Na3V5O10 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(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-20°. In the second Na site, Na(2) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(9) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Na(1)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(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. In the third Na site, Na(3) is bonded to one O(2), one O(6), two equivalent O(10), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-18°. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form VO6 octahedra that share 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(4)O6 octahedra, and edges with four equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. In the third V site, V(3) is bonded to one O(10), one O(3), 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(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)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(6)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-18°. In the fourth V site, V(4) is bonded to one O(10), one O(4), one O(5), one O(6), one O(8), and one O(9) 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(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-14°. In the fifth V site, V(5) is bonded to one O(3), one O(6), one O(7), one O(9), and two equivalent O(1) atoms to form VO6 octahedra that share  a cornercorner with one Na(3)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, edges with two equivalent Na(2)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 13-18°. In the sixth V site, V(6) is bonded to one O(10), one O(4), one O(5), one O(8), and two equivalent O(2) 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(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(6)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 14-20°. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one V(2), and two equivalent V(5) atoms to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the second O site, O(2) is bonded to one Na(1), one Na(3), one V(1), and two equivalent V(6) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the third O site, O(3) is bonded to two equivalent Na(2), one V(2), one V(3), and one V(5) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the fourth O site, O(4) is bonded to two equivalent Na(3), one V(1), one V(4), and one V(6) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one V(3), one V(4), and one V(6) atom to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one V(3), one V(4), and one V(5) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Na(1), one V(2), one V(3), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Na(1), one V(1), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded to two equivalent Na(2), one V(3), one V(4), and one V(5) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the tenth O site, O(10) is bonded to two equivalent Na(3), one V(3), one V(4), and one V(6) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids.
Na3V5O10 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(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO6 octahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-20°. The Na(1)-O(1) bond length is 2.45 Å. The Na(1)-O(2) bond length is 2.50 Å. The Na(1)-O(5) bond length is 2.46 Å. The Na(1)-O(6) bond length is 2.46 Å. The Na(1)-O(7) bond length is 2.40 Å. The Na(1)-O(8) bond length is 2.40 Å. In the second Na site, Na(2) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(9) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Na(1)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(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. The Na(2)-O(1) bond length is 2.42 Å. The Na(2)-O(5) bond length is 2.47 Å. There is one shorter (2.39 Å) and one longer (2.47 Å) Na(2)-O(3) bond length. There is one shorter (2.36 Å) and one longer (2.55 Å) Na(2)-O(9) bond length. In the third Na site, Na(3) is bonded to one O(2), one O(6), two equivalent O(10), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-18°. The Na(3)-O(2) bond length is 2.43 Å. The Na(3)-O(6) bond length is 2.42 Å. There is one shorter (2.44 Å) and one longer (2.48 Å) Na(3)-O(10) bond length. There is one shorter (2.41 Å) and one longer (2.47 Å) Na(3)-O(4) bond length. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form VO6 octahedra that share 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(4)O6 octahedra, and edges with four equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. Both V(1)-O(2) bond lengths are 1.90 Å. Both V(1)-O(4) bond lengths are 2.05 Å. Both V(1)-O(8) bond lengths are 2.01 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. Both V(2)-O(1) bond lengths are 1.91 Å. Both V(2)-O(3) bond lengths are 2.04 Å. Both V(2)-O(7) bond lengths are 2.01 Å. In the third V site, V(3) is bonded to one O(10), one O(3), 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(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Na(3)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(6)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-18°. The V(3)-O(10) bond length is 2.15 Å. The V(3)-O(3) bond length is 2.08 Å. The V(3)-O(5) bond length is 2.09 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-O(7) bond length is 2.00 Å. The V(3)-O(9) bond length is 2.00 Å. In the fourth V site, V(4) is bonded to one O(10), one O(4), one O(5), one O(6), one O(8), and one O(9) 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(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-14°. The V(4)-O(10) bond length is 1.90 Å. The V(4)-O(4) bond length is 2.06 Å. The V(4)-O(5) bond length is 1.94 Å. The V(4)-O(6) bond length is 2.02 Å. The V(4)-O(8) bond length is 2.02 Å. The V(4)-O(9) bond length is 2.00 Å. In the fifth V site, V(5) is bonded to one O(3), one O(6), one O(7), one O(9), and two equivalent O(1) atoms to form VO6 octahedra that share  a cornercorner with one Na(3)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, edges with two equivalent Na(2)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 13-18°. The V(5)-O(3) bond length is 2.03 Å. The V(5)-O(6) bond length is 2.05 Å. The V(5)-O(7) bond length is 2.01 Å. The V(5)-O(9) bond length is 2.09 Å. There is one shorter (2.09 Å) and one longer (2.10 Å) V(5)-O(1) bond length. In the sixth V site, V(6) is bonded to one O(10), one O(4), one O(5), one O(8), and two equivalent O(2) 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(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(6)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 14-20°. The V(6)-O(10) bond length is 2.07 Å. The V(6)-O(4) bond length is 2.04 Å. The V(6)-O(5) bond length is 2.05 Å. The V(6)-O(8) bond length is 1.99 Å. There is one shorter (2.08 Å) and one longer (2.11 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(2), one V(2), and two equivalent V(5) atoms to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the second O site, O(2) is bonded to one Na(1), one Na(3), one V(1), and two equivalent V(6) atoms to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the third O site, O(3) is bonded to two equivalent Na(2), one V(2), one V(3), and one V(5) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the fourth O site, O(4) is bonded to two equivalent Na(3), one V(1), one V(4), and one V(6) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one V(3), one V(4), and one V(6) atom to form a mixture of distorted edge and corner-sharing ONa2V3 square pyramids. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one V(3), one V(4), and one V(5) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Na(1), one V(2), one V(3), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Na(1), one V(1), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded to two equivalent Na(2), one V(3), one V(4), and one V(5) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the tenth O site, O(10) is bonded to two equivalent Na(3), one V(3), one V(4), and one V(6) atom to form a mixture of edge and corner-sharing ONa2V3 square pyramids.