Nb4CrS8 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Nb(2)S6 pentagonal pyramids, and edges with four equivalent Nb(1)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. In the second Nb site, Nb(2) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share edges with six equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Cr(1)S6 octahedra. Cr(1) is bonded to six equivalent S(1) atoms to form CrS6 octahedra that share corners with twelve equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Nb(2)S6 pentagonal pyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Nb(2), two equivalent Nb(1), and one Cr(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Nb(1) atoms.
Nb4CrS8 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Nb(2)S6 pentagonal pyramids, and edges with four equivalent Nb(1)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. Both Nb(1)-S(2) bond lengths are 2.45 Å. All Nb(1)-S(1) bond lengths are 2.52 Å. In the second Nb site, Nb(2) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share edges with six equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Cr(1)S6 octahedra. All Nb(2)-S(1) bond lengths are 2.48 Å. Cr(1) is bonded to six equivalent S(1) atoms to form CrS6 octahedra that share corners with twelve equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Nb(2)S6 pentagonal pyramids. All Cr(1)-S(1) bond lengths are 2.42 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 Nb(2), two equivalent Nb(1), and one Cr(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Nb(1) atoms.