NaHf2TiF11 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one F(3), one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(7) atoms to form distorted NaF8 hexagonal bipyramids that share  a cornercorner with one Hf(1)F7 pentagonal bipyramid,  a cornercorner with one Hf(2)F7 pentagonal bipyramid, edges with two equivalent Ti(1)F6 octahedra, edges with two equivalent Hf(1)F7 pentagonal bipyramids, and edges with two equivalent Hf(2)F7 pentagonal bipyramids. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one F(3), one F(6), one F(8), two equivalent F(1), and two equivalent F(7) atoms to form HfF7 pentagonal bipyramids that share  a cornercorner with one Na(1)F8 hexagonal bipyramid, corners with three equivalent Ti(1)F6 octahedra,  a cornercorner with one Hf(2)F7 pentagonal bipyramid, edges with two equivalent Na(1)F8 hexagonal bipyramids, and  an edgeedge with one Hf(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 0-32°. In the second Hf site, Hf(2) is bonded to one F(4), one F(5), one F(8), two equivalent F(2), and two equivalent F(7) atoms to form HfF7 pentagonal bipyramids that share  a cornercorner with one Na(1)F8 hexagonal bipyramid, corners with three equivalent Ti(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 5-32°. Ti(1) is bonded to one F(5), one F(6), two equivalent F(1), and two equivalent F(2) atoms to form TiF6 octahedra that share corners with three equivalent Hf(1)F7 pentagonal bipyramids, corners with three equivalent Hf(2)F7 pentagonal bipyramids, and edges with two equivalent Na(1)F8 hexagonal bipyramids. There are eight 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 Ti(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Hf(2), and one Ti(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Na(1) and one Hf(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Na(1) and one Hf(2) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Hf(2) and one Ti(1) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Hf(1) and one Ti(1) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Na(1), one Hf(1), and one Hf(2) atom. In the eighth F site, F(8) is bonded in a linear geometry to one Hf(1) and one Hf(2) atom.
NaHf2TiF11 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one F(3), one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(7) atoms to form distorted NaF8 hexagonal bipyramids that share  a cornercorner with one Hf(1)F7 pentagonal bipyramid,  a cornercorner with one Hf(2)F7 pentagonal bipyramid, edges with two equivalent Ti(1)F6 octahedra, edges with two equivalent Hf(1)F7 pentagonal bipyramids, and edges with two equivalent Hf(2)F7 pentagonal bipyramids. The Na(1)-F(3) bond length is 2.25 Å. The Na(1)-F(4) bond length is 2.24 Å. Both Na(1)-F(1) bond lengths are 2.77 Å. Both Na(1)-F(2) bond lengths are 2.78 Å. Both Na(1)-F(7) bond lengths are 2.30 Å. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one F(3), one F(6), one F(8), two equivalent F(1), and two equivalent F(7) atoms to form HfF7 pentagonal bipyramids that share  a cornercorner with one Na(1)F8 hexagonal bipyramid, corners with three equivalent Ti(1)F6 octahedra,  a cornercorner with one Hf(2)F7 pentagonal bipyramid, edges with two equivalent Na(1)F8 hexagonal bipyramids, and  an edgeedge with one Hf(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 0-32°. The Hf(1)-F(3) bond length is 1.96 Å. The Hf(1)-F(6) bond length is 2.04 Å. The Hf(1)-F(8) bond length is 2.10 Å. Both Hf(1)-F(1) bond lengths are 2.06 Å. Both Hf(1)-F(7) bond lengths are 2.16 Å. In the second Hf site, Hf(2) is bonded to one F(4), one F(5), one F(8), two equivalent F(2), and two equivalent F(7) atoms to form HfF7 pentagonal bipyramids that share  a cornercorner with one Na(1)F8 hexagonal bipyramid, corners with three equivalent Ti(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 5-32°. The Hf(2)-F(4) bond length is 1.96 Å. The Hf(2)-F(5) bond length is 2.04 Å. The Hf(2)-F(8) bond length is 2.12 Å. Both Hf(2)-F(2) bond lengths are 2.05 Å. Both Hf(2)-F(7) bond lengths are 2.15 Å. Ti(1) is bonded to one F(5), one F(6), two equivalent F(1), and two equivalent F(2) atoms to form TiF6 octahedra that share corners with three equivalent Hf(1)F7 pentagonal bipyramids, corners with three equivalent Hf(2)F7 pentagonal bipyramids, and edges with two equivalent Na(1)F8 hexagonal bipyramids. The Ti(1)-F(5) bond length is 2.10 Å. The Ti(1)-F(6) bond length is 2.09 Å. Both Ti(1)-F(1) bond lengths are 2.15 Å. Both Ti(1)-F(2) bond lengths are 2.14 Å. There are eight 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 Ti(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Hf(2), and one Ti(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Na(1) and one Hf(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Na(1) and one Hf(2) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Hf(2) and one Ti(1) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Hf(1) and one Ti(1) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Na(1), one Hf(1), and one Hf(2) atom. In the eighth F site, F(8) is bonded in a linear geometry to one Hf(1) and one Hf(2) atom.