Na(V3S4)2 crystallizes in the trigonal P-3 space group. Na(1) is bonded in a 6-coordinate geometry to six equivalent S(2) atoms. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of distorted face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to one Na(1) and four equivalent V(1) atoms. In the second S site, S(1) is bonded to six equivalent V(1) atoms to form distorted face-sharing SV6 pentagonal pyramids.
Na(V3S4)2 crystallizes in the trigonal P-3 space group. Na(1) is bonded in a 6-coordinate geometry to six equivalent S(2) atoms. All Na(1)-S(2) bond lengths are 3.02 Å. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of distorted face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. Both V(1)-S(1) bond lengths are 2.46 Å. There are a spread of V(1)-S(2) bond distances ranging from 2.32-2.59 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to one Na(1) and four equivalent V(1) atoms. In the second S site, S(1) is bonded to six equivalent V(1) atoms to form distorted face-sharing SV6 pentagonal pyramids.