Na6PbO5 crystallizes in the orthorhombic Cmcm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1) and four equivalent O(2) atoms. In the second Na site, Na(2) is bonded to one O(1) and four equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Na(3)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid,  a cornercorner with one Pb(1)O5 trigonal bipyramid, edges with two equivalent Na(3)O4 tetrahedra, edges with two equivalent Na(2)O5 trigonal bipyramids, and edges with two equivalent Pb(1)O5 trigonal bipyramids. In the third Na site, Na(3) is bonded to four equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with four equivalent Na(2)O5 trigonal bipyramids, corners with four equivalent Pb(1)O5 trigonal bipyramids, edges with two equivalent Na(3)O4 tetrahedra, and edges with two equivalent Na(2)O5 trigonal bipyramids. Pb(1) is bonded to one O(1) and four equivalent O(2) atoms to form distorted PbO5 trigonal bipyramids that share corners with eight equivalent Na(3)O4 tetrahedra, corners with two equivalent Na(2)O5 trigonal bipyramids, and edges with four equivalent Na(2)O5 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one Pb(1) atom. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Pb(1) atom to form a mixture of distorted face, corner, and edge-sharing ONa6Pb pentagonal bipyramids.
Na6PbO5 crystallizes in the orthorhombic Cmcm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1) and four equivalent O(2) atoms. The Na(1)-O(1) bond length is 2.25 Å. There are two shorter (2.41 Å) and two longer (2.63 Å) Na(1)-O(2) bond lengths. In the second Na site, Na(2) is bonded to one O(1) and four equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Na(3)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid,  a cornercorner with one Pb(1)O5 trigonal bipyramid, edges with two equivalent Na(3)O4 tetrahedra, edges with two equivalent Na(2)O5 trigonal bipyramids, and edges with two equivalent Pb(1)O5 trigonal bipyramids. The Na(2)-O(1) bond length is 2.42 Å. There are two shorter (2.45 Å) and two longer (2.46 Å) Na(2)-O(2) bond lengths. In the third Na site, Na(3) is bonded to four equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with four equivalent Na(2)O5 trigonal bipyramids, corners with four equivalent Pb(1)O5 trigonal bipyramids, edges with two equivalent Na(3)O4 tetrahedra, and edges with two equivalent Na(2)O5 trigonal bipyramids. There are two shorter (2.23 Å) and two longer (2.29 Å) Na(3)-O(2) bond lengths. Pb(1) is bonded to one O(1) and four equivalent O(2) atoms to form distorted PbO5 trigonal bipyramids that share corners with eight equivalent Na(3)O4 tetrahedra, corners with two equivalent Na(2)O5 trigonal bipyramids, and edges with four equivalent Na(2)O5 trigonal bipyramids. The Pb(1)-O(1) bond length is 2.13 Å. All Pb(1)-O(2) bond lengths are 2.17 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one Pb(1) atom. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Pb(1) atom to form a mixture of distorted face, corner, and edge-sharing ONa6Pb pentagonal bipyramids.