. The Ti(2)-S(2) bond length is 2.73 Å. The Ti(2)-S(3) bond length is 2.42 Å. The Ti(2)-S(4) bond length is 2.28 Å. The Ti(2)-S(7) bond length is 2.48 Å. The Ti(2)-S(8) bond length is 2.67 Å. The Ti(2)-O(1) bond length is 1.86 Å. In the third Ti site, Ti(3) is bonded to two equivalent S(1), two equivalent S(5), and two equivalent S(6) atoms to form face-sharing TiS6 octahedra. Both Ti(3)-S(1) bond lengths are 2.43 Å. Both Ti(3)-S(5) bond lengths are 2.33 Å. Both Ti(3)-S(6) bond lengths are 2.58 Å. There are eight inequivalent S sites. In the first S site, S(8) is bonded in a 6-coordinate geometry to one Ba(2), three equivalent Ba(1), one Ti(1), and one Ti(2) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to three equivalent Ba(3), one Ti(1), and one Ti(3) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), two equivalent Ba(3), one Ti(1), and one Ti(2) atom. In the fourth S site, S(3) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ti(1), and one Ti(2) atom. In the fifth S site, S(4) is bonded in a 5-coordinate geometry to one Ba(1), three equivalent Ba(2), and one Ti(2) atom. In the sixth S site, S(5) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), one Ti(1), and one Ti(3) atom to form a mixture of distorted face, corner, and edge-sharing SBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. In the seventh S site, S(6) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), one Ti(1), and one Ti(3) atom to form a mixture of distorted face, corner, and edge-sharing SBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 7-64°. In the eighth S site, S(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Ti(2) atoms to form distorted corner-sharing SBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 8-64°. O(1) is bonded in a linear geometry to two equivalent Ba(1) and two equivalent Ti(2) atoms.