Na2Zn3Se4 crystallizes in the orthorhombic Ibam space group. Na(1) is bonded in a 8-coordinate geometry to eight equivalent Se(1) atoms. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to four equivalent Se(1) atoms to form a mixture of edge and corner-sharing ZnSe4 tetrahedra. In the second Zn site, Zn(2) is bonded to four equivalent Se(1) atoms to form a mixture of distorted edge and corner-sharing ZnSe4 tetrahedra. Se(1) is bonded in a 7-coordinate geometry to four equivalent Na(1), one Zn(1), and two equivalent Zn(2) atoms.
Na2Zn3Se4 crystallizes in the orthorhombic Ibam space group. Na(1) is bonded in a 8-coordinate geometry to eight equivalent Se(1) atoms. There are a spread of Na(1)-Se(1) bond distances ranging from 3.19-3.56 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to four equivalent Se(1) atoms to form a mixture of edge and corner-sharing ZnSe4 tetrahedra. All Zn(1)-Se(1) bond lengths are 2.49 Å. In the second Zn site, Zn(2) is bonded to four equivalent Se(1) atoms to form a mixture of distorted edge and corner-sharing ZnSe4 tetrahedra. There are two shorter (2.44 Å) and two longer (2.60 Å) Zn(2)-Se(1) bond lengths. Se(1) is bonded in a 7-coordinate geometry to four equivalent Na(1), one Zn(1), and two equivalent Zn(2) atoms.