NaFeAsO4F 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. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra and corners with four equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. 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 Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 40-54°. 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 Fe(1), and one As(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Fe(1), and one As(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Fe(1) atoms.
NaFeAsO4F 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 2.47 Å. There are two shorter (2.45 Å) and two longer (2.78 Å) Na(1)-O(1) bond lengths. The Na(1)-F(1) bond length is 2.25 Å. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra and corners with four equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. Both Fe(1)-O(1) bond lengths are 2.03 Å. Both Fe(1)-O(2) bond lengths are 2.00 Å. Both Fe(1)-F(1) bond lengths are 1.99 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 Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 40-54°. Both As(1)-O(1) bond lengths are 1.73 Å. Both As(1)-O(2) bond lengths are 1.72 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 Fe(1), and one As(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Fe(1), and one As(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Fe(1) atoms.