Fe2(HPO3)F2 crystallizes in the orthorhombic Pnma space group. Fe(1) is bonded to one O(2), two equivalent O(1), and three equivalent F(1) atoms to form FeO3F3 octahedra that share corners with five equivalent Fe(1)O3F3 octahedra, corners with three equivalent P(1)HO3 tetrahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 54-56°. P(1) is bonded to one H(1), one O(2), and two equivalent O(1) atoms to form distorted PHO3 tetrahedra that share corners with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. H(1) is bonded in a single-bond geometry to one P(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Fe(1) and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Fe(1) and one P(1) atom. F(1) is bonded in a trigonal planar geometry to three equivalent Fe(1) atoms.
Fe2(HPO3)F2 crystallizes in the orthorhombic Pnma space group. Fe(1) is bonded to one O(2), two equivalent O(1), and three equivalent F(1) atoms to form FeO3F3 octahedra that share corners with five equivalent Fe(1)O3F3 octahedra, corners with three equivalent P(1)HO3 tetrahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 54-56°. The Fe(1)-O(2) bond length is 2.18 Å. There is one shorter (2.13 Å) and one longer (2.19 Å) Fe(1)-O(1) bond length. There are a spread of Fe(1)-F(1) bond distances ranging from 2.09-2.19 Å. P(1) is bonded to one H(1), one O(2), and two equivalent O(1) atoms to form distorted PHO3 tetrahedra that share corners with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. The P(1)-H(1) bond length is 1.40 Å. The P(1)-O(2) bond length is 1.56 Å. Both P(1)-O(1) bond lengths are 1.54 Å. H(1) is bonded in a single-bond geometry to one P(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Fe(1) and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Fe(1) and one P(1) atom. F(1) is bonded in a trigonal planar geometry to three equivalent Fe(1) atoms.