NaV3O8 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form edge-sharing NaO6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(5), one O(8), and three equivalent O(1) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), and three equivalent O(7) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(8), and two equivalent O(5) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one V(3) and three equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(2) atoms. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(1) and one V(3) atom.
NaV3O8 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form edge-sharing NaO6 octahedra. The Na(1)-O(4) bond length is 2.35 Å. The Na(1)-O(6) bond length is 2.33 Å. Both Na(1)-O(2) bond lengths are 2.40 Å. Both Na(1)-O(3) bond lengths are 2.39 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(5), one O(8), and three equivalent O(1) atoms. The V(1)-O(2) bond length is 1.62 Å. The V(1)-O(5) bond length is 2.10 Å. The V(1)-O(8) bond length is 1.76 Å. There are two shorter (1.87 Å) and one longer (2.43 Å) V(1)-O(1) bond length. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), and three equivalent O(7) atoms. The V(2)-O(3) bond length is 1.63 Å. The V(2)-O(4) bond length is 1.72 Å. There are two shorter (1.88 Å) and one longer (2.01 Å) V(2)-O(7) bond length. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(8), and two equivalent O(5) atoms. The V(3)-O(1) bond length is 2.27 Å. The V(3)-O(4) bond length is 2.01 Å. The V(3)-O(6) bond length is 1.61 Å. The V(3)-O(8) bond length is 1.84 Å. Both V(3)-O(5) bond lengths are 1.88 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one V(3) and three equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(2) atoms. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(1) and one V(3) atom.