RbVBr3 crystallizes in the hexagonal P6_3cm space group. Rb(1) is bonded to four equivalent Br(2) and eight equivalent Br(1) atoms to form distorted RbBr12 cuboctahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, corners with two equivalent V(1)Br6 octahedra, corners with four equivalent V(2)Br6 octahedra, faces with eight equivalent Rb(1)Br12 cuboctahedra, faces with two equivalent V(1)Br6 octahedra, and faces with four equivalent V(2)Br6 octahedra. The corner-sharing octahedral tilt angles range from 16-20°. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent Br(2) atoms to form VBr6 octahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, faces with six equivalent Rb(1)Br12 cuboctahedra, and faces with two equivalent V(1)Br6 octahedra. In the second V site, V(2) is bonded to six equivalent Br(1) atoms to form VBr6 octahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, faces with six equivalent Rb(1)Br12 cuboctahedra, and faces with two equivalent V(2)Br6 octahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 2-coordinate geometry to four equivalent Rb(1) and two equivalent V(2) atoms. In the second Br site, Br(2) is bonded in a 2-coordinate geometry to four equivalent Rb(1) and two equivalent V(1) atoms.
RbVBr3 crystallizes in the hexagonal P6_3cm space group. Rb(1) is bonded to four equivalent Br(2) and eight equivalent Br(1) atoms to form distorted RbBr12 cuboctahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, corners with two equivalent V(1)Br6 octahedra, corners with four equivalent V(2)Br6 octahedra, faces with eight equivalent Rb(1)Br12 cuboctahedra, faces with two equivalent V(1)Br6 octahedra, and faces with four equivalent V(2)Br6 octahedra. The corner-sharing octahedral tilt angles range from 16-20°. There are a spread of Rb(1)-Br(2) bond distances ranging from 3.72-4.03 Å. There are a spread of Rb(1)-Br(1) bond distances ranging from 3.72-4.13 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent Br(2) atoms to form VBr6 octahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, faces with six equivalent Rb(1)Br12 cuboctahedra, and faces with two equivalent V(1)Br6 octahedra. There are three shorter (2.64 Å) and three longer (2.65 Å) V(1)-Br(2) bond lengths. In the second V site, V(2) is bonded to six equivalent Br(1) atoms to form VBr6 octahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, faces with six equivalent Rb(1)Br12 cuboctahedra, and faces with two equivalent V(2)Br6 octahedra. There are three shorter (2.64 Å) and three longer (2.65 Å) V(2)-Br(1) bond lengths. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 2-coordinate geometry to four equivalent Rb(1) and two equivalent V(2) atoms. In the second Br site, Br(2) is bonded in a 2-coordinate geometry to four equivalent Rb(1) and two equivalent V(1) atoms.