Na3V5O10 crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(6), and two equivalent O(7) atoms. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms to form distorted NaO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(6)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-18°. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(3), one O(4), one O(6), and one O(9) atom. In the fourth Na site, Na(4) is bonded to one O(10), one O(2), one O(3), one O(4), one O(5), and one O(9) atom to form distorted NaO6 octahedra that share  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with three equivalent V(6)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-18°. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms to form VO6 octahedra that share edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(6)O6 octahedra. In the second V site, V(2) is bonded to one O(10), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. In the third V site, V(3) is bonded to one O(4), one O(6), one O(7), one O(9), and two equivalent O(1) atoms to form VO6 octahedra that share  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Na(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. In the fifth V site, V(5) is bonded to one O(10), one O(4), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(4)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-15°. In the sixth V site, V(6) is bonded to one O(10), one O(3), one O(5), one O(8), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with three equivalent Na(4)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)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 14-18°. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one V(4), and two equivalent V(3) atoms to form distorted ONa2V3 square pyramids that share  a cornercorner with one O(10)Na2V3 square pyramid,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid,  a cornercorner with one O(9)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(9)Na2V3 square pyramid, edges with two equivalent O(4)Na2V3 square pyramids, edges with two equivalent O(6)Na2V3 square pyramids, and edges with two equivalent O(7)NaV3 trigonal pyramids. In the second O site, O(2) is bonded to one Na(2), one Na(4), one V(1), and two equivalent V(6) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 square pyramids. In the third O site, O(3) is bonded to one Na(3), one Na(4), one V(1), one V(2), and one V(6) atom to form a mixture of corner and edge-sharing ONa2V3 square pyramids. In the fourth O site, O(4) is bonded to one Na(3), one Na(4), one V(3), one V(4), and one V(5) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with three equivalent O(10)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid, edges with two equivalent O(1)Na2V3 square pyramids, edges with two equivalent O(9)Na2V3 square pyramids, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the fifth O site, O(5) is bonded to one Na(2), one Na(4), one V(2), one V(5), and one V(6) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid,  a cornercorner with one O(9)Na2V3 square pyramid, corners with two equivalent O(10)Na2V3 square pyramids,  a cornercorner with one O(7)NaV3 trigonal pyramid,  an edgeedge with one O(10)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(9)Na2V3 square pyramid, and edges with two equivalent O(2)Na2V3 square pyramids. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one V(2), one V(3), and one V(5) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(10)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(9)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(10)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(5)Na2V3 square pyramid,  an edgeedge with one O(9)Na2V3 square pyramid, edges with two equivalent O(1)Na2V3 square pyramids, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the seventh O site, O(7) is bonded to one Na(1), one V(3), one V(4), and one V(5) atom to form distorted ONaV3 trigonal pyramids that share  a cornercorner with one O(10)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(4)Na2V3 square pyramids, corners with two equivalent O(6)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(9)Na2V3 square pyramid, and edges with two equivalent O(1)Na2V3 square pyramids. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Na(2), one V(1), one V(2), and one V(6) atom. In the ninth O site, O(9) is bonded to one Na(3), one Na(4), one V(2), one V(3), and one V(5) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid, corners with two equivalent O(6)Na2V3 square pyramids, corners with three equivalent O(3)Na2V3 square pyramids,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid, edges with two equivalent O(10)Na2V3 square pyramids, edges with two equivalent O(4)Na2V3 square pyramids, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the tenth O site, O(10) is bonded to one Na(3), one Na(4), one V(2), one V(5), and one V(6) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(5)Na2V3 square pyramids, corners with three equivalent O(4)Na2V3 square pyramids,  a cornercorner with one O(7)NaV3 trigonal pyramid,  an edgeedge with one O(2)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid, edges with two equivalent O(3)Na2V3 square pyramids, and edges with two equivalent O(9)Na2V3 square pyramids.
Na3V5O10 crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(6), and two equivalent O(7) atoms. Both Na(1)-O(1) bond lengths are 2.48 Å. Both Na(1)-O(6) bond lengths are 2.40 Å. Both Na(1)-O(7) bond lengths are 2.41 Å. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms to form distorted NaO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(6)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-18°. Both Na(2)-O(2) bond lengths are 2.45 Å. Both Na(2)-O(5) bond lengths are 2.52 Å. Both Na(2)-O(8) bond lengths are 2.44 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(3), one O(4), one O(6), and one O(9) atom. The Na(3)-O(1) bond length is 2.44 Å. The Na(3)-O(10) bond length is 2.37 Å. The Na(3)-O(3) bond length is 2.44 Å. The Na(3)-O(4) bond length is 2.40 Å. The Na(3)-O(6) bond length is 2.45 Å. The Na(3)-O(9) bond length is 2.46 Å. In the fourth Na site, Na(4) is bonded to one O(10), one O(2), one O(3), one O(4), one O(5), and one O(9) atom to form distorted NaO6 octahedra that share  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with three equivalent V(6)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-18°. The Na(4)-O(10) bond length is 2.48 Å. The Na(4)-O(2) bond length is 2.43 Å. The Na(4)-O(3) bond