Na2VF5 crystallizes in the monoclinic P2_1/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 F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 46°. In the second V site, V(2) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one V(1) atom. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form distorted FNa3V tetrahedra that share corners with three equivalent F(2)Na3V tetrahedra, corners with three equivalent F(3)Na2V2 trigonal pyramids, corners with four equivalent F(4)Na3V trigonal pyramids, and  an edgeedge with one F(3)Na2V2 trigonal pyramid. In the third F site, F(3) is bonded to one Na(1), one Na(2), one V(1), and one V(2) atom to form distorted FNa2V2 trigonal pyramids that share corners with three equivalent F(2)Na3V tetrahedra, corners with two equivalent F(3)Na2V2 trigonal pyramids, corners with three equivalent F(4)Na3V trigonal pyramids,  an edgeedge with one F(2)Na3V tetrahedra, and  an edgeedge with one F(4)Na3V trigonal pyramid. In the fourth F site, F(4) is bonded to one Na(1), two equivalent Na(2), and one V(2) atom to form distorted FNa3V trigonal pyramids that share corners with four equivalent F(2)Na3V tetrahedra, corners with three equivalent F(3)Na2V2 trigonal pyramids, corners with three equivalent F(4)Na3V trigonal pyramids, and  an edgeedge with one F(3)Na2V2 trigonal pyramid. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one V(2) atom.
Na2VF5 crystallizes in the monoclinic P2_1/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 F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms. The Na(1)-F(3) bond length is 2.38 Å. The Na(1)-F(4) bond length is 2.60 Å. The Na(1)-F(5) bond length is 2.23 Å. There is one shorter (2.24 Å) and one longer (2.26 Å) Na(1)-F(1) bond length. There is one shorter (2.37 Å) and one longer (2.47 Å) Na(1)-F(2) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms. The Na(2)-F(1) bond length is 2.76 Å. The Na(2)-F(2) bond length is 2.26 Å. The Na(2)-F(3) bond length is 2.35 Å. There is one shorter (2.23 Å) and one longer (2.29 Å) Na(2)-F(4) bond length. There is one shorter (2.43 Å) and one longer (2.53 Å) Na(2)-F(5) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both V(1)-F(1) bond lengths are 1.91 Å. Both V(1)-F(2) bond lengths are 1.91 Å. Both V(1)-F(3) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both V(2)-F(3) bond lengths are 2.01 Å. Both V(2)-F(4) bond lengths are 1.93 Å. Both V(2)-F(5) bond lengths are 1.90 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one V(1) atom. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form distorted FNa3V tetrahedra that share corners with three equivalent F(2)Na3V tetrahedra, corners with three equivalent F(3)Na2V2 trigonal pyramids, corners with four equivalent F(4)Na3V trigonal pyramids, and  an edgeedge with one F(3)Na2V2 trigonal pyramid. In the third F site, F(3) is bonded to one Na(1), one Na(2), one V(1), and one V(2) atom to form distorted FNa2V2 trigonal pyramids that share corners with three equivalent F(2)Na3V tetrahedra, corners with two equivalent F(3)Na2V2 trigonal pyramids, corners with three equivalent F(4)Na3V trigonal pyramids,  an edgeedge with one F(2)Na3V tetrahedra, and  an edgeedge with one F(4)Na3V trigonal pyramid. In the fourth F site, F(4) is bonded to one Na(1), two equivalent Na(2), and one V(2) atom to form distorted FNa3V trigonal pyramids that share corners with four equivalent F(2)Na3V tetrahedra, corners with three equivalent F(3)Na2V2 trigonal pyramids, corners with three equivalent F(4)Na3V trigonal pyramids, and  an edgeedge with one F(3)Na2V2 trigonal pyramid. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one V(2) atom.