Na4PbP6O18 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(13), one O(14), one O(16), one O(3), one O(8), and one O(9) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(13), one O(14), one O(15), one O(2), one O(4), and one O(7) atom. In the third Na site, Na(3) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(9) atom to form NaO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(7), and one O(9) atom. Pb(1) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(4), one O(7), and one O(8) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(14), one O(16), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the second P site, P(2) is bonded to one O(11), one O(13), one O(15), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. In the third P site, P(3) is bonded to one O(10), one O(16), one O(18), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. In the fourth P site, P(4) is bonded to one O(15), one O(17), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. In the fifth P site, P(5) is bonded to one O(1), one O(17), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. In the sixth P site, P(6) is bonded to one O(18), one O(2), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)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 54°. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one P(5) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(2), one Na(3), and one P(6) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Pb(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(2) and one P(5) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(6) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one Na(4), one Pb(1), and one P(5) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Na(1), one Pb(1), and one P(6) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(4), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Na(2), one Na(3), one Pb(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(3), one Na(4), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(3), one Pb(1), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Pb(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(4), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Na(2), one P(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 120 degrees geometry to one Na(1), one P(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one P(4) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one P(3) and one P(6) atom.
Na4PbP6O18 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(13), one O(14), one O(16), one O(3), one O(8), and one O(9) atom. The Na(1)-O(1) bond length is 2.38 Å. The Na(1)-O(13) bond length is 2.53 Å. The Na(1)-O(14) bond length is 2.44 Å. The Na(1)-O(16) bond length is 2.90 Å. The Na(1)-O(3) bond length is 2.68 Å. The Na(1)-O(8) bond length is 2.52 Å. The Na(1)-O(9) bond length is 2.40 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(13), one O(14), one O(15), one O(2), one O(4), and one O(7) atom. The Na(2)-O(10) bond length is 2.51 Å. The Na(2)-O(13) bond length is 2.46 Å. The Na(2)-O(14) bond length is 2.47 Å. The Na(2)-O(15) bond length is 2.92 Å. The Na(2)-O(2) bond length is 2.41 Å. The Na(2)-O(4) bond length is 2.57 Å. The Na(2)-O(7) bond length is 2.46 Å. In the third Na site, Na(3) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(9) atom to form NaO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Na(3)-O(1) bond length is 2.40 Å. The Na(3)-O(10) bond length is 2.75 Å. The Na(3)-O(11) bond length is 2.40 Å. The Na(3)-O(12) bond length is 2.40 Å. The Na(3)-O(2) bond length is 2.39 Å. The Na(3)-O(9) bond length is 2.55 Å. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(7), and one O(9) atom. The Na(4)-O(11) bond length is 2.34 Å. The Na(4)-O(14) bond length is 2.42 Å. The Na(4)-O(7) bond length is 2.50 Å. The Na(4)-O(9) bond length is 2.57 Å. Pb(1) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(4), one O(7), and one O(8) atom. The Pb(1)-O(10) bond length is 2.76 Å. The Pb(1)-O(12) bond length is 2.63 Å. The Pb(1)-O(13) bond length is 2.60 Å. The Pb(1)-O(4) bond length is 2.71 Å. The Pb(1)-O(7) bond length is 2.74 Å. The Pb(1)-O(8) bond length is 2.46 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(14), one O(16), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The P(1)-O(12) bond length is 1.50 Å. The P(1)-O(14) bond length is 1.50 Å. The P(1)-O(16) bond length is 1.63 Å. The P(1)-O(6) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(11), one O(13), one O(15), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. The P(2)-O(11) bond length is 1.49 Å. The P(2)-O(13) bond length is 1.51 Å. The P(2)-O(15) bond length is 1.63 Å. The P(2)-O(5) bond length is 1.62 Å. In the third P site, P(3) is bonded to one O(10), one O(16), one O(18), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. The P(3)-O(10) bond length is 1.51 Å. The P(3)-O(16) bond length is 1.65 Å. The P(3)-O(18) bond length is 1.63 Å. The P(3)-O(3) bond length is 1.49 Å. In the fourth P site, P(4) is bonded to one O(15), one O(17), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The P(4)-O(15) bond length is 1.65 Å. The P(4)-O(17) bond length is 1.63 Å. The P(4)-O(4) bond length is 1.50 Å. The P(4)-O(9) bond length is 1.50 Å. In the fifth P site, P(5) is bonded to one O(1), one O(17), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. The P(5)-O(1) bond length is 1.49 Å. The P(5)-O(17) bond length is 1.62 Å. The P(5)-O(5) bond length is 1.63 Å. The P(5)-O(7) bond length is 1.51 Å. In the sixth P site, P(6) is bonded to one O(18), one O(2), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(3)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 54°. The P(6)-O(18) bond length is 1.63 Å. The P(6)-O(2) bond length is 1.49 Å. The P(6)-O(6) bond length is 1.63 Å. The P(6)-O(8) bond length is 1.52 Å. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one P(5) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(2), one Na(3), and one P(6) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Pb(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(2) and one P(5) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(6) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one Na(2), one Na(4), one Pb(1), and one P(5) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Na(1), one Pb(1), and one P(6) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(4), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Na(2), one Na(3), one Pb(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(3), one Na(4), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(3), one Pb(1), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Pb(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(4), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Na(2), one P(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 120 degrees geometry to one Na(1), one P(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one P(4) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one P(3) and one P(6) atom.