NaV2O4 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form edge-sharing VO6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form edge-sharing VO6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form edge-sharing VO6 octahedra. In the fourth V site, V(4) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form edge-sharing VO6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one V(1), one V(2), and one V(3) atom to form distorted ONa2V3 trigonal bipyramids that share  a cornercorner with one O(6)NaV3 trigonal pyramid,  a cornercorner with one O(7)NaV3 trigonal pyramid,  a cornercorner with one O(8)NaV3 trigonal pyramid, corners with two equivalent O(5)NaV3 trigonal pyramids, edges with two equivalent O(3)Na2V3 trigonal bipyramids,  an edgeedge with one O(5)NaV3 trigonal pyramid,  an edgeedge with one O(6)NaV3 trigonal pyramid,  an edgeedge with one O(7)NaV3 trigonal pyramid, and  an edgeedge with one O(8)NaV3 trigonal pyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one V(1), one V(3), and one V(4) atom. In the third O site, O(3) is bonded to one Na(1), one Na(2), one V(2), one V(3), and one V(4) atom to form distorted ONa2V3 trigonal bipyramids that share  a cornercorner with one O(5)NaV3 trigonal pyramid,  a cornercorner with one O(6)NaV3 trigonal pyramid,  a cornercorner with one O(8)NaV3 trigonal pyramid, corners with two equivalent O(7)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 trigonal bipyramids,  an edgeedge with one O(5)NaV3 trigonal pyramid,  an edgeedge with one O(6)NaV3 trigonal pyramid,  an edgeedge with one O(7)NaV3 trigonal pyramid, and  an edgeedge with one O(8)NaV3 trigonal pyramid. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one V(1), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded to one Na(1), one V(1), one V(2), and one V(3) atom to form ONaV3 trigonal pyramids that share  a cornercorner with one O(3)Na2V3 trigonal bipyramid, corners with two equivalent O(1)Na2V3 trigonal bipyramids, corners with two equivalent O(8)NaV3 trigonal pyramids, corners with three equivalent O(6)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(1), one V(1), one V(3), and one V(4) atom to form distorted ONaV3 trigonal pyramids that share  a cornercorner with one O(1)Na2V3 trigonal bipyramid,  a cornercorner with one O(3)Na2V3 trigonal bipyramid, corners with two equivalent O(7)NaV3 trigonal pyramids, corners with three equivalent O(5)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(8)NaV3 trigonal pyramid. In the seventh O site, O(7) is bonded to one Na(2), one V(2), one V(3), and one V(4) atom to form ONaV3 trigonal pyramids that share  a cornercorner with one O(1)Na2V3 trigonal bipyramid, corners with two equivalent O(3)Na2V3 trigonal bipyramids, corners with two equivalent O(6)NaV3 trigonal pyramids, corners with three equivalent O(8)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(5)NaV3 trigonal pyramid. In the eighth O site, O(8) is bonded to one Na(2), one V(1), one V(2), and one V(4) atom to form distorted ONaV3 trigonal pyramids that share  a cornercorner with one O(1)Na2V3 trigonal bipyramid,  a cornercorner with one O(3)Na2V3 trigonal bipyramid, corners with two equivalent O(5)NaV3 trigonal pyramids, corners with three equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(6)NaV3 trigonal pyramid.
