Na3V3O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a hexagonal planar geometry to one O(3); one O(5); one O(6); one O(8); and two equivalent O(4,7) atoms. In the second Na site, Na(2) is bonded in a distorted single-bond geometry to one O(1,2) atom. In the third Na site, Na(3) is bonded in a distorted single-bond geometry to one O(1,2) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(8) atoms to form corner-sharing VO6 octahedra. In the second V site, V(2) is bonded to two equivalent O(5) and four equivalent O(4,7) atoms to form corner-sharing VO6 octahedra. In the third V site, V(3) is bonded to one O(1,2); one O(3); one O(5); and one O(8) atom to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles are 15°. In the fourth V site, V(4) is bonded to one O(1,2); one O(6); and two equivalent O(4,7) atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles are 15°. There are six inequivalent O sites. In the first O site, O(1,2) is bonded in a linear geometry to one Na(2) and one V(4) atom. In the second O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), one V(1), and one V(3) atom. In the third O site, O(4,7) is bonded in a 2-coordinate geometry to one Na(1), one V(2), and one V(4) atom. In the fourth O site, O(5) is bonded in a 2-coordinate geometry to one Na(1), one V(2), and one V(3) atom. In the fifth O site, O(6) is bonded in a 2-coordinate geometry to one Na(1), one V(1), and one V(4) atom. In the sixth O site, O(8) is bonded in a 2-coordinate geometry to one Na(1), one V(1), and one V(3) atom.
Na3V3O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a hexagonal planar geometry to one O(3); one O(5); one O(6); one O(8); and two equivalent O(4,7) atoms. The Na(1)-O(3) bond length is 2.75 Å. The Na(1)-O(5) bond length is 2.75 Å. The Na(1)-O(6) bond length is 2.76 Å. The Na(1)-O(8) bond length is 2.74 Å. There is one shorter (2.75 Å) and one longer (2.76 Å) Na(1)-O(4,7) bond length. In the second Na site, Na(2) is bonded in a distorted single-bond geometry to one O(1,2) atom. The Na(2)-O(1,2) bond length is 2.21 Å. In the third Na site, Na(3) is bonded in a distorted single-bond geometry to one O(1,2) atom. The Na(3)-O(1,2) bond length is 2.21 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(8) atoms to form corner-sharing VO6 octahedra. Both V(1)-O(3) bond lengths are 2.02 Å. Both V(1)-O(6) bond lengths are 2.02 Å. Both V(1)-O(8) bond lengths are 2.03 Å. In the second V site, V(2) is bonded to two equivalent O(5) and four equivalent O(4,7) atoms to form corner-sharing VO6 octahedra. Both V(2)-O(5) bond lengths are 2.03 Å. All V(2)-O(4,7) bond lengths are 2.02 Å. In the third V site, V(3) is bonded to one O(1,2); one O(3); one O(5); and one O(8) atom to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles are 15°. The V(3)-O(1,2) bond length is 1.68 Å. The V(3)-O(3) bond length is 1.76 Å. The V(3)-O(5) bond length is 1.76 Å. The V(3)-O(8) bond length is 1.76 Å. In the fourth V site, V(4) is bonded to one O(1,2); one O(6); and two equivalent O(4,7) atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles are 15°. The V(4)-O(1,2) bond length is 1.68 Å. The V(4)-O(6) bond length is 1.76 Å. Both V(4)-O(4,7) bond lengths are 1.76 Å. There are six inequivalent O sites. In the first O site, O(1,2) is bonded in a linear geometry to one Na(2) and one V(4) atom. In the second O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), one V(1), and one V(3) atom. In the third O site, O(4,7) is bonded in a 2-coordinate geometry to one Na(1), one V(2), and one V(4) atom. In the fourth O site, O(5) is bonded in a 2-coordinate geometry to one Na(1), one V(2), and one V(3) atom. In the fifth O site, O(6) is bonded in a 2-coordinate geometry to one Na(1), one V(1), and one V(4) atom. In the sixth O site, O(8) is bonded in a 2-coordinate geometry to one Na(1), one V(1), and one V(3) atom.