NaNb7V2O14 crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent O(2) and three equivalent O(3) atoms to form NbO5 trigonal bipyramids that share corners with six equivalent V(1)O6 octahedra and corners with six equivalent Nb(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 39°. In the second Nb site, Nb(2) is bonded to one O(2), two equivalent O(1), and two equivalent O(4) atoms to form NbO5 square pyramids that share corners with two equivalent V(1)O6 octahedra, corners with six equivalent Nb(2)O5 square pyramids,  a cornercorner with one Nb(1)O5 trigonal bipyramid, and edges with two equivalent Nb(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 48°. V(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Nb(2)O5 square pyramids, corners with three equivalent Nb(1)O5 trigonal bipyramids, and  a faceface with one V(1)O6 octahedra. There are four inequivalent O sites. In the first O site, O(2) is bonded in a rectangular see-saw-like geometry to one Nb(1) and three equivalent Nb(2) atoms. In the second O site, O(3) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent V(1) atoms. In the third O site, O(4) is bonded in a square co-planar geometry to four equivalent Nb(2) atoms. In the fourth O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(2), and one V(1) atom.
NaNb7V2O14 crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. All Na(1)-O(1) bond lengths are 2.81 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent O(2) and three equivalent O(3) atoms to form NbO5 trigonal bipyramids that share corners with six equivalent V(1)O6 octahedra and corners with six equivalent Nb(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 39°. Both Nb(1)-O(2) bond lengths are 2.06 Å. All Nb(1)-O(3) bond lengths are 1.91 Å. In the second Nb site, Nb(2) is bonded to one O(2), two equivalent O(1), and two equivalent O(4) atoms to form NbO5 square pyramids that share corners with two equivalent V(1)O6 octahedra, corners with six equivalent Nb(2)O5 square pyramids,  a cornercorner with one Nb(1)O5 trigonal bipyramid, and edges with two equivalent Nb(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 48°. The Nb(2)-O(2) bond length is 2.30 Å. Both Nb(2)-O(1) bond lengths are 2.05 Å. Both Nb(2)-O(4) bond lengths are 2.16 Å. V(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Nb(2)O5 square pyramids, corners with three equivalent Nb(1)O5 trigonal bipyramids, and  a faceface with one V(1)O6 octahedra. All V(1)-O(1) bond lengths are 1.98 Å. All V(1)-O(3) bond lengths are 2.06 Å. There are four inequivalent O sites. In the first O site, O(2) is bonded in a rectangular see-saw-like geometry to one Nb(1) and three equivalent Nb(2) atoms. In the second O site, O(3) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent V(1) atoms. In the third O site, O(4) is bonded in a square co-planar geometry to four equivalent Nb(2) atoms. In the fourth O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nb(2), and one V(1) atom.