Na2ZnBr4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Br(1), two equivalent Br(2), and two equivalent Br(3) atoms to form NaBr6 octahedra that share corners with four equivalent Na(2)Br6 octahedra, corners with two equivalent Zn(1)Br4 tetrahedra, edges with two equivalent Na(1)Br6 octahedra, edges with two equivalent Na(2)Br6 octahedra, and edges with two equivalent Zn(1)Br4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-59°. In the second Na site, Na(2) is bonded to one Br(1), one Br(2), and four equivalent Br(3) atoms to form NaBr6 octahedra that share corners with four equivalent Na(1)Br6 octahedra, corners with four equivalent Na(2)Br6 octahedra, corners with four equivalent Zn(1)Br4 tetrahedra, edges with two equivalent Na(1)Br6 octahedra, and  an edgeedge with one Zn(1)Br4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-59°. Zn(1) is bonded to one Br(1), one Br(2), and two equivalent Br(3) atoms to form ZnBr4 tetrahedra that share corners with two equivalent Na(1)Br6 octahedra, corners with four equivalent Na(2)Br6 octahedra,  an edgeedge with one Na(2)Br6 octahedra, and edges with two equivalent Na(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to one Na(2), two equivalent Na(1), and one Zn(1) atom to form distorted corner-sharing BrNa3Zn trigonal pyramids. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Zn(1) atom. In the third Br site, Br(3) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Zn(1) atom.
Na2ZnBr4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Br(1), two equivalent Br(2), and two equivalent Br(3) atoms to form NaBr6 octahedra that share corners with four equivalent Na(2)Br6 octahedra, corners with two equivalent Zn(1)Br4 tetrahedra, edges with two equivalent Na(1)Br6 octahedra, edges with two equivalent Na(2)Br6 octahedra, and edges with two equivalent Zn(1)Br4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-59°. Both Na(1)-Br(1) bond lengths are 2.98 Å. Both Na(1)-Br(2) bond lengths are 2.92 Å. Both Na(1)-Br(3) bond lengths are 2.97 Å. In the second Na site, Na(2) is bonded to one Br(1), one Br(2), and four equivalent Br(3) atoms to form NaBr6 octahedra that share corners with four equivalent Na(1)Br6 octahedra, corners with four equivalent Na(2)Br6 octahedra, corners with four equivalent Zn(1)Br4 tetrahedra, edges with two equivalent Na(1)Br6 octahedra, and  an edgeedge with one Zn(1)Br4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-59°. The Na(2)-Br(1) bond length is 3.00 Å. The Na(2)-Br(2) bond length is 2.91 Å. There are two shorter (2.96 Å) and two longer (3.01 Å) Na(2)-Br(3) bond lengths. Zn(1) is bonded to one Br(1), one Br(2), and two equivalent Br(3) atoms to form ZnBr4 tetrahedra that share corners with two equivalent Na(1)Br6 octahedra, corners with four equivalent Na(2)Br6 octahedra,  an edgeedge with one Na(2)Br6 octahedra, and edges with two equivalent Na(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. The Zn(1)-Br(1) bond length is 2.39 Å. The Zn(1)-Br(2) bond length is 2.44 Å. Both Zn(1)-Br(3) bond lengths are 2.43 Å. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to one Na(2), two equivalent Na(1), and one Zn(1) atom to form distorted corner-sharing BrNa3Zn trigonal pyramids. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Zn(1) atom. In the third Br site, Br(3) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Zn(1) atom.