Rb2TeBr6 crystallizes in the tetragonal I4/m space group. Rb(1) is bonded to four equivalent Br(2) and eight equivalent Br(1) atoms to form RbBr12 cuboctahedra that share corners with twelve equivalent Rb(1)Br12 cuboctahedra, faces with six equivalent Rb(1)Br12 cuboctahedra, and faces with four equivalent Te(1)Br6 octahedra. Te(1) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form TeBr6 octahedra that share faces with eight equivalent Rb(1)Br12 cuboctahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 5-coordinate geometry to four equivalent Rb(1) and one Te(1) atom. In the second Br site, Br(2) is bonded to four equivalent Rb(1) and one Te(1) atom to form a mixture of edge and corner-sharing BrRb4Te square pyramids.
Rb2TeBr6 crystallizes in the tetragonal I4/m space group. Rb(1) is bonded to four equivalent Br(2) and eight equivalent Br(1) atoms to form RbBr12 cuboctahedra that share corners with twelve equivalent Rb(1)Br12 cuboctahedra, faces with six equivalent Rb(1)Br12 cuboctahedra, and faces with four equivalent Te(1)Br6 octahedra. All Rb(1)-Br(2) bond lengths are 3.82 Å. There are four shorter (3.68 Å) and four longer (4.03 Å) Rb(1)-Br(1) bond lengths. Te(1) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form TeBr6 octahedra that share faces with eight equivalent Rb(1)Br12 cuboctahedra. Both Te(1)-Br(2) bond lengths are 2.72 Å. All Te(1)-Br(1) bond lengths are 2.71 Å. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 5-coordinate geometry to four equivalent Rb(1) and one Te(1) atom. In the second Br site, Br(2) is bonded to four equivalent Rb(1) and one Te(1) atom to form a mixture of edge and corner-sharing BrRb4Te square pyramids.