NaV6O11 crystallizes in the hexagonal P6_3mc space group. Na(1) is bonded in a 12-coordinate geometry to three equivalent O(2), three equivalent O(5), and six equivalent O(4) atoms. There are four inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second V site, V(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the third V site, V(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the fourth V site, V(4) is bonded to one O(1), one O(3), and three equivalent O(4) atoms to form corner-sharing VO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-57°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one V(4) and three equivalent V(3) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one V(2), and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one V(4) and three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(1), one V(1), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one V(1), and two equivalent V(3) atoms.
NaV6O11 crystallizes in the hexagonal P6_3mc space group. Na(1) is bonded in a 12-coordinate geometry to three equivalent O(2), three equivalent O(5), and six equivalent O(4) atoms. All Na(1)-O(2) bond lengths are 3.01 Å. All Na(1)-O(5) bond lengths are 2.71 Å. All Na(1)-O(4) bond lengths are 2.95 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. All V(1)-O(4) bond lengths are 2.03 Å. All V(1)-O(5) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, corners with three equivalent V(4)O5 trigonal bipyramids, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. All V(2)-O(2) bond lengths are 2.04 Å. All V(2)-O(4) bond lengths are 2.03 Å. In the third V site, V(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The V(3)-O(1) bond length is 2.04 Å. The V(3)-O(3) bond length is 2.03 Å. Both V(3)-O(2) bond lengths are 1.94 Å. Both V(3)-O(5) bond lengths are 1.94 Å. In the fourth V site, V(4) is bonded to one O(1), one O(3), and three equivalent O(4) atoms to form corner-sharing VO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-57°. The V(4)-O(1) bond length is 2.24 Å. The V(4)-O(3) bond length is 2.27 Å. All V(4)-O(4) bond lengths are 1.89 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one V(4) and three equivalent V(3) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one V(2), and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one V(4) and three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(1), one V(1), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one V(1), and two equivalent V(3) atoms.