Zn5SeS4 is Chalcopyrite-like structured and crystallizes in the tetragonal I-4m2 space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form ZnSe2S2 tetrahedra that share corners with four equivalent Zn(2)S4 tetrahedra and corners with eight equivalent Zn(1)Se2S2 tetrahedra. In the second Zn site, Zn(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form ZnS4 tetrahedra that share corners with four equivalent Zn(2)S4 tetrahedra, corners with four equivalent Zn(3)S4 tetrahedra, and corners with four equivalent Zn(1)Se2S2 tetrahedra. In the third Zn site, Zn(3) is bonded to four equivalent S(2) atoms to form corner-sharing ZnS4 tetrahedra. Se(1) is bonded to four equivalent Zn(1) atoms to form SeZn4 tetrahedra that share corners with four equivalent Se(1)Zn4 tetrahedra and corners with eight equivalent S(1)Zn4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Zn(1) and two equivalent Zn(2) atoms to form SZn4 tetrahedra that share corners with four equivalent Se(1)Zn4 tetrahedra, corners with four equivalent S(1)Zn4 tetrahedra, and corners with four equivalent S(2)Zn4 tetrahedra. In the second S site, S(2) is bonded to two equivalent Zn(2) and two equivalent Zn(3) atoms to form corner-sharing SZn4 tetrahedra.
Zn5SeS4 is Chalcopyrite-like structured and crystallizes in the tetragonal I-4m2 space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent Se(1) and two equivalent S(1) atoms to form ZnSe2S2 tetrahedra that share corners with four equivalent Zn(2)S4 tetrahedra and corners with eight equivalent Zn(1)Se2S2 tetrahedra. Both Zn(1)-Se(1) bond lengths are 2.43 Å. Both Zn(1)-S(1) bond lengths are 2.34 Å. In the second Zn site, Zn(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form ZnS4 tetrahedra that share corners with four equivalent Zn(2)S4 tetrahedra, corners with four equivalent Zn(3)S4 tetrahedra, and corners with four equivalent Zn(1)Se2S2 tetrahedra. Both Zn(2)-S(1) bond lengths are 2.34 Å. Both Zn(2)-S(2) bond lengths are 2.34 Å. In the third Zn site, Zn(3) is bonded to four equivalent S(2) atoms to form corner-sharing ZnS4 tetrahedra. All Zn(3)-S(2) bond lengths are 2.34 Å. Se(1) is bonded to four equivalent Zn(1) atoms to form SeZn4 tetrahedra that share corners with four equivalent Se(1)Zn4 tetrahedra and corners with eight equivalent S(1)Zn4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Zn(1) and two equivalent Zn(2) atoms to form SZn4 tetrahedra that share corners with four equivalent Se(1)Zn4 tetrahedra, corners with four equivalent S(1)Zn4 tetrahedra, and corners with four equivalent S(2)Zn4 tetrahedra. In the second S site, S(2) is bonded to two equivalent Zn(2) and two equivalent Zn(3) atoms to form corner-sharing SZn4 tetrahedra.