Cs4Mg(TiS3)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one Mg(1), one S(2), one S(3), one S(4), and two equivalent S(1) atoms. In the second Cs site, Cs(2) is bonded in a 5-coordinate geometry to one S(1), one S(3), one S(4), and two equivalent S(2) atoms. Mg(1) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one S(3), and two equivalent S(2) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(1), and two equivalent S(2) atoms. In the second Ti site, Ti(2) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(2) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Ti(1), and one Ti(2) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Cs(1), two equivalent Cs(2), one Mg(1), one Ti(1), and one Ti(2) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Mg(1), and one Ti(1) atom. In the fourth S site, S(4) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Ti(2) atom.
Cs4Mg(TiS3)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one Mg(1), one S(2), one S(3), one S(4), and two equivalent S(1) atoms. The Cs(1)-Mg(1) bond length is 3.52 Å. The Cs(1)-S(2) bond length is 3.87 Å. The Cs(1)-S(3) bond length is 3.50 Å. The Cs(1)-S(4) bond length is 3.71 Å. There is one shorter (3.25 Å) and one longer (3.56 Å) Cs(1)-S(1) bond length. In the second Cs site, Cs(2) is bonded in a 5-coordinate geometry to one S(1), one S(3), one S(4), and two equivalent S(2) atoms. The Cs(2)-S(1) bond length is 3.52 Å. The Cs(2)-S(3) bond length is 3.85 Å. The Cs(2)-S(4) bond length is 3.75 Å. There is one shorter (3.63 Å) and one longer (3.64 Å) Cs(2)-S(2) bond length. Mg(1) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one S(3), and two equivalent S(2) atoms. The Mg(1)-S(3) bond length is 2.40 Å. Both Mg(1)-S(2) bond lengths are 2.45 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(1), and two equivalent S(2) atoms. The Ti(1)-S(3) bond length is 2.34 Å. Both Ti(1)-S(1) bond lengths are 2.33 Å. Both Ti(1)-S(2) bond lengths are 2.64 Å. In the second Ti site, Ti(2) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(2) atoms. The Ti(2)-S(4) bond length is 2.25 Å. Both Ti(2)-S(1) bond lengths are 2.46 Å. Both Ti(2)-S(2) bond lengths are 2.56 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Ti(1), and one Ti(2) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Cs(1), two equivalent Cs(2), one Mg(1), one Ti(1), and one Ti(2) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Mg(1), and one Ti(1) atom. In the fourth S site, S(4) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Ti(2) atom.