Mg2TiIn3S8 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one S(1), one S(4), and two equivalent S(5) atoms to form MgS4 tetrahedra that share corners with three equivalent Ti(1)S6 octahedra, corners with three equivalent In(1)S6 octahedra, and corners with six equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-59°. In the second Mg site, Mg(2) is bonded to one S(3), one S(6), and two equivalent S(2) atoms to form MgS4 tetrahedra that share corners with three equivalent Ti(1)S6 octahedra, corners with three equivalent In(1)S6 octahedra, and corners with six equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. Ti(1) is bonded to one S(1), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form TiS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent In(2)S6 octahedra. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form InS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent In(2)S6 octahedra. In the second In site, In(2) 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 InS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent In(2)S6 octahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), and two equivalent In(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(2), one Ti(1), one In(1), and one In(2) atom. In the third S site, S(3) is bonded to one Mg(2), one In(1), and two equivalent In(2) atoms to form distorted corner-sharing SMgIn3 trigonal pyramids. In the fourth S site, S(4) is bonded to one Mg(1), one In(1), and two equivalent In(2) atoms to form distorted corner-sharing SMgIn3 trigonal pyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one In(1), and one In(2) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Mg(2), one Ti(1), and two equivalent In(2) atoms.
Mg2TiIn3S8 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one S(1), one S(4), and two equivalent S(5) atoms to form MgS4 tetrahedra that share corners with three equivalent Ti(1)S6 octahedra, corners with three equivalent In(1)S6 octahedra, and corners with six equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-59°. The Mg(1)-S(1) bond length is 2.50 Å. The Mg(1)-S(4) bond length is 2.46 Å. Both Mg(1)-S(5) bond lengths are 2.50 Å. In the second Mg site, Mg(2) is bonded to one S(3), one S(6), and two equivalent S(2) atoms to form MgS4 tetrahedra that share corners with three equivalent Ti(1)S6 octahedra, corners with three equivalent In(1)S6 octahedra, and corners with six equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. The Mg(2)-S(3) bond length is 2.46 Å. The Mg(2)-S(6) bond length is 2.49 Å. Both Mg(2)-S(2) bond lengths are 2.50 Å. Ti(1) is bonded to one S(1), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form TiS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent In(2)S6 octahedra. The Ti(1)-S(1) bond length is 2.52 Å. The Ti(1)-S(6) bond length is 2.52 Å. Both Ti(1)-S(2) bond lengths are 2.52 Å. Both Ti(1)-S(5) bond lengths are 2.52 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form InS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent In(2)S6 octahedra. The In(1)-S(3) bond length is 2.62 Å. The In(1)-S(4) bond length is 2.61 Å. Both In(1)-S(2) bond lengths are 2.66 Å. Both In(1)-S(5) bond lengths are 2.66 Å. In the second In site, In(2) 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 InS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent In(2)S6 octahedra. The In(2)-S(1) bond length is 2.66 Å. The In(2)-S(2) bond length is 2.66 Å. The In(2)-S(3) bond length is 2.61 Å. The In(2)-S(4) bond length is 2.61 Å. The In(2)-S(5) bond length is 2.66 Å. The In(2)-S(6) bond length is 2.66 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), and two equivalent In(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(2), one Ti(1), one In(1), and one In(2) atom. In the third S site, S(3) is bonded to one Mg(2), one In(1), and two equivalent In(2) atoms to form distorted corner-sharing SMgIn3 trigonal pyramids. In the fourth S site, S(4) is bonded to one Mg(1), one In(1), and two equivalent In(2) atoms to form distorted corner-sharing SMgIn3 trigonal pyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one In(1), and one In(2) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Mg(2), one Ti(1), and two equivalent In(2) atoms.