MgIn2S4 crystallizes in the orthorhombic Pnma space group. Mg(1) is bonded in a rectangular see-saw-like geometry to one S(2), one S(3), and two equivalent S(1) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(2), two equivalent S(1), and two equivalent S(3) atoms to form a mixture of corner and edge-sharing InS5 trigonal bipyramids. In the second In site, In(2) is bonded to one S(2) and four equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing InS5 trigonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1), one In(1), and two equivalent In(2) atoms to form a mixture of distorted corner and edge-sharing SMgIn3 trigonal pyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Mg(1), one In(1), and one In(2) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Mg(1) and two equivalent In(1) atoms.
MgIn2S4 crystallizes in the orthorhombic Pnma space group. Mg(1) is bonded in a rectangular see-saw-like geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Mg(1)-S(2) bond length is 2.55 Å. The Mg(1)-S(3) bond length is 2.44 Å. Both Mg(1)-S(1) bond lengths are 2.56 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(2), two equivalent S(1), and two equivalent S(3) atoms to form a mixture of corner and edge-sharing InS5 trigonal bipyramids. The In(1)-S(2) bond length is 2.51 Å. Both In(1)-S(1) bond lengths are 2.70 Å. There is one shorter (2.48 Å) and one longer (2.52 Å) In(1)-S(3) bond length. In the second In site, In(2) is bonded to one S(2) and four equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing InS5 trigonal bipyramids. The In(2)-S(2) bond length is 2.56 Å. There are two shorter (2.66 Å) and two longer (2.69 Å) In(2)-S(1) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1), one In(1), and two equivalent In(2) atoms to form a mixture of distorted corner and edge-sharing SMgIn3 trigonal pyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Mg(1), one In(1), and one In(2) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Mg(1) and two equivalent In(1) atoms.