Ba6Mg(TiS5)2 crystallizes in the triclinic P1 space group. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(2), one S(4), one S(5), one S(6), one S(7), and one S(9) atom. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(2), one S(3), one S(5), one S(6), one S(8), and one S(9) atom. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one Mg(1), one S(1), one S(10), one S(2), one S(3), one S(4), one S(7), one S(8), and one S(9) atom. In the fourth Ba site, Ba(4) is bonded in a 8-coordinate geometry to one S(10), one S(3), one S(4), one S(5), one S(6), one S(7), one S(8), and one S(9) atom. In the fifth Ba site, Ba(5) is bonded in a 8-coordinate geometry to one Mg(1), one S(1), one S(10), one S(2), one S(3), one S(4), one S(6), and one S(9) atom. In the sixth Ba site, Ba(6) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(4), one S(6), one S(7), one S(8), and one S(9) atom. Mg(1) is bonded in a 3-coordinate geometry to one Ba(3), one Ba(5), one S(10), one S(5), one S(7), and one S(8) atom. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a distorted tetrahedral geometry to one S(2), one S(3), one S(6), and one S(7) atom. In the second Ti site, Ti(2) is bonded in a distorted tetrahedral geometry to one S(1), one S(4), one S(5), and one S(8) atom. There are ten inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(5), one Ba(6), and one Ti(2) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(5), and one Ti(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(5), one Ba(6), and one Ti(1) atom. In the fourth S site, S(4) is bonded to one Ba(1), one Ba(3), one Ba(4), one Ba(5), one Ba(6), and one Ti(2) atom to form a mixture of distorted corner and face-sharing SBa5Ti octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), one Mg(1), and one Ti(2) atom. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), one Ba(5), one Ba(6), and one Ti(1) atom. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), one Ba(4), one Ba(6), one Mg(1), and one Ti(1) atom. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(6), one Mg(1), and one Ti(2) atom. In the ninth S site, S(9) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Ba(5), and one Ba(6) atom to form a mixture of corner and face-sharing SBa6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the tenth S site, S(10) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Ba(5), and one Mg(1) atom.
Ba6Mg(TiS5)2 crystallizes in the triclinic P1 space group. There are six inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(2), one S(4), one S(5), one S(6), one S(7), and one S(9) atom. The Ba(1)-S(1) bond length is 3.48 Å. The Ba(1)-S(10) bond length is 3.19 Å. The Ba(1)-S(2) bond length is 3.09 Å. The Ba(1)-S(4) bond length is 3.38 Å. The Ba(1)-S(5) bond length is 3.53 Å. The Ba(1)-S(6) bond length is 3.22 Å. The Ba(1)-S(7) bond length is 3.60 Å. The Ba(1)-S(9) bond length is 3.30 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(2), one S(3), one S(5), one S(6), one S(8), and one S(9) atom. The Ba(2)-S(1) bond length is 3.48 Å. The Ba(2)-S(10) bond length is 3.72 Å. The Ba(2)-S(2) bond length is 3.36 Å. The Ba(2)-S(3) bond length is 3.38 Å. The Ba(2)-S(5) bond length is 3.12 Å. The Ba(2)-S(6) bond length is 3.13 Å. The Ba(2)-S(8) bond length is 3.31 Å. The Ba(2)-S(9) bond length is 3.19 Å. