NaV6O11 crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded to six equivalent O(1) and six equivalent O(3) atoms to form distorted NaO12 cuboctahedra that share corners with six equivalent Na(1)O12 cuboctahedra, edges with six equivalent V(3)O6 octahedra, edges with three equivalent V(1)O5 trigonal bipyramids, and faces with six equivalent V(2)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and three equivalent O(3) atoms to form VO5 trigonal bipyramids that share corners with six equivalent V(2)O6 octahedra, corners with six equivalent V(3)O6 octahedra, and edges with three equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the second V site, V(2) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids, faces with three equivalent Na(1)O12 cuboctahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the third V site, V(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Na(1)O12 cuboctahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and two equivalent V(3) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one V(1) and three equivalent V(3) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Na(1), one V(1), and two equivalent V(2) atoms.
NaV6O11 crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded to six equivalent O(1) and six equivalent O(3) atoms to form distorted NaO12 cuboctahedra that share corners with six equivalent Na(1)O12 cuboctahedra, edges with six equivalent V(3)O6 octahedra, edges with three equivalent V(1)O5 trigonal bipyramids, and faces with six equivalent V(2)O6 octahedra. All Na(1)-O(1) bond lengths are 2.87 Å. All Na(1)-O(3) bond lengths are 2.94 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and three equivalent O(3) atoms to form VO5 trigonal bipyramids that share corners with six equivalent V(2)O6 octahedra, corners with six equivalent V(3)O6 octahedra, and edges with three equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 42-56°. Both V(1)-O(2) bond lengths are 2.26 Å. All V(1)-O(3) bond lengths are 1.89 Å. In the second V site, V(2) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids, faces with three equivalent Na(1)O12 cuboctahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. All V(2)-O(1) bond lengths are 2.04 Å. All V(2)-O(3) bond lengths are 2.03 Å. In the third V site, V(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Na(1)O12 cuboctahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. Both V(3)-O(2) bond lengths are 2.03 Å. All V(3)-O(1) bond lengths are 1.94 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and two equivalent V(3) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one V(1) and three equivalent V(3) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Na(1), one V(1), and two equivalent V(2) atoms.