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 6-coordinate geometry to one S(1), one S(2), one S(3), one S(6), and two equivalent S(4) atoms. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to one S(1), one S(5), and two equivalent S(3) atoms. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(5), one S(6), and two equivalent S(4) atoms. In the fourth Cs site, Cs(4) is bonded in a 9-coordinate geometry to one Mg(1), one S(2), one S(4), one S(5), one S(6), two equivalent S(1), and two equivalent S(3) atoms. Mg(1) is bonded in a distorted see-saw-like geometry to one Cs(4), one S(1), one S(2), one S(4), one S(5), and one S(6) atom. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), one S(3), one S(5), and one S(6) atom. In the second Ti site, Ti(2) is bonded in a distorted trigonal bipyramidal geometry to one S(1), one S(2), one S(4), one S(5), and one S(6) atom. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), two equivalent Cs(4), one Mg(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), one Cs(3), one Cs(4), one Mg(1), one Ti(1), and one Ti(2) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), two equivalent Cs(4), and one Ti(1) atom. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), one Mg(1), and one Ti(2) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), one Mg(1), one Ti(1), and one Ti(2) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Mg(1), 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 6-coordinate geometry to one S(1), one S(2), one S(3), one S(6), and two equivalent S(4) atoms. The Cs(1)-S(1) bond length is 4.00 Å. The Cs(1)-S(2) bond length is 3.57 Å. The Cs(1)-S(3) bond length is 3.69 Å. The Cs(1)-S(6) bond length is 3.62 Å. There is one shorter (3.57 Å) and one longer (3.74 Å) Cs(1)-S(4) bond length. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to one S(1), one S(5), and two equivalent S(3) atoms. The Cs(2)-S(1) bond length is 3.31 Å. The Cs(2)-S(5) bond length is 3.32 Å. There is one shorter (3.40 Å) and one longer (3.52 Å) Cs(2)-S(3) bond length. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(5), one S(6), and two equivalent S(4) atoms. The Cs(3)-S(1) bond length is 3.53 Å. The Cs(3)-S(2) bond length is 3.33 Å. The Cs(3)-S(3) bond length is 3.69 Å. The Cs(3)-S(5) bond length is 3.52 Å. The Cs(3)-S(6) bond length is 3.52 Å. There is one shorter (3.50 Å) and one longer (3.65 Å) Cs(3)-S(4) bond length. In the fourth Cs site, Cs(4) is bonded in a 9-coordinate geometry to one Mg(1), one S(2), one S(4), one S(5), one S(6), two equivalent S(1), and two equivalent S(3) atoms. The Cs(4)-Mg(1) bond length is 3.33 Å. The Cs(4)-S(2) bond length is 3.72 Å. The Cs(4)-S(4) bond length is 3.53 Å. The Cs(4)-S(5) bond length is 3.72 Å. The Cs(4)-S(6) bond length is 3.48 Å. There is one shorter (3.83 Å) and one longer (4.01 Å) Cs(4)-S(1) bond length. There is one shorter (3.60 Å) and one longer (3.63 Å) Cs(4)-S(3) bond length. Mg(1) is bonded in a distorted see-saw-like geometry to one Cs(4), one S(1), one S(2), one S(4), one S(5), and one S(6) atom. The Mg(1)-S(1) bond length is 3.17 Å. The Mg(1)-S(2) bond length is 2.58 Å. The Mg(1)-S(4) bond length is 2.52 Å. The Mg(1)-S(5) bond length is 2.55 Å. The Mg(1)-S(6) bond length is 2.53 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), one S(3), one S(5), and one S(6) atom. The Ti(1)-S(1) bond length is 2.59 Å. The Ti(1)-S(2) bond length is 2.43 Å. The Ti(1)-S(3) bond length is 2.30 Å. The Ti(1)-S(5) bond length is 2.42 Å. The Ti(1)-S(6) bond length is 2.71 Å. In the second Ti site, Ti(2) is bonded in a distorted trigonal bipyramidal geometry to one S(1), one S(2), one S(4), one S(5), and one S(6) atom. The Ti(2)-S(1) bond length is 2.44 Å. The Ti(2)-S(2) bond length is 2.35 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 2.59 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), two equivalent Cs(4), one Mg(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), one Cs(3), one Cs(4), one Mg(1), one Ti(1), and one Ti(2) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), two equivalent Cs(4), and one Ti(1) atom. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), one Mg(1), and one Ti(2) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), one Mg(1), one Ti(1), and one Ti(2) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Mg(1), one Ti(1), and one Ti(2) atom.