Na2AuBi5O11 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. Au(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted BiO5 square pyramids that share corners with two equivalent Bi(2)O6 octahedra,  a cornercorner with one Bi(1)O5 square pyramid, and edges with two equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 60°. In the second Bi site, Bi(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Bi(2)O6 octahedra and corners with eight equivalent Bi(1)O5 square pyramids. The corner-sharing octahedra are not tilted. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Bi(2), and two equivalent Bi(1) atoms to form distorted ONaBi3 tetrahedra that share corners with four equivalent O(3)Na2Bi2 tetrahedra, corners with four equivalent O(1)NaBi3 tetrahedra, and  an edgeedge with one O(1)NaBi3 tetrahedra. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Au(1), and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded to two equivalent Na(1) and two equivalent Bi(1) atoms to form ONa2Bi2 tetrahedra that share corners with two equivalent O(3)Na2Bi2 tetrahedra and corners with eight equivalent O(1)NaBi3 tetrahedra. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Bi(2) atoms.
Na2AuBi5O11 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 2.54 Å. Both Na(1)-O(2) bond lengths are 2.55 Å. Both Na(1)-O(3) bond lengths are 2.46 Å. Au(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. All Au(1)-O(2) bond lengths are 2.04 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted BiO5 square pyramids that share corners with two equivalent Bi(2)O6 octahedra,  a cornercorner with one Bi(1)O5 square pyramid, and edges with two equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 60°. The Bi(1)-O(3) bond length is 2.15 Å. Both Bi(1)-O(1) bond lengths are 2.40 Å. Both Bi(1)-O(2) bond lengths are 2.49 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Bi(2)O6 octahedra and corners with eight equivalent Bi(1)O5 square pyramids. The corner-sharing octahedra are not tilted. Both Bi(2)-O(4) bond lengths are 1.96 Å. All Bi(2)-O(1) bond lengths are 2.14 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Bi(2), and two equivalent Bi(1) atoms to form distorted ONaBi3 tetrahedra that share corners with four equivalent O(3)Na2Bi2 tetrahedra, corners with four equivalent O(1)NaBi3 tetrahedra, and  an edgeedge with one O(1)NaBi3 tetrahedra. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Au(1), and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded to two equivalent Na(1) and two equivalent Bi(1) atoms to form ONa2Bi2 tetrahedra that share corners with two equivalent O(3)Na2Bi2 tetrahedra and corners with eight equivalent O(1)NaBi3 tetrahedra. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Bi(2) atoms.