Cs4Mg(TiS3)2 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(5) atom. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. In the third Cs site, Cs(3) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(5) atom. In the fourth Cs site, Cs(4) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. Mg(1) is bonded in a distorted bent 120 degrees geometry to one S(3) and one S(4) atom. There are two 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), and one S(6) atom to form distorted edge-sharing TiS5 trigonal bipyramids. In the second Ti site, Ti(2) is bonded to one S(1), one S(2), one S(4), one S(5), and one S(6) atom to form distorted edge-sharing TiS5 trigonal bipyramids. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Ti(1), and one Ti(2) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Ti(1), and one Ti(2) atom. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), one Mg(1), and one Ti(1) atom. In the fourth S site, S(4) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), one Mg(1), and one Ti(2) atom. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Ti(1), and one Ti(2) atom. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Cs(2), one Cs(4), one Ti(1), and one Ti(2) atom.
Cs4Mg(TiS3)2 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(5) atom. The Cs(1)-S(1) bond length is 3.38 Å. The Cs(1)-S(2) bond length is 3.32 Å. The Cs(1)-S(5) bond length is 3.29 Å. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. The Cs(2)-S(1) bond length is 3.72 Å. The Cs(2)-S(2) bond length is 3.91 Å. The Cs(2)-S(3) bond length is 4.02 Å. The Cs(2)-S(4) bond length is 3.62 Å. The Cs(2)-S(5) bond length is 3.52 Å. The Cs(2)-S(6) bond length is 3.39 Å. In the third Cs site, Cs(3) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(5) atom. The Cs(3)-S(1) bond length is 3.38 Å. The Cs(3)-S(2) bond length is 3.32 Å. The Cs(3)-S(5) bond length is 3.29 Å. In the fourth Cs site, Cs(4) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. The Cs(4)-S(1) bond length is 3.73 Å. The Cs(4)-S(2) bond length is 3.93 Å. The Cs(4)-S(3) bond length is 3.62 Å. The Cs(4)-S(4) bond length is 4.02 Å. The Cs(4)-S(5) bond length is 3.52 Å. The Cs(4)-S(6) bond length is 3.39 Å. Mg(1) is bonded in a distorted bent 120 degrees geometry to one S(3) and one S(4) atom. The Mg(1)-S(3) bond length is 2.43 Å. The Mg(1)-S(4) bond length is 2.43 Å. There are two 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), and one S(6) atom to form distorted edge-sharing TiS5 trigonal bipyramids. The Ti(1)-S(1) bond length is 2.48 Å. The Ti(1)-S(2) bond length is 2.39 Å. The Ti(1)-S(3) bond length is 2.39 Å. The Ti(1)-S(5) bond length is 2.43 Å. The Ti(1)-S(6) bond length is 2.48 Å. In the second Ti site, Ti(2) is bonded to one S(1), one S(2), one S(4), one S(5), and one S(6) atom to form distorted edge-sharing TiS5 trigonal bipyramids. The Ti(2)-S(1) bond length is 2.48 Å. The Ti(2)-S(2) bond length is 2.39 Å. The Ti(2)-S(4) bond length is 2.39 Å. The Ti(2)-S(5) bond length is 2.43 Å. The Ti(2)-S(6) bond length is 2.48 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Ti(1), and one Ti(2) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Ti(1), and one Ti(2) atom. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), one Mg(1), and one Ti(1) atom. In the fourth S site, S(4) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), one Mg(1), and one Ti(2) atom. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Ti(1), and one Ti(2) atom. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Cs(2), one Cs(4), one Ti(1), and one Ti(2) atom.