Nb3(BiS3)2 crystallizes in the hexagonal P-62m space group. Nb(1,2) is bonded to two equivalent S(4) and four equivalent S(1) atoms to form distorted edge-sharing NbS6 pentagonal pyramids. Bi(1) is bonded in a linear geometry to one S(1) and one S(2) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to three equivalent Nb(1,2) and one Bi(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to three equivalent Nb(1,2) and one Bi(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to three equivalent Nb(1,2) atoms. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to three equivalent Nb(1,2) atoms.
Nb3(BiS3)2 crystallizes in the hexagonal P-62m space group. Nb(1,2) is bonded to two equivalent S(4) and four equivalent S(1) atoms to form distorted edge-sharing NbS6 pentagonal pyramids. Both Nb(1,2)-S(4) bond lengths are 2.48 Å. All Nb(1,2)-S(1) bond lengths are 2.49 Å. Bi(1) is bonded in a linear geometry to one S(1) and one S(2) atom. The Bi(1)-S(1) bond length is 2.81 Å. The Bi(1)-S(2) bond length is 2.80 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to three equivalent Nb(1,2) and one Bi(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to three equivalent Nb(1,2) and one Bi(1) atom. All S(2)-Nb(1,2) bond lengths are 2.49 Å. In the third S site, S(3) is bonded in a distorted T-shaped geometry to three equivalent Nb(1,2) atoms. All S(3)-Nb(1,2) bond lengths are 2.48 Å. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to three equivalent Nb(1,2) atoms.