ZnAl2(SeS)2 crystallizes in the monoclinic Pm space group. Zn(1) is bonded to one Se(2), two equivalent Se(1), and one S(1) atom to form ZnSe3S tetrahedra that share corners with two equivalent Zn(1)Se3S tetrahedra, corners with four equivalent Al(1)Se3S tetrahedra, and corners with four equivalent Al(2)SeS3 tetrahedra. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one Se(1), two equivalent Se(2), and one S(2) atom to form AlSe3S tetrahedra that share corners with two equivalent Al(1)Se3S tetrahedra, corners with two equivalent Al(2)SeS3 tetrahedra, and corners with four equivalent Zn(1)Se3S tetrahedra. In the second Al site, Al(2) is bonded to one Se(1), one S(2), and two equivalent S(1) atoms to form AlSeS3 tetrahedra that share corners with two equivalent Al(1)Se3S tetrahedra, corners with two equivalent Al(2)SeS3 tetrahedra, and corners with four equivalent Zn(1)Se3S tetrahedra. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Zn(1), one Al(1), and one Al(2) atom to form corner-sharing SeAl2Zn2 tetrahedra. In the second Se site, Se(2) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Al(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Al(2) atoms. In the second S site, S(2) is bonded in a water-like geometry to one Al(1) and one Al(2) atom.
ZnAl2(SeS)2 crystallizes in the monoclinic Pm space group. Zn(1) is bonded to one Se(2), two equivalent Se(1), and one S(1) atom to form ZnSe3S tetrahedra that share corners with two equivalent Zn(1)Se3S tetrahedra, corners with four equivalent Al(1)Se3S tetrahedra, and corners with four equivalent Al(2)SeS3 tetrahedra. The Zn(1)-Se(2) bond length is 2.46 Å. Both Zn(1)-Se(1) bond lengths are 2.51 Å. The Zn(1)-S(1) bond length is 2.34 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one Se(1), two equivalent Se(2), and one S(2) atom to form AlSe3S tetrahedra that share corners with two equivalent Al(1)Se3S tetrahedra, corners with two equivalent Al(2)SeS3 tetrahedra, and corners with four equivalent Zn(1)Se3S tetrahedra. The Al(1)-Se(1) bond length is 2.50 Å. Both Al(1)-Se(2) bond lengths are 2.43 Å. The Al(1)-S(2) bond length is 2.19 Å. In the second Al site, Al(2) is bonded to one Se(1), one S(2), and two equivalent S(1) atoms to form AlSeS3 tetrahedra that share corners with two equivalent Al(1)Se3S tetrahedra, corners with two equivalent Al(2)SeS3 tetrahedra, and corners with four equivalent Zn(1)Se3S tetrahedra. The Al(2)-Se(1) bond length is 2.53 Å. The Al(2)-S(2) bond length is 2.19 Å. Both Al(2)-S(1) bond lengths are 2.32 Å. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Zn(1), one Al(1), and one Al(2) atom to form corner-sharing SeAl2Zn2 tetrahedra. In the second Se site, Se(2) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Al(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Al(2) atoms. In the second S site, S(2) is bonded in a water-like geometry to one Al(1) and one Al(2) atom.