CsAsOF4 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded to one O(1), two equivalent F(1), three equivalent F(2), three equivalent F(3), and three equivalent F(4) atoms to form distorted CsOF11 cuboctahedra that share corners with two equivalent Cs(1)OF11 cuboctahedra, corners with five equivalent As(1)O2F4 octahedra, edges with five equivalent Cs(1)OF11 cuboctahedra,  an edgeedge with one As(1)O2F4 octahedra, faces with two equivalent Cs(1)OF11 cuboctahedra, and faces with two equivalent As(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 14-46°. As(1) is bonded to two equivalent O(1), one F(1), one F(2), one F(3), and one F(4) atom to form AsO2F4 octahedra that share corners with five equivalent Cs(1)OF11 cuboctahedra,  an edgeedge with one Cs(1)OF11 cuboctahedra,  an edgeedge with one As(1)O2F4 octahedra, and faces with two equivalent Cs(1)OF11 cuboctahedra. O(1) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent As(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one As(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one As(1) atom. In the third F site, F(3) is bonded in a single-bond geometry to three equivalent Cs(1) and one As(1) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to three equivalent Cs(1) and one As(1) atom.
CsAsOF4 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded to one O(1), two equivalent F(1), three equivalent F(2), three equivalent F(3), and three equivalent F(4) atoms to form distorted CsOF11 cuboctahedra that share corners with two equivalent Cs(1)OF11 cuboctahedra, corners with five equivalent As(1)O2F4 octahedra, edges with five equivalent Cs(1)OF11 cuboctahedra,  an edgeedge with one As(1)O2F4 octahedra, faces with two equivalent Cs(1)OF11 cuboctahedra, and faces with two equivalent As(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 14-46°. The Cs(1)-O(1) bond length is 3.10 Å. There is one shorter (3.04 Å) and one longer (3.05 Å) Cs(1)-F(1) bond length. There are a spread of Cs(1)-F(2) bond distances ranging from 3.10-3.53 Å. There are a spread of Cs(1)-F(3) bond distances ranging from 3.11-3.33 Å. There are a spread of Cs(1)-F(4) bond distances ranging from 3.25-3.32 Å. As(1) is bonded to two equivalent O(1), one F(1), one F(2), one F(3), and one F(4) atom to form AsO2F4 octahedra that share corners with five equivalent Cs(1)OF11 cuboctahedra,  an edgeedge with one Cs(1)OF11 cuboctahedra,  an edgeedge with one As(1)O2F4 octahedra, and faces with two equivalent Cs(1)OF11 cuboctahedra. Both As(1)-O(1) bond lengths are 1.80 Å. The As(1)-F(1) bond length is 1.77 Å. The As(1)-F(2) bond length is 1.77 Å. The As(1)-F(3) bond length is 1.79 Å. The As(1)-F(4) bond length is 1.77 Å. O(1) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent As(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one As(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one As(1) atom. In the third F site, F(3) is bonded in a single-bond geometry to three equivalent Cs(1) and one As(1) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to three equivalent Cs(1) and one As(1) atom.