Cs2RbZrOF5 crystallizes in the tetragonal I4mm space group. Cs(1) is bonded to two equivalent O(1), two equivalent F(2), and eight equivalent F(1) atoms to form CsO2F10 cuboctahedra that share corners with twelve equivalent Cs(1)O2F10 cuboctahedra, faces with six equivalent Cs(1)O2F10 cuboctahedra, faces with four equivalent Rb(1)OF5 octahedra, and faces with four equivalent Zr(1)OF5 octahedra. Rb(1) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form RbOF5 octahedra that share corners with six equivalent Zr(1)OF5 octahedra and faces with eight equivalent Cs(1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-6°. Zr(1) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form ZrOF5 octahedra that share corners with six equivalent Rb(1)OF5 octahedra and faces with eight equivalent Cs(1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-6°. O(1) is bonded in a 1-coordinate geometry to four equivalent Cs(1), one Rb(1), and one Zr(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to four equivalent Cs(1), one Rb(1), and one Zr(1) atom. In the second F site, F(2) is bonded in a distorted linear geometry to four equivalent Cs(1), one Rb(1), and one Zr(1) atom.
Cs2RbZrOF5 crystallizes in the tetragonal I4mm space group. Cs(1) is bonded to two equivalent O(1), two equivalent F(2), and eight equivalent F(1) atoms to form CsO2F10 cuboctahedra that share corners with twelve equivalent Cs(1)O2F10 cuboctahedra, faces with six equivalent Cs(1)O2F10 cuboctahedra, faces with four equivalent Rb(1)OF5 octahedra, and faces with four equivalent Zr(1)OF5 octahedra. Both Cs(1)-O(1) bond lengths are 3.43 Å. Both Cs(1)-F(2) bond lengths are 3.42 Å. There are four shorter (3.39 Å) and four longer (3.48 Å) Cs(1)-F(1) bond lengths. Rb(1) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form RbOF5 octahedra that share corners with six equivalent Zr(1)OF5 octahedra and faces with eight equivalent Cs(1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Rb(1)-O(1) bond length is 2.77 Å. The Rb(1)-F(2) bond length is 2.79 Å. All Rb(1)-F(1) bond lengths are 2.73 Å. Zr(1) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form ZrOF5 octahedra that share corners with six equivalent Rb(1)OF5 octahedra and faces with eight equivalent Cs(1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Zr(1)-O(1) bond length is 1.89 Å. The Zr(1)-F(2) bond length is 2.25 Å. All Zr(1)-F(1) bond lengths are 2.10 Å. O(1) is bonded in a 1-coordinate geometry to four equivalent Cs(1), one Rb(1), and one Zr(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to four equivalent Cs(1), one Rb(1), and one Zr(1) atom. In the second F site, F(2) is bonded in a distorted linear geometry to four equivalent Cs(1), one Rb(1), and one Zr(1) atom.