Na2PbO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pb(1)O6 octahedra, corners with two equivalent Pb(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pb(1)O6 octahedra, edges with two equivalent Pb(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Pb(1)O6 octahedra, edges with three equivalent Pb(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pb(1)O6 octahedra, corners with two equivalent Pb(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pb(1)O6 octahedra, edges with two equivalent Pb(2)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form PbO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Pb(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. In the second Pb site, Pb(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form PbO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Pb(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Pb(1), and one Pb(2) atom to form a mixture of edge and corner-sharing ONa4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Pb(1), and one Pb(2) atom to form a mixture of edge and corner-sharing ONa4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Pb(1), and one Pb(2) atom to form a mixture of edge and corner-sharing ONa4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
Na2PbO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pb(1)O6 octahedra, corners with two equivalent Pb(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pb(1)O6 octahedra, edges with two equivalent Pb(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. There is one shorter (2.37 Å) and one longer (2.50 Å) Na(1)-O(1) bond length. There is one shorter (2.42 Å) and one longer (2.43 Å) Na(1)-O(2) bond length. There is one shorter (2.37 Å) and one longer (2.52 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Pb(1)O6 octahedra, edges with three equivalent Pb(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. Both Na(2)-O(1) bond lengths are 2.39 Å. Both Na(2)-O(2) bond lengths are 2.40 Å. Both Na(2)-O(3) bond lengths are 2.39 Å. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pb(1)O6 octahedra, corners with two equivalent Pb(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pb(1)O6 octahedra, edges with two equivalent Pb(2)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. Both Na(3)-O(1) bond lengths are 2.49 Å. Both Na(3)-O(2) bond lengths are 2.32 Å. Both Na(3)-O(3) bond lengths are 2.49 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form PbO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Pb(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. Both Pb(1)-O(1) bond lengths are 2.21 Å. Both Pb(1)-O(2) bond lengths are 2.22 Å. Both Pb(1)-O(3) bond lengths are 2.21 Å. In the second Pb site, Pb(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form PbO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Pb(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. Both Pb(2)-O(1) bond lengths are 2.21 Å. Both Pb(2)-O(2) bond lengths are 2.22 Å. Both Pb(2)-O(3) bond lengths are 2.21 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Pb(1), and one Pb(2) atom to form a mixture of edge and corner-sharing ONa4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Pb(1), and one Pb(2) atom to form a mixture of edge and corner-sharing ONa4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Pb(1), and one Pb(2) atom to form a mixture of edge and corner-sharing ONa4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.