NaV2O4 crystallizes in the monoclinic Cc space group. Na(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form edge-sharing VO6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form edge-sharing VO6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one V(2), and two equivalent V(1) atoms to form distorted ONa2V3 square pyramids that share corners with four equivalent O(2)Na2V3 square pyramids, corners with three equivalent O(3)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 square pyramids, edges with two equivalent O(2)Na2V3 square pyramids, and edges with two equivalent O(3)NaV3 trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONa2V3 square pyramids that share corners with four equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 square pyramids, edges with two equivalent O(2)Na2V3 square pyramids, and edges with two equivalent O(3)NaV3 trigonal pyramids. In the third O site, O(3) is bonded to one Na(1), one V(2), and two equivalent V(1) atoms to form ONaV3 trigonal pyramids that share corners with two equivalent O(2)Na2V3 square pyramids, corners with three equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 square pyramids, and edges with two equivalent O(2)Na2V3 square pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(1), and two equivalent V(2) atoms.
NaV2O4 crystallizes in the monoclinic Cc space group. Na(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms. The Na(1)-O(3) bond length is 2.35 Å. The Na(1)-O(4) bond length is 2.39 Å. There is one shorter (2.41 Å) and one longer (2.77 Å) Na(1)-O(1) bond length. There is one shorter (2.48 Å) and one longer (2.75 Å) Na(1)-O(2) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form edge-sharing VO6 octahedra. The V(1)-O(2) bond length is 2.06 Å. The V(1)-O(4) bond length is 2.06 Å. Both V(1)-O(1) bond lengths are 2.02 Å. There is one shorter (2.05 Å) and one longer (2.08 Å) V(1)-O(3) bond length. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form edge-sharing VO6 octahedra. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(3) bond length is 1.89 Å. Both V(2)-O(2) bond lengths are 2.00 Å. There is one shorter (1.93 Å) and one longer (2.04 Å) V(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one V(2), and two equivalent V(1) atoms to form distorted ONa2V3 square pyramids that share corners with four equivalent O(2)Na2V3 square pyramids, corners with three equivalent O(3)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 square pyramids, edges with two equivalent O(2)Na2V3 square pyramids, and edges with two equivalent O(3)NaV3 trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONa2V3 square pyramids that share corners with four equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 square pyramids, edges with two equivalent O(2)Na2V3 square pyramids, and edges with two equivalent O(3)NaV3 trigonal pyramids. In the third O site, O(3) is bonded to one Na(1), one V(2), and two equivalent V(1) atoms to form ONaV3 trigonal pyramids that share corners with two equivalent O(2)Na2V3 square pyramids, corners with three equivalent O(1)Na2V3 square pyramids, corners with two equivalent O(3)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 square pyramids, and edges with two equivalent O(2)Na2V3 square pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(1), and two equivalent V(2) atoms.