Na2TiF5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted NaF7 pentagonal bipyramids that share  a cornercorner with one Ti(1)F6 octahedra,  a cornercorner with one Ti(2)F6 octahedra,  an edgeedge with one Ti(2)F6 octahedra, edges with two equivalent Ti(1)F6 octahedra, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 24-38°. 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 Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form TiF6 octahedra that share corners with two equivalent Ti(2)F6 octahedra, corners with two equivalent Na(1)F7 pentagonal bipyramids, and edges with four equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. In the second Ti site, Ti(2) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form TiF6 octahedra that share corners with two equivalent Ti(1)F6 octahedra, corners with two equivalent Na(1)F7 pentagonal bipyramids, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. 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 Ti(1) atom. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Ti(1) atom to form distorted FNa3Ti tetrahedra that share corners with three equivalent F(3)Na2Ti2 tetrahedra, corners with three equivalent F(2)Na3Ti tetrahedra, corners with four equivalent F(4)Na3Ti trigonal pyramids, and  an edgeedge with one F(3)Na2Ti2 tetrahedra. In the third F site, F(3) is bonded to one Na(1), one Na(2), one Ti(1), and one Ti(2) atom to form distorted FNa2Ti2 tetrahedra that share corners with two equivalent F(3)Na2Ti2 tetrahedra, corners with three equivalent F(2)Na3Ti tetrahedra, corners with three equivalent F(4)Na3Ti trigonal pyramids,  an edgeedge with one F(2)Na3Ti tetrahedra, and  an edgeedge with one F(4)Na3Ti trigonal pyramid. In the fourth F site, F(4) is bonded to one Na(1), two equivalent Na(2), and one Ti(2) atom to form distorted FNa3Ti trigonal pyramids that share corners with three equivalent F(3)Na2Ti2 tetrahedra, corners with four equivalent F(2)Na3Ti tetrahedra, corners with three equivalent F(4)Na3Ti trigonal pyramids, and  an edgeedge with one F(3)Na2Ti2 tetrahedra. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Ti(2) atom.
Na2TiF5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted NaF7 pentagonal bipyramids that share  a cornercorner with one Ti(1)F6 octahedra,  a cornercorner with one Ti(2)F6 octahedra,  an edgeedge with one Ti(2)F6 octahedra, edges with two equivalent Ti(1)F6 octahedra, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 24-38°. The Na(1)-F(3) bond length is 2.39 Å. The Na(1)-F(4) bond length is 2.52 Å. The Na(1)-F(5) bond length is 2.25 Å. Both Na(1)-F(1) bond lengths are 2.26 Å. There is one shorter (2.34 Å) and one longer (2.48 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 2.71 Å. The Na(2)-F(2) bond length is 2.25 Å. The Na(2)-F(3) bond length is 2.38 Å. There is one shorter (2.21 Å) and one longer (2.28 Å) Na(2)-F(4) bond length. There is one shorter (2.52 Å) and one longer (2.66 Å) Na(2)-F(5) bond length. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form TiF6 octahedra that share corners with two equivalent Ti(2)F6 octahedra, corners with two equivalent Na(1)F7 pentagonal bipyramids, and edges with four equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. Both Ti(1)-F(1) bond lengths are 1.95 Å. Both Ti(1)-F(2) bond lengths are 1.95 Å. Both Ti(1)-F(3) bond lengths are 2.03 Å. In the second Ti site, Ti(2) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form TiF6 octahedra that share corners with two equivalent Ti(1)F6 octahedra, corners with two equivalent Na(1)F7 pentagonal bipyramids, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. Both Ti(2)-F(3) bond lengths are 2.03 Å. Both Ti(2)-F(4) bond lengths are 2.01 Å. Both Ti(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 Ti(1) atom. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Ti(1) atom to form distorted FNa3Ti tetrahedra that share corners with three equivalent F(3)Na2Ti2 tetrahedra, corners with three equivalent F(2)Na3Ti tetrahedra, corners with four equivalent F(4)Na3Ti trigonal pyramids, and  an edgeedge with one F(3)Na2Ti2 tetrahedra. In the third F site, F(3) is bonded to one Na(1), one Na(2), one Ti(1), and one Ti(2) atom to form distorted FNa2Ti2 tetrahedra that share corners with two equivalent F(3)Na2Ti2 tetrahedra, corners with three equivalent F(2)Na3Ti tetrahedra, corners with three equivalent F(4)Na3Ti trigonal pyramids,  an edgeedge with one F(2)Na3Ti tetrahedra, and  an edgeedge with one F(4)Na3Ti trigonal pyramid. In the fourth F site, F(4) is bonded to one Na(1), two equivalent Na(2), and one Ti(2) atom to form distorted FNa3Ti trigonal pyramids that share corners with three equivalent F(3)Na2Ti2 tetrahedra, corners with four equivalent F(2)Na3Ti tetrahedra, corners with three equivalent F(4)Na3Ti trigonal pyramids, and  an edgeedge with one F(3)Na2Ti2 tetrahedra. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Ti(2) atom.