Na3BS3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(1) atoms. In the second Na site, Na(2) is bonded to two equivalent B(1), two equivalent S(2), and four equivalent S(1) atoms to form a mixture of distorted edge and corner-sharing NaB2S6 hexagonal bipyramids. B(1) is bonded in a trigonal planar geometry to two equivalent Na(2), one S(2), and two equivalent S(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to two equivalent Na(2), four equivalent Na(1), and one B(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Na(2), four equivalent Na(1), and one B(1) atom.
Na3BS3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(1) atoms. There is one shorter (2.81 Å) and one longer (3.02 Å) Na(1)-S(2) bond length. There are a spread of Na(1)-S(1) bond distances ranging from 2.79-3.01 Å. In the second Na site, Na(2) is bonded to two equivalent B(1), two equivalent S(2), and four equivalent S(1) atoms to form a mixture of distorted edge and corner-sharing NaB2S6 hexagonal bipyramids. Both Na(2)-B(1) bond lengths are 2.92 Å. Both Na(2)-S(2) bond lengths are 2.78 Å. There are two shorter (2.77 Å) and two longer (3.22 Å) Na(2)-S(1) bond lengths. B(1) is bonded in a trigonal planar geometry to two equivalent Na(2), one S(2), and two equivalent S(1) atoms. The B(1)-S(2) bond length is 1.85 Å. Both B(1)-S(1) bond lengths are 1.83 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to two equivalent Na(2), four equivalent Na(1), and one B(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Na(2), four equivalent Na(1), and one B(1) atom.