NaV2O4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), two equivalent O(4), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second V site, V(2) is bonded to one O(4), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and three equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(1) and three equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one V(2), and two equivalent V(1) atoms.
NaV2O4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. There is one shorter (2.51 Å) and one longer (2.57 Å) Na(1)-O(1) bond length. Both Na(1)-O(2) bond lengths are 2.35 Å. Both Na(1)-O(3) bond lengths are 2.34 Å. Both Na(1)-O(4) bond lengths are 2.58 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), two equivalent O(4), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(1)-O(1) bond length is 1.95 Å. Both V(1)-O(4) bond lengths are 1.99 Å. All V(1)-O(2) bond lengths are 1.98 Å. In the second V site, V(2) is bonded to one O(4), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(2)-O(4) bond length is 1.95 Å. Both V(2)-O(1) bond lengths are 1.97 Å. There are two shorter (1.97 Å) and one longer (2.02 Å) V(2)-O(3) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and three equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(1) and three equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing ONa2V3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one V(2), and two equivalent V(1) atoms.