Na2Zr4As3(PO8)3 crystallizes in the trigonal R32 space group. Na(1) is bonded in a distorted hexagonal planar geometry to three equivalent O(1) and three equivalent O(2) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form ZrO6 octahedra that share corners with three equivalent As(1)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. In the second Zr site, Zr(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form ZrO6 octahedra that share corners with three equivalent As(1)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. As(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form AsO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-40°. P(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-35°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zr(2), and one As(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one As(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(1) atom.
Na2Zr4As3(PO8)3 crystallizes in the trigonal R32 space group. Na(1) is bonded in a distorted hexagonal planar geometry to three equivalent O(1) and three equivalent O(2) atoms. All Na(1)-O(1) bond lengths are 2.66 Å. All Na(1)-O(2) bond lengths are 2.53 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form ZrO6 octahedra that share corners with three equivalent As(1)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. All Zr(1)-O(1) bond lengths are 2.14 Å. All Zr(1)-O(3) bond lengths are 2.06 Å. In the second Zr site, Zr(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form ZrO6 octahedra that share corners with three equivalent As(1)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. All Zr(2)-O(2) bond lengths are 2.13 Å. All Zr(2)-O(4) bond lengths are 2.08 Å. As(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form AsO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-40°. Both As(1)-O(2) bond lengths are 1.70 Å. Both As(1)-O(3) bond lengths are 1.70 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-35°. Both P(1)-O(1) bond lengths are 1.55 Å. Both P(1)-O(4) bond lengths are 1.55 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zr(2), and one As(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one As(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(1) atom.