NaVF4 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to one F(1), one F(2), two equivalent F(4), and three equivalent F(3) atoms. V(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-39°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Na(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(1) atom.
NaVF4 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to one F(1), one F(2), two equivalent F(4), and three equivalent F(3) atoms. The Na(1)-F(1) bond length is 2.30 Å. The Na(1)-F(2) bond length is 2.86 Å. There is one shorter (2.20 Å) and one longer (2.34 Å) Na(1)-F(4) bond length. There are a spread of Na(1)-F(3) bond distances ranging from 2.23-2.70 Å. V(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-39°. The V(1)-F(3) bond length is 1.89 Å. The V(1)-F(4) bond length is 1.87 Å. There is one shorter (1.98 Å) and one longer (2.00 Å) V(1)-F(1) bond length. There is one shorter (1.96 Å) and one longer (1.99 Å) V(1)-F(2) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Na(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(1) atom.