Na3P6(PbO9)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(7), one O(8), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form NaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. Pb(1) is bonded in a distorted T-shaped geometry to one O(3), one O(5), and one O(7) atom. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. In the third P site, P(3) is bonded to one O(2), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), one Pb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Na(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Pb(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Pb(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom.
Na3P6(PbO9)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(7), one O(8), and two equivalent O(5) atoms. The Na(1)-O(2) bond length is 2.37 Å. The Na(1)-O(3) bond length is 2.93 Å. The Na(1)-O(7) bond length is 2.42 Å. The Na(1)-O(8) bond length is 2.38 Å. There is one shorter (2.48 Å) and one longer (2.57 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form NaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. Both Na(2)-O(2) bond lengths are 2.42 Å. Both Na(2)-O(4) bond lengths are 2.52 Å. Both Na(2)-O(8) bond lengths are 2.70 Å. Pb(1) is bonded in a distorted T-shaped geometry to one O(3), one O(5), and one O(7) atom. The Pb(1)-O(3) bond length is 2.58 Å. The Pb(1)-O(5) bond length is 2.68 Å. The Pb(1)-O(7) bond length is 2.48 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The P(1)-O(1) bond length is 1.63 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-O(8) bond length is 1.50 Å. The P(1)-O(9) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The P(2)-O(1) bond length is 1.64 Å. The P(2)-O(4) bond length is 1.49 Å. The P(2)-O(5) bond length is 1.51 Å. The P(2)-O(6) bond length is 1.64 Å. In the third P site, P(3) is bonded to one O(2), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The P(3)-O(2) bond length is 1.49 Å. The P(3)-O(6) bond length is 1.63 Å. The P(3)-O(7) bond length is 1.52 Å. The P(3)-O(9) bond length is 1.62 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), one Pb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Na(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Pb(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Pb(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom.