RbCuF3 crystallizes in the tetragonal I4/mcm space group. Rb(1) is bonded to four equivalent F(2) and eight equivalent F(1) atoms to form RbF12 cuboctahedra that share corners with twelve equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, and faces with eight equivalent Cu(1)F6 octahedra. Cu(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form CuF6 octahedra that share corners with six equivalent Cu(1)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Rb(1) and two equivalent Cu(1) atoms to form a mixture of distorted face, edge, and corner-sharing FRb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°. In the second F site, F(2) is bonded in a linear geometry to four equivalent Rb(1) and two equivalent Cu(1) atoms.
RbCuF3 crystallizes in the tetragonal I4/mcm space group. Rb(1) is bonded to four equivalent F(2) and eight equivalent F(1) atoms to form RbF12 cuboctahedra that share corners with twelve equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, and faces with eight equivalent Cu(1)F6 octahedra. All Rb(1)-F(2) bond lengths are 3.00 Å. All Rb(1)-F(1) bond lengths are 2.90 Å. Cu(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form CuF6 octahedra that share corners with six equivalent Cu(1)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Both Cu(1)-F(2) bond lengths are 1.97 Å. There are two shorter (1.87 Å) and two longer (2.37 Å) Cu(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Rb(1) and two equivalent Cu(1) atoms to form a mixture of distorted face, edge, and corner-sharing FRb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°. In the second F site, F(2) is bonded in a linear geometry to four equivalent Rb(1) and two equivalent Cu(1) atoms.