RbNiF3 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 Ni(1)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, faces with three equivalent Ni(2)F6 octahedra, and faces with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 9°. 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 Ni(2)F6 octahedra, and faces with six equivalent Ni(1)F6 octahedra. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form NiF6 octahedra that share corners with three equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Ni(2)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, and  a faceface with one Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 2°. In the second Ni site, Ni(2) is bonded to six equivalent F(1) atoms to form NiF6 octahedra that share corners with six equivalent Ni(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 2°. 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 Ni(1), and one Ni(2) atom. In the second F site, F(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Ni(1) atoms to form a mixture of distorted face and corner-sharing FRb4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 7-60°.
RbNiF3 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 Ni(1)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, faces with three equivalent Ni(2)F6 octahedra, and faces with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 9°. All Rb(1)-F(2) bond lengths are 2.92 Å. There are six shorter (2.92 Å) and three longer (2.99 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 Ni(2)F6 octahedra, and faces with six equivalent Ni(1)F6 octahedra. All Rb(2)-F(1) bond lengths are 2.95 Å. All Rb(2)-F(2) bond lengths are 2.92 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form NiF6 octahedra that share corners with three equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Ni(2)F6 octahedra, faces with three equivalent Rb(2)F12 cuboctahedra, faces with four equivalent Rb(1)F12 cuboctahedra, and  a faceface with one Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 2°. All Ni(1)-F(1) bond lengths are 2.01 Å. All Ni(1)-F(2) bond lengths are 2.02 Å. In the second Ni site, Ni(2) is bonded to six equivalent F(1) atoms to form NiF6 octahedra that share corners with six equivalent Ni(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 2°. All Ni(2)-F(1) bond lengths are 2.02 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 Ni(1), and one Ni(2) atom. In the second F site, F(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Ni(1) atoms to form a mixture of distorted face and corner-sharing FRb4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 7-60°.