Na4UO5 is Caswellsilverite-like structured and crystallizes in the tetragonal I4/m space group. Na(1) is bonded to one O(2) and five equivalent O(1) atoms to form NaO6 octahedra that share  a cornercorner with one U(1)O6 octahedra, corners with five equivalent Na(1)O6 octahedra, edges with three equivalent U(1)O6 octahedra, and edges with nine equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. U(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form UO6 octahedra that share corners with two equivalent U(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, and edges with twelve equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Na(1) and one U(1) atom to form distorted ONa5U octahedra that share  a cornercorner with one O(2)Na4U2 octahedra, corners with five equivalent O(1)Na5U octahedra, edges with three equivalent O(2)Na4U2 octahedra, and edges with nine equivalent O(1)Na5U octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the second O site, O(2) is bonded to four equivalent Na(1) and two equivalent U(1) atoms to form ONa4U2 octahedra that share corners with two equivalent O(2)Na4U2 octahedra, corners with four equivalent O(1)Na5U octahedra, and edges with twelve equivalent O(1)Na5U octahedra. The corner-sharing octahedral tilt angles range from 0-11°.
Na4UO5 is Caswellsilverite-like structured and crystallizes in the tetragonal I4/m space group. Na(1) is bonded to one O(2) and five equivalent O(1) atoms to form NaO6 octahedra that share  a cornercorner with one U(1)O6 octahedra, corners with five equivalent Na(1)O6 octahedra, edges with three equivalent U(1)O6 octahedra, and edges with nine equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. The Na(1)-O(2) bond length is 2.39 Å. There are a spread of Na(1)-O(1) bond distances ranging from 2.32-2.65 Å. U(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form UO6 octahedra that share corners with two equivalent U(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, and edges with twelve equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both U(1)-O(2) bond lengths are 2.31 Å. All U(1)-O(1) bond lengths are 2.02 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Na(1) and one U(1) atom to form distorted ONa5U octahedra that share  a cornercorner with one O(2)Na4U2 octahedra, corners with five equivalent O(1)Na5U octahedra, edges with three equivalent O(2)Na4U2 octahedra, and edges with nine equivalent O(1)Na5U octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the second O site, O(2) is bonded to four equivalent Na(1) and two equivalent U(1) atoms to form ONa4U2 octahedra that share corners with two equivalent O(2)Na4U2 octahedra, corners with four equivalent O(1)Na5U octahedra, and edges with twelve equivalent O(1)Na5U octahedra. The corner-sharing octahedral tilt angles range from 0-11°.