Mg(TiS2)8 crystallizes in the orthorhombic Pnnm space group. Mg(1) is bonded to two equivalent S(5) and four equivalent S(2) atoms to form MgS6 octahedra that share corners with two equivalent Ti(4)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form TiS6 octahedra that share  an edgeedge with one Mg(1)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Ti(2)S6 octahedra. In the second Ti site, Ti(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Mg(1)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the third Ti site, Ti(3) is bonded to two equivalent S(6) and four equivalent S(2) atoms to form TiS6 octahedra that share edges with two equivalent Mg(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. In the fourth Ti site, Ti(4) is bonded to two equivalent S(5) and four equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Mg(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one Ti(2), and one Ti(3) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(2), and one Ti(4) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(4), and two equivalent Ti(1) atoms. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ti(3) and two equivalent Ti(1) atoms.
Mg(TiS2)8 crystallizes in the orthorhombic Pnnm space group. Mg(1) is bonded to two equivalent S(5) and four equivalent S(2) atoms to form MgS6 octahedra that share corners with two equivalent Ti(4)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. Both Mg(1)-S(5) bond lengths are 2.52 Å. All Mg(1)-S(2) bond lengths are 2.53 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form TiS6 octahedra that share  an edgeedge with one Mg(1)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Ti(2)S6 octahedra. The Ti(1)-S(1) bond length is 2.46 Å. The Ti(1)-S(2) bond length is 2.48 Å. The Ti(1)-S(3) bond length is 2.42 Å. The Ti(1)-S(4) bond length is 2.39 Å. The Ti(1)-S(5) bond length is 2.51 Å. The Ti(1)-S(6) bond length is 2.43 Å. In the second Ti site, Ti(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Mg(1)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 4°. The Ti(2)-S(1) bond length is 2.38 Å. The Ti(2)-S(4) bond length is 2.49 Å. Both Ti(2)-S(2) bond lengths are 2.50 Å. Both Ti(2)-S(3) bond lengths are 2.39 Å. In the third Ti site, Ti(3) is bonded to two equivalent S(6) and four equivalent S(2) atoms to form TiS6 octahedra that share edges with two equivalent Mg(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. Both Ti(3)-S(6) bond lengths are 2.45 Å. All Ti(3)-S(2) bond lengths are 2.46 Å. In the fourth Ti site, Ti(4) is bonded to two equivalent S(5) and four equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Mg(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. Both Ti(4)-S(5) bond lengths are 2.43 Å. All Ti(4)-S(3) bond lengths are 2.44 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one Ti(2), and one Ti(3) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(2), and one Ti(4) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(4), and two equivalent Ti(1) atoms. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ti(3) and two equivalent Ti(1) atoms.