NaV2O4 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.81 Å. The Na(1)-O(2) bond length is 2.87 Å. The Na(1)-O(3) bond length is 2.40 Å. The Na(1)-O(4) bond length is 2.46 Å. The Na(1)-O(5) bond length is 2.36 Å. The Na(1)-O(6) bond length is 2.34 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom. The Na(2)-O(1) bond length is 2.41 Å. The Na(2)-O(2) bond length is 2.46 Å. The Na(2)-O(3) bond length is 2.80 Å. The Na(2)-O(4) bond length is 2.87 Å. The Na(2)-O(7) bond length is 2.36 Å. The Na(2)-O(8) bond length is 2.34 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form edge-sharing VO6 octahedra. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(2) bond length is 2.08 Å. The V(1)-O(4) bond length is 1.90 Å. The V(1)-O(5) bond length is 1.97 Å. The V(1)-O(6) bond length is 2.06 Å. The V(1)-O(8) bond length is 1.92 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form edge-sharing VO6 octahedra. The V(2)-O(1) bond length is 2.03 Å. The V(2)-O(3) bond length is 2.08 Å. The V(2)-O(4) bond length is 2.10 Å. The V(2)-O(5) bond length is 2.01 Å. The V(2)-O(7) bond length is 2.03 Å. The V(2)-O(8) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form edge-sharing VO6 octahedra. The V(3)-O(1) bond length is 2.07 Å. The V(3)-O(2) bond length is 2.10 Å. The V(3)-O(3) bond length is 2.03 Å. The V(3)-O(5) bond length is 2.04 Å. The V(3)-O(6) bond length is 2.08 Å. The V(3)-O(7) bond length is 2.01 Å. In the fourth V site, V(4) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form edge-sharing VO6 octahedra. The V(4)-O(2) bond length is 1.91 Å. The V(4)-O(3) bond length is 1.96 Å. The V(4)-O(4) bond length is 2.08 Å. The V(4)-O(6) bond length is 1.91 Å. The V(4)-O(7) bond length is 1.97 Å. The V(4)-O(8) bond length is 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one V(1), one V(2), and one V(3) atom to form distorted ONa2V3 trigonal bipyramids that share  a cornercorner with one O(6)NaV3 trigonal pyramid,  a cornercorner with one O(7)NaV3 trigonal pyramid,  a cornercorner with one O(8)NaV3 trigonal pyramid, corners with two equivalent O(5)NaV3 trigonal pyramids, edges with two equivalent O(3)Na2V3 trigonal bipyramids,  an edgeedge with one O(5)NaV3 trigonal pyramid,  an edgeedge with one O(6)NaV3 trigonal pyramid,  an edgeedge with one O(7)NaV3 trigonal pyramid, and  an edgeedge with one O(8)NaV3 trigonal pyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one V(1), one V(3), and one V(4) atom. In the third O site, O(3) is bonded to one Na(1), one Na(2), one V(2), one V(3), and one V(4) atom to form distorted ONa2V3 trigonal bipyramids that share  a cornercorner with one O(5)NaV3 trigonal pyramid,  a cornercorner with one O(6)NaV3 trigonal pyramid,  a cornercorner with one O(8)NaV3 trigonal pyramid, corners with two equivalent O(7)NaV3 trigonal pyramids, edges with two equivalent O(1)Na2V3 trigonal bipyramids,  an edgeedge with one O(5)NaV3 trigonal pyramid,  an edgeedge with one O(6)NaV3 trigonal pyramid,  an edgeedge with one O(7)NaV3 trigonal pyramid, and  an edgeedge with one O(8)NaV3 trigonal pyramid. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one V(1), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded to one Na(1), one V(1), one V(2), and one V(3) atom to form ONaV3 trigonal pyramids that share  a cornercorner with one O(3)Na2V3 trigonal bipyramid, corners with two equivalent O(1)Na2V3 trigonal bipyramids, corners with two equivalent O(8)NaV3 trigonal pyramids, corners with three equivalent O(6)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(7)NaV3 trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(1), one V(1), one V(3), and one V(4) atom to form distorted ONaV3 trigonal pyramids that share  a cornercorner with one O(1)Na2V3 trigonal bipyramid,  a cornercorner with one O(3)Na2V3 trigonal bipyramid, corners with two equivalent O(7)NaV3 trigonal pyramids, corners with three equivalent O(5)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(8)NaV3 trigonal pyramid. In the seventh O site, O(7) is bonded to one Na(2), one V(2), one V(3), and one V(4) atom to form ONaV3 trigonal pyramids that share  a cornercorner with one O(1)Na2V3 trigonal bipyramid, corners with two equivalent O(3)Na2V3 trigonal bipyramids, corners with two equivalent O(6)NaV3 trigonal pyramids, corners with three equivalent O(8)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(5)NaV3 trigonal pyramid. In the eighth O site, O(8) is bonded to one Na(2), one V(1), one V(2), and one V(4) atom to form distorted ONaV3 trigonal pyramids that share  a cornercorner with one O(1)Na2V3 trigonal bipyramid,  a cornercorner with one O(3)Na2V3 trigonal bipyramid, corners with two equivalent O(5)NaV3 trigonal pyramids, corners with three equivalent O(7)NaV3 trigonal pyramids,  an edgeedge with one O(1)Na2V3 trigonal bipyramid,  an edgeedge with one O(3)Na2V3 trigonal bipyramid, and  an edgeedge with one O(6)NaV3 trigonal pyramid.