Zn(FeS2)4 crystallizes in the trigonal R-3m space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form FeS6 octahedra that share edges with two equivalent Fe(2)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent Fe(1)S6 octahedra. In the second Fe site, Fe(2) is bonded to six equivalent S(1) atoms to form FeS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. Zn(1) is bonded to six equivalent S(1) atoms to form distorted ZnS6 octahedra that share corners with six equivalent Fe(2)S6 octahedra and edges with six equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Fe(2), two equivalent Fe(1), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Fe(1) atoms.
Zn(FeS2)4 crystallizes in the trigonal R-3m space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form FeS6 octahedra that share edges with two equivalent Fe(2)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent Fe(1)S6 octahedra. Both Fe(1)-S(2) bond lengths are 2.30 Å. All Fe(1)-S(1) bond lengths are 2.30 Å. In the second Fe site, Fe(2) is bonded to six equivalent S(1) atoms to form FeS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. All Fe(2)-S(1) bond lengths are 2.36 Å. Zn(1) is bonded to six equivalent S(1) atoms to form distorted ZnS6 octahedra that share corners with six equivalent Fe(2)S6 octahedra and edges with six equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. All Zn(1)-S(1) bond lengths are 2.56 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Fe(2), two equivalent Fe(1), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Fe(1) atoms.