NaVF6 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(4), two equivalent F(3), and four equivalent F(1) atoms to form distorted NaF7 pentagonal bipyramids that share corners with five equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 20-40°. V(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form VF6 octahedra that share corners with five equivalent Na(1)F7 pentagonal bipyramids and  an edgeedge with one Na(1)F7 pentagonal bipyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one V(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Na(1) and one V(1) atom.
NaVF6 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(4), two equivalent F(3), and four equivalent F(1) atoms to form distorted NaF7 pentagonal bipyramids that share corners with five equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 20-40°. The Na(1)-F(4) bond length is 2.28 Å. Both Na(1)-F(3) bond lengths are 2.30 Å. There are two shorter (2.29 Å) and two longer (2.45 Å) Na(1)-F(1) bond lengths. V(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form VF6 octahedra that share corners with five equivalent Na(1)F7 pentagonal bipyramids and  an edgeedge with one Na(1)F7 pentagonal bipyramid. The V(1)-F(2) bond length is 1.75 Å. The V(1)-F(4) bond length is 1.80 Å. Both V(1)-F(1) bond lengths are 1.82 Å. Both V(1)-F(3) bond lengths are 1.77 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one V(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Na(1) and one V(1) atom.