Na2VOF4 crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(2), one F(4), and three equivalent F(3) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one F(4), two equivalent F(1), and two equivalent F(2) atoms. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form distorted edge-sharing VOF5 octahedra. O(1) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), two equivalent Na(2), and one V(1) atom to form FNa3V tetrahedra that share corners with two equivalent F(1)Na3V tetrahedra, corners with three equivalent F(4)Na2V2 trigonal pyramids, corners with four equivalent F(3)Na3V trigonal pyramids, and  an edgeedge with one F(4)Na2V2 trigonal pyramid. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Na(1), two equivalent Na(2), and one V(1) atom. In the third F site, F(3) is bonded to three equivalent Na(1) and one V(1) atom to form FNa3V trigonal pyramids that share corners with four equivalent F(1)Na3V tetrahedra, corners with two equivalent F(3)Na3V trigonal pyramids, corners with three equivalent F(4)Na2V2 trigonal pyramids,  an edgeedge with one F(4)Na2V2 trigonal pyramid, and edges with two equivalent F(3)Na3V trigonal pyramids. In the fourth F site, F(4) is bonded to one Na(1), one Na(2), and two equivalent V(1) atoms to form distorted FNa2V2 trigonal pyramids that share corners with three equivalent F(1)Na3V tetrahedra, corners with three equivalent F(3)Na3V trigonal pyramids,  an edgeedge with one F(1)Na3V tetrahedra,  an edgeedge with one F(4)Na2V2 trigonal pyramid, and  an edgeedge with one F(3)Na3V trigonal pyramid.
Na2VOF4 crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(2), one F(4), and three equivalent F(3) atoms. The Na(1)-O(1) bond length is 2.83 Å. The Na(1)-F(1) bond length is 2.32 Å. The Na(1)-F(2) bond length is 2.35 Å. The Na(1)-F(4) bond length is 2.62 Å. There are a spread of Na(1)-F(3) bond distances ranging from 2.33-2.40 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one F(4), two equivalent F(1), and two equivalent F(2) atoms. The Na(2)-O(1) bond length is 2.37 Å. The Na(2)-F(4) bond length is 2.32 Å. There is one shorter (2.29 Å) and one longer (2.34 Å) Na(2)-F(1) bond length. There is one shorter (2.44 Å) and one longer (2.55 Å) Na(2)-F(2) bond length. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form distorted edge-sharing VOF5 octahedra. The V(1)-O(1) bond length is 1.65 Å. The V(1)-F(1) bond length is 1.98 Å. The V(1)-F(2) bond length is 1.94 Å. The V(1)-F(3) bond length is 1.97 Å. There is one shorter (2.00 Å) and one longer (2.27 Å) V(1)-F(4) bond length. O(1) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), two equivalent Na(2), and one V(1) atom to form FNa3V tetrahedra that share corners with two equivalent F(1)Na3V tetrahedra, corners with three equivalent F(4)Na2V2 trigonal pyramids, corners with four equivalent F(3)Na3V trigonal pyramids, and  an edgeedge with one F(4)Na2V2 trigonal pyramid. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Na(1), two equivalent Na(2), and one V(1) atom. In the third F site, F(3) is bonded to three equivalent Na(1) and one V(1) atom to form FNa3V trigonal pyramids that share corners with four equivalent F(1)Na3V tetrahedra, corners with two equivalent F(3)Na3V trigonal pyramids, corners with three equivalent F(4)Na2V2 trigonal pyramids,  an edgeedge with one F(4)Na2V2 trigonal pyramid, and edges with two equivalent F(3)Na3V trigonal pyramids. In the fourth F site, F(4) is bonded to one Na(1), one Na(2), and two equivalent V(1) atoms to form distorted FNa2V2 trigonal pyramids that share corners with three equivalent F(1)Na3V tetrahedra, corners with three equivalent F(3)Na3V trigonal pyramids,  an edgeedge with one F(1)Na3V tetrahedra,  an edgeedge with one F(4)Na2V2 trigonal pyramid, and  an edgeedge with one F(3)Na3V trigonal pyramid.