Na4MgC6(NS)6 crystallizes in the trigonal P-31c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent N(1) and three equivalent S(1) atoms. In the second Na site, Na(2) is bonded to six equivalent S(1) atoms to form corner-sharing NaS6 octahedra. In the third Na site, Na(3) is bonded to six equivalent S(1) atoms to form distorted corner-sharing NaS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 11°. Mg(1) is bonded in an octahedral geometry to six equivalent N(1) atoms. C(1) is bonded in a distorted linear geometry to one N(1) and one S(1) atom. N(1) is bonded in a 3-coordinate geometry to one Na(1), one Mg(1), and one C(1) atom. S(1) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one C(1) atom.
Na4MgC6(NS)6 crystallizes in the trigonal P-31c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent N(1) and three equivalent S(1) atoms. All Na(1)-N(1) bond lengths are 2.54 Å. All Na(1)-S(1) bond lengths are 3.03 Å. In the second Na site, Na(2) is bonded to six equivalent S(1) atoms to form corner-sharing NaS6 octahedra. All Na(2)-S(1) bond lengths are 3.08 Å. In the third Na site, Na(3) is bonded to six equivalent S(1) atoms to form distorted corner-sharing NaS6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 11°. All Na(3)-S(1) bond lengths are 3.11 Å. Mg(1) is bonded in an octahedral geometry to six equivalent N(1) atoms. All Mg(1)-N(1) bond lengths are 2.18 Å. C(1) is bonded in a distorted linear geometry to one N(1) and one S(1) atom. The C(1)-N(1) bond length is 1.18 Å. The C(1)-S(1) bond length is 1.63 Å. N(1) is bonded in a 3-coordinate geometry to one Na(1), one Mg(1), and one C(1) atom. S(1) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one C(1) atom.