Nb6V2(CS2)3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one C(2), two equivalent C(1), one S(1), and two equivalent S(2) atoms to form distorted NbC3S3 octahedra that share  a cornercorner with one Nb(2)C3S3 octahedra, corners with two equivalent Nb(1)C3S3 octahedra, corners with three equivalent V(1)S6 octahedra, edges with four equivalent Nb(2)C3S3 octahedra, edges with five equivalent Nb(1)C3S3 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-48°. In the second Nb site, Nb(2) is bonded to one C(2), two equivalent C(1), one S(1), and two equivalent S(2) atoms to form NbC3S3 octahedra that share  a cornercorner with one Nb(2)C3S3 octahedra, corners with two equivalent Nb(1)C3S3 octahedra, corners with six equivalent V(1)S6 octahedra,  an edgeedge with one Nb(2)C3S3 octahedra, and edges with eight equivalent Nb(1)C3S3 octahedra. The corner-sharing octahedral tilt angles range from 0-45°. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Nb(1)C3S3 octahedra, corners with six equivalent Nb(2)C3S3 octahedra, edges with three equivalent V(1)S6 octahedra, and faces with two equivalent Nb(1)C3S3 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. There are two inequivalent C sites. In the first C site, C(1) is bonded to two equivalent Nb(2) and four equivalent Nb(1) atoms to form edge-sharing CNb6 octahedra. In the second C site, C(2) is bonded to two equivalent Nb(2) and four equivalent Nb(1) atoms to form edge-sharing CNb6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Nb(2), two equivalent Nb(1), and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Nb(2), two equivalent Nb(1), and two equivalent V(1) atoms.
Nb6V2(CS2)3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one C(2), two equivalent C(1), one S(1), and two equivalent S(2) atoms to form distorted NbC3S3 octahedra that share  a cornercorner with one Nb(2)C3S3 octahedra, corners with two equivalent Nb(1)C3S3 octahedra, corners with three equivalent V(1)S6 octahedra, edges with four equivalent Nb(2)C3S3 octahedra, edges with five equivalent Nb(1)C3S3 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-48°. The Nb(1)-C(2) bond length is 2.22 Å. There is one shorter (2.22 Å) and one longer (2.23 Å) Nb(1)-C(1) bond length. The Nb(1)-S(1) bond length is 2.61 Å. There is one shorter (2.62 Å) and one longer (2.63 Å) Nb(1)-S(2) bond length. In the second Nb site, Nb(2) is bonded to one C(2), two equivalent C(1), one S(1), and two equivalent S(2) atoms to form NbC3S3 octahedra that share  a cornercorner with one Nb(2)C3S3 octahedra, corners with two equivalent Nb(1)C3S3 octahedra, corners with six equivalent V(1)S6 octahedra,  an edgeedge with one Nb(2)C3S3 octahedra, and edges with eight equivalent Nb(1)C3S3 octahedra. The corner-sharing octahedral tilt angles range from 0-45°. The Nb(2)-C(2) bond length is 2.22 Å. Both Nb(2)-C(1) bond lengths are 2.23 Å. The Nb(2)-S(1) bond length is 2.56 Å. Both Nb(2)-S(2) bond lengths are 2.56 Å. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Nb(1)C3S3 octahedra, corners with six equivalent Nb(2)C3S3 octahedra, edges with three equivalent V(1)S6 octahedra, and faces with two equivalent Nb(1)C3S3 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. Both V(1)-S(1) bond lengths are 2.41 Å. There are two shorter (2.38 Å) and two longer (2.39 Å) V(1)-S(2) bond lengths. There are two inequivalent C sites. In the first C site, C(1) is bonded to two equivalent Nb(2) and four equivalent Nb(1) atoms to form edge-sharing CNb6 octahedra. In the second C site, C(2) is bonded to two equivalent Nb(2) and four equivalent Nb(1) atoms to form edge-sharing CNb6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Nb(2), two equivalent Nb(1), and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Nb(2), two equivalent Nb(1), and two equivalent V(1) atoms.