NaAlPO4F crystallizes in the monoclinic C2/c space group. Na(1) is bonded in a 7-coordinate geometry to two equivalent O(2), four equivalent O(1), and one F(1) atom. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with two equivalent Al(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 37°. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 32-49°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Al(1) atoms.
NaAlPO4F crystallizes in the monoclinic C2/c space group. Na(1) is bonded in a 7-coordinate geometry to two equivalent O(2), four equivalent O(1), and one F(1) atom. Both Na(1)-O(2) bond lengths are 2.33 Å. There are two shorter (2.43 Å) and two longer (2.60 Å) Na(1)-O(1) bond lengths. The Na(1)-F(1) bond length is 2.18 Å. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with two equivalent Al(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 37°. Both Al(1)-O(1) bond lengths are 1.92 Å. Both Al(1)-O(2) bond lengths are 1.91 Å. Both Al(1)-F(1) bond lengths are 1.84 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 32-49°. Both P(1)-O(1) bond lengths are 1.56 Å. Both P(1)-O(2) bond lengths are 1.55 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Al(1) atoms.