NaAlAsO4F 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 As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. As(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form AsO4 tetrahedra that share corners with four equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 37-54°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Al(1), and one As(1) atom to form a mixture of distorted edge and corner-sharing ONa2AlAs tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one As(1) atom. F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent Al(1) atoms.
NaAlAsO4F 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 2.43 Å. There are two shorter (2.42 Å) and two longer (2.60 Å) Na(1)-O(1) bond lengths. The Na(1)-F(1) bond length is 2.27 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 As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. Both Al(1)-O(1) bond lengths are 1.91 Å. Both Al(1)-O(2) bond lengths are 1.90 Å. Both Al(1)-F(1) bond lengths are 1.87 Å. As(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form AsO4 tetrahedra that share corners with four equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 37-54°. Both As(1)-O(1) bond lengths are 1.72 Å. Both As(1)-O(2) bond lengths are 1.71 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Al(1), and one As(1) atom to form a mixture of distorted edge and corner-sharing ONa2AlAs tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Al(1), and one As(1) atom. F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent Al(1) atoms.