In4N2S3 crystallizes in the monoclinic C2/m space group. There are two inequivalent In sites. In the first In site, In(1) is bonded in a 6-coordinate geometry to three equivalent N(1), one S(1), and two equivalent S(2) atoms. In the second In site, In(2) is bonded to one N(1), two equivalent S(1), and three equivalent S(2) atoms to form a mixture of distorted edge and corner-sharing InS5N octahedra. The corner-sharing octahedra are not tilted. N(1) is bonded in a see-saw-like geometry to one In(2) and three equivalent In(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent In(1) and four equivalent In(2) atoms to form SIn6 octahedra that share corners with four equivalent S(2)In5 square pyramids, edges with two equivalent S(1)In6 octahedra, and edges with six equivalent S(2)In5 square pyramids. In the second S site, S(2) is bonded to two equivalent In(1) and three equivalent In(2) atoms to form SIn5 square pyramids that share corners with two equivalent S(1)In6 octahedra, edges with three equivalent S(1)In6 octahedra, and edges with four equivalent S(2)In5 square pyramids. The corner-sharing octahedral tilt angles are 10°.
In4N2S3 crystallizes in the monoclinic C2/m space group. There are two inequivalent In sites. In the first In site, In(1) is bonded in a 6-coordinate geometry to three equivalent N(1), one S(1), and two equivalent S(2) atoms. There is one shorter (2.20 Å) and two longer (2.24 Å) In(1)-N(1) bond lengths. The In(1)-S(1) bond length is 2.68 Å. Both In(1)-S(2) bond lengths are 3.00 Å. In the second In site, In(2) is bonded to one N(1), two equivalent S(1), and three equivalent S(2) atoms to form a mixture of distorted edge and corner-sharing InS5N octahedra. The corner-sharing octahedra are not tilted. The In(2)-N(1) bond length is 2.15 Å. Both In(2)-S(1) bond lengths are 2.82 Å. There are two shorter (2.65 Å) and one longer (2.66 Å) In(2)-S(2) bond length. N(1) is bonded in a see-saw-like geometry to one In(2) and three equivalent In(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent In(1) and four equivalent In(2) atoms to form SIn6 octahedra that share corners with four equivalent S(2)In5 square pyramids, edges with two equivalent S(1)In6 octahedra, and edges with six equivalent S(2)In5 square pyramids. In the second S site, S(2) is bonded to two equivalent In(1) and three equivalent In(2) atoms to form SIn5 square pyramids that share corners with two equivalent S(1)In6 octahedra, edges with three equivalent S(1)In6 octahedra, and edges with four equivalent S(2)In5 square pyramids. The corner-sharing octahedral tilt angles are 10°.