KNa2(PO3)3 crystallizes in the triclinic P-1 space group. K(1) is bonded in a 5-coordinate geometry to one O(1), one O(6), one O(8), and two equivalent O(9) atoms. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(6), one O(8), and two equivalent O(7) atoms to form distorted NaO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, edges with two equivalent Na(2)O6 octahedra, and  an edgeedge with one Na(1)O5 square pyramid. In the second Na site, Na(2) is bonded to one O(1), one O(6), one O(7), one O(9), and two equivalent O(5) atoms to form NaO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(2)O6 octahedra, and edges with two equivalent Na(1)O5 square pyramids. There are three 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(5) atom to form PO4 tetrahedra that share corners with three equivalent Na(2)O6 octahedra,  a cornercorner with one Na(1)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with three equivalent Na(1)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. In the third P site, P(3) is bonded to one O(2), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Na(2)O6 octahedra,  a cornercorner with one Na(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-57°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one K(1), one Na(1), one Na(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Na(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one K(1), one Na(1), one Na(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one K(1), one Na(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent K(1), one Na(2), and one P(3) atom.
KNa2(PO3)3 crystallizes in the triclinic P-1 space group. K(1) is bonded in a 5-coordinate geometry to one O(1), one O(6), one O(8), and two equivalent O(9) atoms. The K(1)-O(1) bond length is 2.79 Å. The K(1)-O(6) bond length is 2.81 Å. The K(1)-O(8) bond length is 2.74 Å. There is one shorter (2.80 Å) and one longer (3.04 Å) K(1)-O(9) bond length. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(6), one O(8), and two equivalent O(7) atoms to form distorted NaO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, edges with two equivalent Na(2)O6 octahedra, and  an edgeedge with one Na(1)O5 square pyramid. The Na(1)-O(1) bond length is 2.44 Å. The Na(1)-O(6) bond length is 2.38 Å. The Na(1)-O(8) bond length is 2.57 Å. There is one shorter (2.44 Å) and one longer (2.45 Å) Na(1)-O(7) bond length. In the second Na site, Na(2) is bonded to one O(1), one O(6), one O(7), one O(9), and two equivalent O(5) atoms to form NaO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(2)O6 octahedra, and edges with two equivalent Na(1)O5 square pyramids. The Na(2)-O(1) bond length is 2.43 Å. The Na(2)-O(6) bond length is 2.55 Å. The Na(2)-O(7) bond length is 2.60 Å. The Na(2)-O(9) bond length is 2.46 Å. There is one shorter (2.42 Å) and one longer (2.52 Å) Na(2)-O(5) bond length. There are three 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(5) atom to form PO4 tetrahedra that share corners with three equivalent Na(2)O6 octahedra,  a cornercorner with one Na(1)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-54°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(2) bond length is 1.64 Å. The P(1)-O(3) bond length is 1.64 Å. The P(1)-O(5) bond length is 1.49 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with three equivalent Na(1)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. The P(2)-O(3) bond length is 1.64 Å. The P(2)-O(4) bond length is 1.65 Å. The P(2)-O(7) bond length is 1.50 Å. The P(2)-O(8) bond length is 1.49 Å. In the third P site, P(3) is bonded to one O(2), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Na(2)O6 octahedra,  a cornercorner with one Na(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-57°. The P(3)-O(2) bond length is 1.64 Å. The P(3)-O(4) bond length is 1.64 Å. The P(3)-O(6) bond length is 1.50 Å. The P(3)-O(9) bond length is 1.50 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one K(1), one Na(1), one Na(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Na(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one K(1), one Na(1), one Na(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one K(1), one Na(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent K(1), one Na(2), and one P(3) atom.