NiIn2S4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ni(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form NiS6 octahedra that share corners with six equivalent In(1)S4 tetrahedra, edges with two equivalent Ni(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 two equivalent S(1) and two equivalent S(2) atoms to form InS4 tetrahedra that share corners with six equivalent Ni(1)S6 octahedra and corners with six equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-69°. In the second In site, In(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form InS6 octahedra that share corners with six equivalent In(1)S4 tetrahedra, edges with two equivalent In(2)S6 octahedra, and edges with four equivalent Ni(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ni(1), one In(1), and one In(2) atom to form a mixture of distorted corner and edge-sharing SIn2Ni2 trigonal pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ni(1), one In(1), and two equivalent In(2) atoms.
NiIn2S4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ni(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form NiS6 octahedra that share corners with six equivalent In(1)S4 tetrahedra, edges with two equivalent Ni(1)S6 octahedra, and edges with four equivalent In(2)S6 octahedra. Both Ni(1)-S(2) bond lengths are 2.37 Å. All Ni(1)-S(1) bond lengths are 2.42 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form InS4 tetrahedra that share corners with six equivalent Ni(1)S6 octahedra and corners with six equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-69°. Both In(1)-S(1) bond lengths are 2.55 Å. Both In(1)-S(2) bond lengths are 2.54 Å. In the second In site, In(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form InS6 octahedra that share corners with six equivalent In(1)S4 tetrahedra, edges with two equivalent In(2)S6 octahedra, and edges with four equivalent Ni(1)S6 octahedra. Both In(2)-S(1) bond lengths are 2.63 Å. All In(2)-S(2) bond lengths are 2.62 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ni(1), one In(1), and one In(2) atom to form a mixture of distorted corner and edge-sharing SIn2Ni2 trigonal pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ni(1), one In(1), and two equivalent In(2) atoms.