NaZnAsO4 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form NaO6 octahedra that share corners with six equivalent Zn(1)O4 tetrahedra and corners with six equivalent As(1)O4 tetrahedra. In the second Na site, Na(2) is bonded in a 3-coordinate geometry to three equivalent O(4) atoms. In the third Na site, Na(3) is bonded in a distorted trigonal planar geometry to three equivalent O(2) atoms. Zn(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form ZnO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and corners with four equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 65-73°. As(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AsO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and corners with four equivalent Zn(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-63°. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(2), one Zn(1), and one As(1) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one As(1) atom. In the third O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(3), one Zn(1), and one As(1) atom. In the fourth O site, O(3) is bonded in a trigonal planar geometry to one Na(1), one Zn(1), and one As(1) atom.
NaZnAsO4 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form NaO6 octahedra that share corners with six equivalent Zn(1)O4 tetrahedra and corners with six equivalent As(1)O4 tetrahedra. All Na(1)-O(1) bond lengths are 2.55 Å. All Na(1)-O(3) bond lengths are 2.47 Å. In the second Na site, Na(2) is bonded in a 3-coordinate geometry to three equivalent O(4) atoms. All Na(2)-O(4) bond lengths are 2.46 Å. In the third Na site, Na(3) is bonded in a distorted trigonal planar geometry to three equivalent O(2) atoms. All Na(3)-O(2) bond lengths are 2.32 Å. Zn(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form ZnO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and corners with four equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 65-73°. The Zn(1)-O(1) bond length is 2.00 Å. The Zn(1)-O(2) bond length is 1.98 Å. The Zn(1)-O(3) bond length is 1.96 Å. The Zn(1)-O(4) bond length is 1.99 Å. As(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AsO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and corners with four equivalent Zn(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-63°. The As(1)-O(1) bond length is 1.74 Å. The As(1)-O(2) bond length is 1.72 Å. The As(1)-O(3) bond length is 1.72 Å. The As(1)-O(4) bond length is 1.72 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(2), one Zn(1), and one As(1) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one As(1) atom. In the third O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(3), one Zn(1), and one As(1) atom. In the fourth O site, O(3) is bonded in a trigonal planar geometry to one Na(1), one Zn(1), and one As(1) atom.