Zn(NiS2)4 crystallizes in the trigonal R-3m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form NiS6 octahedra that share edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent Ni(1)S6 octahedra. In the second Ni site, Ni(2) is bonded to six equivalent S(1) atoms to form NiS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent Ni(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. Zn(1) is bonded to six equivalent S(1) atoms to form ZnS6 octahedra that share corners with six equivalent Ni(2)S6 octahedra and edges with six equivalent Ni(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 Ni(2), two equivalent Ni(1), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Ni(1) atoms.
Zn(NiS2)4 crystallizes in the trigonal R-3m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form NiS6 octahedra that share edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent Ni(1)S6 octahedra. Both Ni(1)-S(2) bond lengths are 2.27 Å. All Ni(1)-S(1) bond lengths are 2.27 Å. In the second Ni site, Ni(2) is bonded to six equivalent S(1) atoms to form NiS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent Ni(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. All Ni(2)-S(1) bond lengths are 2.33 Å. Zn(1) is bonded to six equivalent S(1) atoms to form ZnS6 octahedra that share corners with six equivalent Ni(2)S6 octahedra and edges with six equivalent Ni(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. All Zn(1)-S(1) bond lengths are 2.53 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 Ni(2), two equivalent Ni(1), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Ni(1) atoms.