RbZnF3 is (Cubic) Perovskite-like structured and crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form RbF12 cuboctahedra that share corners with three equivalent Rb(2)F12 cuboctahedra, corners with six equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Zn(1)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, faces with three equivalent Zn(2)F6 octahedra, and faces with four equivalent Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 8°. In the second Rb site, Rb(2) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form RbF12 cuboctahedra that share corners with six equivalent Rb(1)F12 cuboctahedra, corners with six equivalent Rb(2)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, faces with two equivalent Zn(2)F6 octahedra, and faces with six equivalent Zn(1)F6 octahedra. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form ZnF6 octahedra that share corners with three equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Zn(2)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, and  a faceface with one Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the second Zn site, Zn(2) is bonded to six equivalent F(1) atoms to form ZnF6 octahedra that share corners with six equivalent Zn(1)F6 octahedra, faces with two equivalent Rb(2)F12 cuboctahedra, and faces with six equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Rb(2), three equivalent Rb(1), one Zn(1), and one Zn(2) atom. In the second F site, F(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Zn(1) atoms to form a mixture of distorted corner and face-sharing FRb4Zn2 octahedra. The corner-sharing octahedral tilt angles range from 6-60°.
RbZnF3 is (Cubic) Perovskite-like structured and crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form RbF12 cuboctahedra that share corners with three equivalent Rb(2)F12 cuboctahedra, corners with six equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Zn(1)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, faces with three equivalent Zn(2)F6 octahedra, and faces with four equivalent Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 8°. All Rb(1)-F(2) bond lengths are 2.90 Å. There are six shorter (2.95 Å) and three longer (3.06 Å) Rb(1)-F(1) bond lengths. In the second Rb site, Rb(2) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form RbF12 cuboctahedra that share corners with six equivalent Rb(1)F12 cuboctahedra, corners with six equivalent Rb(2)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, faces with two equivalent Zn(2)F6 octahedra, and faces with six equivalent Zn(1)F6 octahedra. All Rb(2)-F(1) bond lengths are 2.98 Å. All Rb(2)-F(2) bond lengths are 2.95 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form ZnF6 octahedra that share corners with three equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Zn(2)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, and  a faceface with one Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 3°. All Zn(1)-F(1) bond lengths are 2.01 Å. All Zn(1)-F(2) bond lengths are 2.07 Å. In the second Zn site, Zn(2) is bonded to six equivalent F(1) atoms to form ZnF6 octahedra that share corners with six equivalent Zn(1)F6 octahedra, faces with two equivalent Rb(2)F12 cuboctahedra, and faces with six equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 3°. All Zn(2)-F(1) bond lengths are 2.04 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Rb(2), three equivalent Rb(1), one Zn(1), and one Zn(2) atom. In the second F site, F(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Zn(1) atoms to form a mixture of distorted corner and face-sharing FRb4Zn2 octahedra. The corner-sharing octahedral tilt angles range from 6-60°.