AgInAl4S8 is Spinel-derived structured and crystallizes in the trigonal R3m space group. Ag(1) is bonded to one S(2) and three equivalent S(1) atoms to form AgS4 tetrahedra that share corners with three equivalent In(1)S6 octahedra and corners with nine equivalent Al(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. In(1) is bonded to three equivalent S(1) and three equivalent S(3) atoms to form InS6 octahedra that share corners with three equivalent Ag(1)S4 tetrahedra, corners with three equivalent Al(1)S4 tetrahedra, and edges with six equivalent Al(2)S6 octahedra. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one S(4) and three equivalent S(3) atoms to form AlS4 tetrahedra that share corners with three equivalent In(1)S6 octahedra and corners with nine equivalent Al(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 58-63°. In the second Al site, Al(2) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form AlS6 octahedra that share corners with three equivalent Ag(1)S4 tetrahedra, corners with three equivalent Al(1)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent Al(2)S6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ag(1), one In(1), and two equivalent Al(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ag(1) and three equivalent Al(2) atoms. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one In(1), one Al(1), and two equivalent Al(2) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal pyramidal geometry to one Al(1) and three equivalent Al(2) atoms.
AgInAl4S8 is Spinel-derived structured and crystallizes in the trigonal R3m space group. Ag(1) is bonded to one S(2) and three equivalent S(1) atoms to form AgS4 tetrahedra that share corners with three equivalent In(1)S6 octahedra and corners with nine equivalent Al(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. The Ag(1)-S(2) bond length is 2.44 Å. All Ag(1)-S(1) bond lengths are 2.45 Å. In(1) is bonded to three equivalent S(1) and three equivalent S(3) atoms to form InS6 octahedra that share corners with three equivalent Ag(1)S4 tetrahedra, corners with three equivalent Al(1)S4 tetrahedra, and edges with six equivalent Al(2)S6 octahedra. All In(1)-S(1) bond lengths are 2.55 Å. All In(1)-S(3) bond lengths are 2.66 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one S(4) and three equivalent S(3) atoms to form AlS4 tetrahedra that share corners with three equivalent In(1)S6 octahedra and corners with nine equivalent Al(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 58-63°. The Al(1)-S(4) bond length is 2.42 Å. All Al(1)-S(3) bond lengths are 2.35 Å. In the second Al site, Al(2) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form AlS6 octahedra that share corners with three equivalent Ag(1)S4 tetrahedra, corners with three equivalent Al(1)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent Al(2)S6 octahedra. The Al(2)-S(2) bond length is 2.38 Å. The Al(2)-S(4) bond length is 2.60 Å. Both Al(2)-S(1) bond lengths are 2.35 Å. Both Al(2)-S(3) bond lengths are 2.56 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ag(1), one In(1), and two equivalent Al(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ag(1) and three equivalent Al(2) atoms. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one In(1), one Al(1), and two equivalent Al(2) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal pyramidal geometry to one Al(1) and three equivalent Al(2) atoms.