NiV2S4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with six equivalent Ni(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and  a faceface with one Ni(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. Ni(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form NiS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Ni(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Ni(1) atoms.
NiV2S4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with six equivalent Ni(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and  a faceface with one Ni(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. All V(1)-S(1) bond lengths are 2.29 Å. There are two shorter (2.45 Å) and one longer (2.53 Å) V(1)-S(2) bond length. Ni(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form NiS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with two equivalent Ni(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. Both Ni(1)-S(1) bond lengths are 2.36 Å. All Ni(1)-S(2) bond lengths are 2.36 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Ni(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Ni(1) atoms.