Na2Hg3S4 crystallizes in the orthorhombic Pbca space group. Na(1) is bonded in a 5-coordinate geometry to two equivalent S(2) and three equivalent S(1) atoms. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted trigonal planar geometry to one S(1) and two equivalent S(2) atoms. In the second Hg site, Hg(2) is bonded in a linear geometry to two equivalent S(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1), one Hg(1), and one Hg(2) atom to form a mixture of corner and edge-sharing SNa3Hg2 trigonal bipyramids. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent Hg(1) atoms.
Na2Hg3S4 crystallizes in the orthorhombic Pbca space group. Na(1) is bonded in a 5-coordinate geometry to two equivalent S(2) and three equivalent S(1) atoms. Both Na(1)-S(2) bond lengths are 2.95 Å. There are a spread of Na(1)-S(1) bond distances ranging from 2.86-2.95 Å. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted trigonal planar geometry to one S(1) and two equivalent S(2) atoms. The Hg(1)-S(1) bond length is 2.55 Å. There is one shorter (2.43 Å) and one longer (2.56 Å) Hg(1)-S(2) bond length. In the second Hg site, Hg(2) is bonded in a linear geometry to two equivalent S(1) atoms. Both Hg(2)-S(1) bond lengths are 2.36 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1), one Hg(1), and one Hg(2) atom to form a mixture of corner and edge-sharing SNa3Hg2 trigonal bipyramids. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent Hg(1) atoms.