Na5V7O14 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the third Na site, Na(3) is bonded to one O(4), one O(6), two equivalent O(5), and two equivalent O(7) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-17°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-16°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with three equivalent Na(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. In the third V site, V(3) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-14°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one V(1), one V(2), and one V(4) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)Na2V3 square pyramids, corners with two equivalent O(4)Na2V3 square pyramids, corners with two equivalent O(5)Na2V3 square pyramids, edges with three equivalent O(2)Na3V3 octahedra,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(6)Na2V3 square pyramids. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(1), one V(1), one V(2), and one V(3) atom to form ONa3V3 octahedra that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(7)Na2V3 square pyramid, corners with two equivalent O(6)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, edges with two equivalent O(4)Na2V3 square pyramids, edges with three equivalent O(1)Na2V3 square pyramids, and edges with three equivalent O(3)Na2V3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Na(1), one Na(2), one V(1), and two equivalent V(3) atoms to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid,  a cornercorner with one O(7)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(4)Na2V3 square pyramids, edges with three equivalent O(2)Na3V3 octahedra,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(4)Na2V3 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the fourth O site, O(4) is bonded to one Na(1), one Na(3), one V(1), and two equivalent V(3) atoms to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(5)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)Na2V3 square pyramids, corners with three equivalent O(7)Na2V3 square pyramids, edges with two equivalent O(2)Na3V3 octahedra,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(3)Na2V3 square pyramids. The corner-sharing octahedral tilt angles are 5°. In the fifth O site, O(5) is bonded to two equivalent Na(3), one V(1), one V(2), and one V(4) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(6)Na2V3 square pyramids, corners with two equivalent O(7)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid, edges with two equivalent O(6)Na2V3 square pyramids, and edges with two equivalent O(7)Na2V3 square pyramids. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one V(4), and two equivalent V(2) atoms to form distorted ONa2V3 square pyramids that share corners with two equivalent O(2)Na3V3 octahedra,  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(5)Na2V3 square pyramids, corners with two equivalent O(7)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, edges with two equivalent O(1)Na2V3 square pyramids, and edges with two equivalent O(5)Na2V3 square pyramids. The corner-sharing octahedral tilt angles range from 4-6°. In the seventh O site, O(7) is bonded to two equivalent Na(3), one V(1), one V(2), and one V(3) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(3)Na2V3 square pyramid, corners with two equivalent O(5)Na2V3 square pyramids, corners with two equivalent O(6)Na2V3 square pyramids, corners with three equivalent O(4)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(5)Na2V3 square pyramids. The corner-sharing octahedral tilt angles are 3°.
Na5V7O14 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. The Na(1)-O(1) bond length is 2.42 Å. The Na(1)-O(3) bond length is 2.42 Å. The Na(1)-O(4) bond length is 2.37 Å. The Na(1)-O(6) bond length is 2.37 Å. There is one shorter (2.43 Å) and one longer (2.50 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Na(2)-O(1) bond lengths are 2.43 Å. Both Na(2)-O(2) bond lengths are 2.37 Å. Both Na(2)-O(3) bond lengths are 2.47 Å. In the third Na site, Na(3) is bonded to one O(4), one O(6), two equivalent O(5), and two equivalent O(7) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-17°. The Na(3)-O(4) bond length is 2.46 Å. The Na(3)-O(6) bond length is 2.46 Å. There is one shorter (2.40 Å) and one longer (2.46 Å) Na(3)-O(5) bond length. There is one shorter (2.38 Å) and one longer (2.46 Å) Na(3)-O(7) bond length. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-16°. The V(1)-O(1) bond length is 2.06 Å. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 2.10 Å. The V(1)-O(5) bond length is 2.02 Å. The V(1)-O(7) bond length is 2.07 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with three equivalent Na(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(2) bond length is 2.04 Å. The V(2)-O(5) bond length is 2.04 Å. The V(2)-O(7) bond length is 2.07 Å. There is one shorter (2.08 Å) and one longer (2.12 Å) V(2)-O(6) bond length. In the third V site, V(3) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. The V(3)-O(2) bond length is 2.10 Å. The V(3)-O(7) bond length is 1.99 Å. There is one shorter (1.99 Å) and one longer (2.08 Å) V(3)-O(3) bond length. There is one shorter (1.99 Å) and one longer (2.00 Å) V(3)-O(4) bond length. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-14°. Both V(4)-O(1) bond lengths are 2.02 Å. Both V(4)-O(5) bond lengths are 2.06 Å. Both V(4)-O(6) bond lengths are 1.91 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one V(1), one V(2), and one V(4) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)Na2V3 square pyramids, corners with two equivalent O(4)Na2V3 square pyramids, corners with two equivalent O(5)Na2V3 square pyramids, edges with three equivalent O(2)Na3V3 octahedra,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(6)Na2V3 square pyramids. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(1), one V(1), one V(2), and one V(3) atom to form ONa3V3 octahedra that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(7)Na2V3 square pyramid, corners with two equivalent O(6)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, edges with two equivalent O(4)Na2V3 square pyramids, edges with three equivalent O(1)Na2V3 square pyramids, and edges with three equivalent O(3)Na2V3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Na(1), one Na(2), one V(1), and two equivalent V(3) atoms to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid,  a cornercorner with one O(7)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(4)Na2V3 square pyramids, edges with three equivalent O(2)Na3V3 octahedra,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(4)Na2V3 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the fourth O site, O(4) is bonded to one Na(1), one Na(3), one V(1), and two equivalent V(3) atoms to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(5)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)Na2V3 square pyramids, corners with three equivalent O(7)Na2V3 square pyramids, edges with two equivalent O(2)Na3V3 octahedra,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(3)Na2V3 square pyramids. The corner-sharing octahedral tilt angles are 5°. In the fifth O site, O(5) is bonded to two equivalent Na(3), one V(1), one V(2), and one V(4) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(6)Na2V3 square pyramids, corners with two equivalent O(7)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid, edges with two equivalent O(6)Na2V3 square pyramids, and edges with two equivalent O(7)Na2V3 square pyramids. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one V(4), and two equivalent V(2) atoms to form distorted ONa2V3 square pyramids that share corners with two equivalent O(2)Na3V3 octahedra,  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(5)Na2V3 square pyramids, corners with two equivalent O(7)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, edges with two equivalent O(1)Na2V3 square pyramids, and edges with two equivalent O(5)Na2V3 square pyramids. The corner-sharing octahedral tilt angles range from 4-6°. In the seventh O site, O(7) is bonded to two equivalent Na(3), one V(1), one V(2), and one V(3) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na3V3 octahedra,  a cornercorner with one O(3)Na2V3 square pyramid, corners with two equivalent O(5)Na2V3 square pyramids, corners with two equivalent O(6)Na2V3 square pyramids, corners with three equivalent O(4)Na2V3 square pyramids,  an edgeedge with one O(2)Na3V3 octahedra,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(7)Na2V3 square pyramid, and edges with two equivalent O(5)Na2V3 square pyramids. The corner-sharing octahedral tilt angles are 3°.