NaV2O4F crystallizes in the orthorhombic Pmn2_1 space group. Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(3), two equivalent O(4), and two equivalent F(1) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), two equivalent O(2), and one F(1) atom to form distorted VO4F trigonal bipyramids that share  a cornercorner with one V(2)O5 trigonal bipyramid, corners with two equivalent V(1)O4F trigonal bipyramids, and edges with two equivalent V(2)O5 trigonal bipyramids. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one V(1)O4F trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, and edges with two equivalent V(1)O4F trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent Na(1), one V(1), and one V(2) atom to form distorted corner-sharing ONa2V2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(2) atom. F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one V(1) atom.
NaV2O4F crystallizes in the orthorhombic Pmn2_1 space group. Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(3), two equivalent O(4), and two equivalent F(1) atoms. The Na(1)-O(1) bond length is 2.68 Å. The Na(1)-O(2) bond length is 2.80 Å. Both Na(1)-O(3) bond lengths are 2.47 Å. Both Na(1)-O(4) bond lengths are 2.59 Å. Both Na(1)-F(1) bond lengths are 2.61 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), two equivalent O(2), and one F(1) atom to form distorted VO4F trigonal bipyramids that share  a cornercorner with one V(2)O5 trigonal bipyramid, corners with two equivalent V(1)O4F trigonal bipyramids, and edges with two equivalent V(2)O5 trigonal bipyramids. The V(1)-O(1) bond length is 1.94 Å. The V(1)-O(3) bond length is 1.76 Å. Both V(1)-O(2) bond lengths are 1.96 Å. The V(1)-F(1) bond length is 1.87 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one V(1)O4F trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, and edges with two equivalent V(1)O4F trigonal bipyramids. The V(2)-O(2) bond length is 1.97 Å. The V(2)-O(3) bond length is 1.96 Å. The V(2)-O(4) bond length is 1.66 Å. Both V(2)-O(1) bond lengths are 2.00 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent Na(1), one V(1), and one V(2) atom to form distorted corner-sharing ONa2V2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(2) atom. F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one V(1) atom.