NaZrP2O9 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 3-coordinate geometry to one O(2), one O(5), and one O(8) atom. Zr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form ZrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-43°. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-28°. There are nine inequivalent O sites. In the first O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one P(2) atom. In the second O site, O(6) is bonded in a linear geometry to one Zr(1) and one P(2) atom. In the third O site, O(7) is bonded in a distorted single-bond geometry to one P(1) and one O(9) atom. In the fourth O site, O(8) is bonded in a distorted linear geometry to one Na(1) and one P(2) atom. In the fifth O site, O(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the sixth O site, O(9) is bonded in a single-bond geometry to one O(7) atom. In the seventh O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one P(1) atom. In the eighth O site, O(3) is bonded in a 2-coordinate geometry to one Zr(1) and one P(1) atom. In the ninth O site, O(4) is bonded in a distorted linear geometry to one Zr(1) and one P(2) atom.
NaZrP2O9 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 3-coordinate geometry to one O(2), one O(5), and one O(8) atom. The Na(1)-O(2) bond length is 2.60 Å. The Na(1)-O(5) bond length is 2.62 Å. The Na(1)-O(8) bond length is 2.20 Å. Zr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form ZrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Zr(1)-O(1) bond length is 2.12 Å. The Zr(1)-O(2) bond length is 2.17 Å. The Zr(1)-O(3) bond length is 2.16 Å. The Zr(1)-O(4) bond length is 2.06 Å. The Zr(1)-O(5) bond length is 2.08 Å. The Zr(1)-O(6) bond length is 2.05 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-43°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(7) bond length is 1.70 Å. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-28°. The P(2)-O(4) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.49 Å. There are nine inequivalent O sites. In the first O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one P(2) atom. In the second O site, O(6) is bonded in a linear geometry to one Zr(1) and one P(2) atom. In the third O site, O(7) is bonded in a distorted single-bond geometry to one P(1) and one O(9) atom. The O(7)-O(9) bond length is 1.35 Å. In the fourth O site, O(8) is bonded in a distorted linear geometry to one Na(1) and one P(2) atom. In the fifth O site, O(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the sixth O site, O(9) is bonded in a single-bond geometry to one O(7) atom. In the seventh O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one P(1) atom. In the eighth O site, O(3) is bonded in a 2-coordinate geometry to one Zr(1) and one P(1) atom. In the ninth O site, O(4) is bonded in a distorted linear geometry to one Zr(1) and one P(2) atom.