NaAuBi2O5 crystallizes in the tetragonal P4/mbm space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. There are two inequivalent Au sites. In the first Au site, Au(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms. In the second Au site, Au(2) is bonded in a square co-planar geometry to four equivalent O(3) atoms. Bi(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of edge and corner-sharing BiO5 square pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Au(1), and two equivalent Bi(1) atoms to form ONaBi2Au tetrahedra that share corners with four equivalent O(2)Na2Bi2 tetrahedra, corners with four equivalent O(1)NaBi2Au tetrahedra, and  an edgeedge with one O(1)NaBi2Au tetrahedra. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Bi(1) atoms to form ONa2Bi2 tetrahedra that share corners with two equivalent O(2)Na2Bi2 tetrahedra and corners with eight equivalent O(1)NaBi2Au tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one Au(2), and two equivalent Bi(1) atoms.
NaAuBi2O5 crystallizes in the tetragonal P4/mbm space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(1)-O(1) bond lengths are 2.50 Å. Both Na(1)-O(2) bond lengths are 2.40 Å. Both Na(1)-O(3) bond lengths are 2.57 Å. There are two inequivalent Au sites. In the first Au site, Au(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms. All Au(1)-O(1) bond lengths are 2.03 Å. In the second Au site, Au(2) is bonded in a square co-planar geometry to four equivalent O(3) atoms. All Au(2)-O(3) bond lengths are 2.04 Å. Bi(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of edge and corner-sharing BiO5 square pyramids. The Bi(1)-O(2) bond length is 2.15 Å. Both Bi(1)-O(1) bond lengths are 2.35 Å. Both Bi(1)-O(3) bond lengths are 2.46 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Au(1), and two equivalent Bi(1) atoms to form ONaBi2Au tetrahedra that share corners with four equivalent O(2)Na2Bi2 tetrahedra, corners with four equivalent O(1)NaBi2Au tetrahedra, and  an edgeedge with one O(1)NaBi2Au tetrahedra. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Bi(1) atoms to form ONa2Bi2 tetrahedra that share corners with two equivalent O(2)Na2Bi2 tetrahedra and corners with eight equivalent O(1)NaBi2Au tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one Au(2), and two equivalent Bi(1) atoms.