length is 2.43 Å. The Na(4)-O(4) bond length is 2.46 Å. The Na(4)-O(5) bond length is 2.42 Å. The Na(4)-O(9) bond length is 2.44 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms to form VO6 octahedra that share edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(6)O6 octahedra. Both V(1)-O(2) bond lengths are 1.92 Å. Both V(1)-O(3) bond lengths are 2.03 Å. Both V(1)-O(8) bond lengths are 2.00 Å. In the second V site, V(2) is bonded to one O(10), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The V(2)-O(10) bond length is 2.08 Å. The V(2)-O(3) bond length is 2.04 Å. The V(2)-O(5) bond length is 2.10 Å. The V(2)-O(6) bond length is 2.04 Å. The V(2)-O(8) bond length is 2.02 Å. The V(2)-O(9) bond length is 2.05 Å. In the third V site, V(3) is bonded to one O(4), one O(6), one O(7), one O(9), and two equivalent O(1) atoms to form VO6 octahedra that share  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The V(3)-O(4) bond length is 2.08 Å. The V(3)-O(6) bond length is 2.03 Å. The V(3)-O(7) bond length is 2.08 Å. The V(3)-O(9) bond length is 2.01 Å. There is one shorter (2.06 Å) and one longer (2.11 Å) V(3)-O(1) bond length. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Na(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. Both V(4)-O(1) bond lengths are 1.92 Å. Both V(4)-O(4) bond lengths are 2.02 Å. Both V(4)-O(7) bond lengths are 2.01 Å. In the fifth V site, V(5) is bonded to one O(10), one O(4), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(4)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-15°. The V(5)-O(10) bond length is 1.99 Å. The V(5)-O(4) bond length is 2.05 Å. The V(5)-O(5) bond length is 1.89 Å. The V(5)-O(6) bond length is 2.01 Å. The V(5)-O(7) bond length is 1.95 Å. The V(5)-O(9) bond length is 2.01 Å. In the sixth V site, V(6) is bonded to one O(10), one O(3), one O(5), one O(8), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with three equivalent Na(4)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)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 14-18°. The V(6)-O(10) bond length is 2.02 Å. The V(6)-O(3) bond length is 2.07 Å. The V(6)-O(5) bond length is 2.12 Å. The V(6)-O(8) bond length is 2.01 Å. There is one shorter (2.06 Å) and one longer (2.13 Å) V(6)-O(2) bond length. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one V(4), and two equivalent V(3) atoms to form distorted ONa2V3 square pyramids that share  a cornercorner with one O(10)Na2V3 square pyramid,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid,  a cornercorner with one O(9)Na2V3 square pyramid, corners with two equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(9)Na2V3 square pyramid, edges with two equivalent O(4)Na2V3 square pyramids, edges with two equivalent O(6)Na2V3 square pyramids, and edges with two equivalent O(7)NaV3 trigonal pyramids. In the second O site, O(2) is bonded to one Na(2), one Na(4), one V(1), and two equivalent V(6) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 square pyramids. In the third O site, O(3) is bonded to one Na(3), one Na(4), one V(1), one V(2), and one V(6) atom to form a mixture of corner and edge-sharing ONa2V3 square pyramids. In the fourth O site, O(4) is bonded to one Na(3), one Na(4), one V(3), one V(4), and one V(5) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with three equivalent O(10)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(3)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid, edges with two equivalent O(1)Na2V3 square pyramids, edges with two equivalent O(9)Na2V3 square pyramids, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the fifth O site, O(5) is bonded to one Na(2), one Na(4), one V(2), one V(5), and one V(6) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(3)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid,  a cornercorner with one O(9)Na2V3 square pyramid, corners with two equivalent O(10)Na2V3 square pyramids,  a cornercorner with one O(7)NaV3 trigonal pyramid,  an edgeedge with one O(10)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(9)Na2V3 square pyramid, and edges with two equivalent O(2)Na2V3 square pyramids. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one V(2), one V(3), and one V(5) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(10)Na2V3 square pyramid,  a cornercorner with one O(4)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(9)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(10)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(5)Na2V3 square pyramid,  an edgeedge with one O(9)Na2V3 square pyramid, edges with two equivalent O(1)Na2V3 square pyramids, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the seventh O site, O(7) is bonded to one Na(1), one V(3), one V(4), and one V(5) atom to form distorted ONaV3 trigonal pyramids that share  a cornercorner with one O(10)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(4)Na2V3 square pyramids, corners with two equivalent O(6)Na2V3 square pyramids, corners with two equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(4)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid,  an edgeedge with one O(9)Na2V3 square pyramid, and edges with two equivalent O(1)Na2V3 square pyramids. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Na(2), one V(1), one V(2), and one V(6) atom. In the ninth O site, O(9) is bonded to one Na(3), one Na(4), one V(2), one V(3), and one V(5) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(5)Na2V3 square pyramid, corners with two equivalent O(6)Na2V3 square pyramids, corners with three equivalent O(3)Na2V3 square pyramids,  an edgeedge with one O(1)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid, edges with two equivalent O(10)Na2V3 square pyramids, edges with two equivalent O(4)Na2V3 square pyramids, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the tenth O site, O(10) is bonded to one Na(3), one Na(4), one V(2), one V(5), and one V(6) atom to form ONa2V3 square pyramids that share  a cornercorner with one O(1)Na2V3 square pyramid,  a cornercorner with one O(2)Na2V3 square pyramid,  a cornercorner with one O(6)Na2V3 square pyramid, corners with two equivalent O(5)Na2V3 square pyramids, corners with three equivalent O(4)Na2V3 square pyramids,  a cornercorner with one O(7)NaV3 trigonal pyramid,  an edgeedge with one O(2)Na2V3 square pyramid,  an edgeedge with one O(5)Na2V3 square pyramid,  an edgeedge with one O(6)Na2V3 square pyramid, edges with two equivalent O(3)Na2V3 square pyramids, and edges with two equivalent O(9)Na2V3 square pyramids.