RbVBr3 crystallizes in the hexagonal P6_3/mmc space group. Rb(1) is bonded to twelve equivalent Br(1) atoms to form RbBr12 cuboctahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, corners with six equivalent V(1)Br6 octahedra, faces with eight equivalent Rb(1)Br12 cuboctahedra, and faces with six equivalent V(1)Br6 octahedra. The corner-sharing octahedral tilt angles are 18°. V(1) 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(1)Br6 octahedra. Br(1) is bonded to four equivalent Rb(1) and two equivalent V(1) atoms to form a mixture of distorted corner, edge, and face-sharing BrRb4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°.
RbVBr3 crystallizes in the hexagonal P6_3/mmc space group. Rb(1) is bonded to twelve equivalent Br(1) atoms to form RbBr12 cuboctahedra that share corners with six equivalent Rb(1)Br12 cuboctahedra, corners with six equivalent V(1)Br6 octahedra, faces with eight equivalent Rb(1)Br12 cuboctahedra, and faces with six equivalent V(1)Br6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are six shorter (3.72 Å) and six longer (3.91 Å) Rb(1)-Br(1) bond lengths. V(1) 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(1)Br6 octahedra. All V(1)-Br(1) bond lengths are 2.65 Å. Br(1) is bonded to four equivalent Rb(1) and two equivalent V(1) atoms to form a mixture of distorted corner, edge, and face-sharing BrRb4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°.