RbTlF3 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to two equivalent F(2) and four equivalent F(3) atoms. Tl(1) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(3) atoms to form corner-sharing TlF6 octahedra. The corner-sharing octahedral tilt angles range from 18-27°. There are five inequivalent F sites. In the first F site, F(4) is bonded in a distorted see-saw-like geometry to two equivalent Rb(1) and two equivalent Tl(1) atoms. In the second F site, F(5) is bonded in a 4-coordinate geometry to two equivalent Rb(1) and two equivalent Tl(1) atoms. In the third F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Rb(1) and two equivalent Tl(1) atoms. In the fourth F site, F(2) is bonded in a 4-coordinate geometry to two equivalent Rb(2) and two equivalent Tl(1) atoms. In the fifth F site, F(3) is bonded to two equivalent Rb(2) and two equivalent Tl(1) atoms to form a mixture of distorted edge and corner-sharing FRb2Tl2 trigonal pyramids.
RbTlF3 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms. There is one shorter (2.88 Å) and one longer (3.32 Å) Rb(1)-F(1) bond length. Both Rb(1)-F(4) bond lengths are 2.94 Å. Both Rb(1)-F(5) bond lengths are 2.99 Å. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to two equivalent F(2) and four equivalent F(3) atoms. There is one shorter (2.87 Å) and one longer (3.17 Å) Rb(2)-F(2) bond length. There are two shorter (2.93 Å) and two longer (3.01 Å) Rb(2)-F(3) bond lengths. Tl(1) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(3) atoms to form corner-sharing TlF6 octahedra. The corner-sharing octahedral tilt angles range from 18-27°. The Tl(1)-F(1) bond length is 2.39 Å. The Tl(1)-F(2) bond length is 2.39 Å. The Tl(1)-F(4) bond length is 2.39 Å. The Tl(1)-F(5) bond length is 2.42 Å. Both Tl(1)-F(3) bond lengths are 2.40 Å. There are five inequivalent F sites. In the first F site, F(4) is bonded in a distorted see-saw-like geometry to two equivalent Rb(1) and two equivalent Tl(1) atoms. In the second F site, F(5) is bonded in a 4-coordinate geometry to two equivalent Rb(1) and two equivalent Tl(1) atoms. In the third F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Rb(1) and two equivalent Tl(1) atoms. In the fourth F site, F(2) is bonded in a 4-coordinate geometry to two equivalent Rb(2) and two equivalent Tl(1) atoms. In the fifth F site, F(3) is bonded to two equivalent Rb(2) and two equivalent Tl(1) atoms to form a mixture of distorted edge and corner-sharing FRb2Tl2 trigonal pyramids.