Zn(NiS2)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form NiS6 octahedra that share edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. In the second Ni site, Ni(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form NiS6 octahedra that share corners with six equivalent Zn(2)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, and edges with two equivalent Zn(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. In the third Ni site, Ni(3) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form NiS6 octahedra that share edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. In the fourth Ni site, Ni(4) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form NiS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form ZnS6 octahedra that share corners with six equivalent Ni(4)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. In the second Zn site, Zn(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form ZnS6 octahedra that share corners with six equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, and edges with two equivalent Zn(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ni(1), one Ni(3), one Ni(4), and one Zn(1) atom. In the second S site, S(2) is bonded to one Ni(1), one Ni(2), one Ni(4), one Zn(1), and one Zn(2) atom to form a mixture of edge and corner-sharing SZn2Ni3 square pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ni(1), one Ni(2), one Ni(3), and one Zn(2) atom. In the fourth S site, S(4) is bonded to one Ni(2), one Ni(3), one Ni(4), one Zn(1), and one Zn(2) atom to form a mixture of edge and corner-sharing SZn2Ni3 square pyramids.
Zn(NiS2)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form NiS6 octahedra that share edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. Both Ni(1)-S(1) bond lengths are 2.28 Å. Both Ni(1)-S(2) bond lengths are 2.27 Å. Both Ni(1)-S(3) bond lengths are 2.31 Å. In the second Ni site, Ni(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form NiS6 octahedra that share corners with six equivalent Zn(2)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, and edges with two equivalent Zn(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both Ni(2)-S(2) bond lengths are 2.49 Å. Both Ni(2)-S(3) bond lengths are 2.31 Å. Both Ni(2)-S(4) bond lengths are 2.33 Å. In the third Ni site, Ni(3) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form NiS6 octahedra that share edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. Both Ni(3)-S(1) bond lengths are 2.28 Å. Both Ni(3)-S(3) bond lengths are 2.29 Å. Both Ni(3)-S(4) bond lengths are 2.30 Å. In the fourth Ni site, Ni(4) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form NiS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. Both Ni(4)-S(1) bond lengths are 2.47 Å. Both Ni(4)-S(2) bond lengths are 2.32 Å. Both Ni(4)-S(4) bond lengths are 2.31 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form ZnS6 octahedra that share corners with six equivalent Ni(4)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, and edges with two equivalent Zn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. Both Zn(1)-S(1) bond lengths are 2.41 Å. Both Zn(1)-S(2) bond lengths are 2.57 Å. Both Zn(1)-S(4) bond lengths are 2.61 Å. In the second Zn site, Zn(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form ZnS6 octahedra that share corners with six equivalent Ni(2)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, edges with two equivalent Ni(3)S6 octahedra, edges with two equivalent Ni(4)S6 octahedra, and edges with two equivalent Zn(1)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both Zn(2)-S(2) bond lengths are 2.44 Å. Both Zn(2)-S(3) bond lengths are 2.57 Å. Both Zn(2)-S(4) bond lengths are 2.57 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 Ni(1), one Ni(3), one Ni(4), and one Zn(1) atom. In the second S site, S(2) is bonded to one Ni(1), one Ni(2), one Ni(4), one Zn(1), and one Zn(2) atom to form a mixture of edge and corner-sharing SZn2Ni3 square pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ni(1), one Ni(2), one Ni(3), and one Zn(2) atom. In the fourth S site, S(4) is bonded to one Ni(2), one Ni(3), one Ni(4), one Zn(1), and one Zn(2) atom to form a mixture of edge and corner-sharing SZn2Ni3 square pyramids.