Na3GaS3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Ga(1), one S(2), two equivalent S(1), and two equivalent S(3) atoms. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(3) atoms. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(3) atoms. Ga(1) is bonded to one Na(1), one S(1), one S(3), and two equivalent S(2) atoms to form distorted edge-sharing GaNaS4 tetrahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Ga(1) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom.
Na3GaS3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Ga(1), one S(2), two equivalent S(1), and two equivalent S(3) atoms. The Na(1)-Ga(1) bond length is 3.06 Å. The Na(1)-S(2) bond length is 2.77 Å. There is one shorter (2.80 Å) and one longer (3.21 Å) Na(1)-S(1) bond length. There is one shorter (2.91 Å) and one longer (2.98 Å) Na(1)-S(3) bond length. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(3) atoms. There is one shorter (2.75 Å) and one longer (2.93 Å) Na(2)-S(1) bond length. There is one shorter (2.77 Å) and one longer (2.96 Å) Na(2)-S(3) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(3) atoms. There is one shorter (2.85 Å) and one longer (2.91 Å) Na(3)-S(1) bond length. There is one shorter (2.86 Å) and one longer (2.89 Å) Na(3)-S(3) bond length. Ga(1) is bonded to one Na(1), one S(1), one S(3), and two equivalent S(2) atoms to form distorted edge-sharing GaNaS4 tetrahedra. The Ga(1)-S(1) bond length is 2.23 Å. The Ga(1)-S(3) bond length is 2.24 Å. There is one shorter (2.30 Å) and one longer (2.35 Å) Ga(1)-S(2) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Ga(1) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom.