CrNb3S6 is Corundum-derived structured and crystallizes in the hexagonal P6_322 space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra and edges with six equivalent Nb(2)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 46°. In the second Nb site, Nb(2) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with three equivalent Cr(1)S6 octahedra, edges with three equivalent Nb(1)S6 pentagonal pyramids, edges with three equivalent Nb(2)S6 pentagonal pyramids, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. Cr(1) is bonded to six equivalent S(1) atoms to form CrS6 octahedra that share corners with six equivalent Nb(1)S6 pentagonal pyramids, corners with six equivalent Nb(2)S6 pentagonal pyramids, and faces with two equivalent Nb(2)S6 pentagonal pyramids. S(1) is bonded in a rectangular see-saw-like geometry to one Nb(1), two equivalent Nb(2), and one Cr(1) atom.
CrNb3S6 is Corundum-derived structured and crystallizes in the hexagonal P6_322 space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra and edges with six equivalent Nb(2)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 46°. All Nb(1)-S(1) bond lengths are 2.50 Å. In the second Nb site, Nb(2) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with three equivalent Cr(1)S6 octahedra, edges with three equivalent Nb(1)S6 pentagonal pyramids, edges with three equivalent Nb(2)S6 pentagonal pyramids, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. There are three shorter (2.48 Å) and three longer (2.51 Å) Nb(2)-S(1) bond lengths. Cr(1) is bonded to six equivalent S(1) atoms to form CrS6 octahedra that share corners with six equivalent Nb(1)S6 pentagonal pyramids, corners with six equivalent Nb(2)S6 pentagonal pyramids, and faces with two equivalent Nb(2)S6 pentagonal pyramids. All Cr(1)-S(1) bond lengths are 2.42 Å. S(1) is bonded in a rectangular see-saw-like geometry to one Nb(1), two equivalent Nb(2), and one Cr(1) atom.