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one Mg(1), one S(1), one S(10), one S(2), one S(3), one S(4), one S(7), one S(8), and one S(9) atom. The Ba(3)-Mg(1) bond length is 3.35 Å. The Ba(3)-S(1) bond length is 3.33 Å. The Ba(3)-S(10) bond length is 3.71 Å. The Ba(3)-S(2) bond length is 3.28 Å. The Ba(3)-S(3) bond length is 3.30 Å. The Ba(3)-S(4) bond length is 3.08 Å. The Ba(3)-S(7) bond length is 3.26 Å. The Ba(3)-S(8) bond length is 3.47 Å. The Ba(3)-S(9) bond length is 3.14 Å. In the fourth Ba site, Ba(4) is bonded in a 8-coordinate geometry to one S(10), one S(3), one S(4), one S(5), one S(6), one S(7), one S(8), and one S(9) atom. The Ba(4)-S(10) bond length is 3.25 Å. The Ba(4)-S(3) bond length is 3.33 Å. The Ba(4)-S(4) bond length is 3.39 Å. The Ba(4)-S(5) bond length is 3.50 Å. The Ba(4)-S(6) bond length is 3.80 Å. The Ba(4)-S(7) bond length is 3.19 Å. The Ba(4)-S(8) bond length is 3.07 Å. The Ba(4)-S(9) bond length is 3.31 Å. In the fifth Ba site, Ba(5) is bonded in a 8-coordinate geometry to one Mg(1), one S(1), one S(10), one S(2), one S(3), one S(4), one S(6), and one S(9) atom. The Ba(5)-Mg(1) bond length is 3.40 Å. The Ba(5)-S(1) bond length is 3.39 Å. The Ba(5)-S(10) bond length is 3.24 Å. The Ba(5)-S(2) bond length is 3.41 Å. The Ba(5)-S(3) bond length is 3.60 Å. The Ba(5)-S(4) bond length is 3.19 Å. The Ba(5)-S(6) bond length is 3.27 Å. The Ba(5)-S(9) bond length is 3.18 Å. In the sixth Ba site, Ba(6) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(4), one S(6), one S(7), one S(8), and one S(9) atom. The Ba(6)-S(1) bond length is 3.32 Å. The Ba(6)-S(3) bond length is 3.56 Å. The Ba(6)-S(4) bond length is 3.44 Å. The Ba(6)-S(6) bond length is 3.27 Å. The Ba(6)-S(7) bond length is 3.38 Å. The Ba(6)-S(8) bond length is 3.32 Å. The Ba(6)-S(9) bond length is 3.18 Å. Mg(1) is bonded in a 3-coordinate geometry to one Ba(3), one Ba(5), one S(10), one S(5), one S(7), and one S(8) atom. The Mg(1)-S(10) bond length is 2.44 Å. The Mg(1)-S(5) bond length is 2.49 Å. The Mg(1)-S(7) bond length is 2.41 Å. The Mg(1)-S(8) bond length is 2.94 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a distorted tetrahedral geometry to one S(2), one S(3), one S(6), and one S(7) atom. The Ti(1)-S(2) bond length is 2.28 Å. The Ti(1)-S(3) bond length is 2.34 Å. The Ti(1)-S(6) bond length is 2.33 Å. The Ti(1)-S(7) bond length is 2.41 Å. In the second Ti site, Ti(2) is bonded in a distorted tetrahedral geometry to one S(1), one S(4), one S(5), and one S(8) atom. The Ti(2)-S(1) bond length is 2.28 Å. The Ti(2)-S(4) bond length is 2.36 Å. The Ti(2)-S(5) bond length is 2.37 Å. The Ti(2)-S(8) bond length is 2.24 Å. There are ten inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(5), one Ba(6), and one Ti(2) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(5), and one Ti(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(5), one Ba(6), and one Ti(1) atom. In the fourth S site, S(4) is bonded to one Ba(1), one Ba(3), one Ba(4), one Ba(5), one Ba(6), and one Ti(2) atom to form a mixture of distorted corner and face-sharing SBa5Ti octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), one Mg(1), and one Ti(2) atom. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), one Ba(5), one Ba(6), and one Ti(1) atom. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), one Ba(4), one Ba(6), one Mg(1), and one Ti(1) atom. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), one Ba(6), one Mg(1), and one Ti(2) atom. In the ninth S site, S(9) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Ba(5), and one Ba(6) atom to form a mixture of corner and face-sharing SBa6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the tenth S site, S(10) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one Ba(5), and one Mg(1) atom.