Na2Zn3S4 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 Zn sites. In the first Zn site, Zn(1) is bonded to one S(1) and three equivalent S(2) atoms to form distorted corner-sharing ZnS4 tetrahedra. In the second Zn site, Zn(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 in a 5-coordinate geometry to three equivalent Na(1), one Zn(1), and one Zn(2) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Na(1) and three equivalent Zn(1) atoms.
Na2Zn3S4 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 is one shorter (2.83 Å) and one longer (3.02 Å) Na(1)-S(2) bond length. There are two shorter (2.80 Å) and one longer (2.94 Å) Na(1)-S(1) bond length. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1) and three equivalent S(2) atoms to form distorted corner-sharing ZnS4 tetrahedra. The Zn(1)-S(1) bond length is 2.36 Å. There are a spread of Zn(1)-S(2) bond distances ranging from 2.34-2.49 Å. In the second Zn site, Zn(2) is bonded in a linear geometry to two equivalent S(1) atoms. Both Zn(2)-S(1) bond lengths are 2.18 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Zn(1), and one Zn(2) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Na(1) and three equivalent Zn(1) atoms.