NaHf2VF11 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent F(3), two equivalent F(5), and four equivalent F(1) atoms to form distorted NaF8 hexagonal bipyramids that share corners with two equivalent Hf(1)F7 pentagonal bipyramids, edges with two equivalent V(1)F6 octahedra, and edges with four equivalent Hf(1)F7 pentagonal bipyramids. Hf(1) is bonded to one F(2), one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form HfF7 pentagonal bipyramids that share  a cornercorner with one Na(1)F8 hexagonal bipyramid, corners with three equivalent V(1)F6 octahedra,  a cornercorner with one Hf(1)F7 pentagonal bipyramid, edges with two equivalent Na(1)F8 hexagonal bipyramids, and  an edgeedge with one Hf(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 5-33°. V(1) is bonded to two equivalent F(4) and four equivalent F(1) atoms to form VF6 octahedra that share corners with six equivalent Hf(1)F7 pentagonal bipyramids and edges with two equivalent Na(1)F8 hexagonal bipyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Hf(1), and one V(1) atom. In the second F site, F(2) is bonded in a linear geometry to two equivalent Hf(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Hf(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one Hf(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Na(1) and one Hf(1) atom.
NaHf2VF11 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent F(3), two equivalent F(5), and four equivalent F(1) atoms to form distorted NaF8 hexagonal bipyramids that share corners with two equivalent Hf(1)F7 pentagonal bipyramids, edges with two equivalent V(1)F6 octahedra, and edges with four equivalent Hf(1)F7 pentagonal bipyramids. Both Na(1)-F(3) bond lengths are 2.28 Å. Both Na(1)-F(5) bond lengths are 2.25 Å. All Na(1)-F(1) bond lengths are 2.76 Å. Hf(1) is bonded to one F(2), one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form HfF7 pentagonal bipyramids that share  a cornercorner with one Na(1)F8 hexagonal bipyramid, corners with three equivalent V(1)F6 octahedra,  a cornercorner with one Hf(1)F7 pentagonal bipyramid, edges with two equivalent Na(1)F8 hexagonal bipyramids, and  an edgeedge with one Hf(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 5-33°. The Hf(1)-F(2) bond length is 2.09 Å. The Hf(1)-F(4) bond length is 2.02 Å. The Hf(1)-F(5) bond length is 1.96 Å. Both Hf(1)-F(1) bond lengths are 2.05 Å. Both Hf(1)-F(3) bond lengths are 2.15 Å. V(1) is bonded to two equivalent F(4) and four equivalent F(1) atoms to form VF6 octahedra that share corners with six equivalent Hf(1)F7 pentagonal bipyramids and edges with two equivalent Na(1)F8 hexagonal bipyramids. Both V(1)-F(4) bond lengths are 2.12 Å. All V(1)-F(1) bond lengths are 2.13 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Hf(1), and one V(1) atom. In the second F site, F(2) is bonded in a linear geometry to two equivalent Hf(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Hf(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one Hf(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Na(1) and one Hf(1) atom.