RbVI3 crystallizes in the hexagonal P6_3cm space group. Rb(1) is bonded in a distorted q6 geometry to three equivalent I(1) and six equivalent I(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent I(2) atoms to form face-sharing VI6 octahedra. In the second V site, V(2) is bonded to six equivalent I(1) atoms to form face-sharing VI6 octahedra. There are two inequivalent I sites. In the first I site, I(1) is bonded to three equivalent Rb(1) and two equivalent V(2) atoms to form a mixture of distorted edge, face, and corner-sharing IRb3V2 square pyramids. In the second I site, I(2) is bonded to three equivalent Rb(1) and two equivalent V(1) atoms to form a mixture of distorted edge, face, and corner-sharing IRb3V2 square pyramids.
RbVI3 crystallizes in the hexagonal P6_3cm space group. Rb(1) is bonded in a distorted q6 geometry to three equivalent I(1) and six equivalent I(2) atoms. There is one shorter (3.99 Å) and two longer (4.04 Å) Rb(1)-I(1) bond lengths. There are a spread of Rb(1)-I(2) bond distances ranging from 3.99-4.10 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent I(2) atoms to form face-sharing VI6 octahedra. There are three shorter (2.85 Å) and three longer (2.86 Å) V(1)-I(2) bond lengths. In the second V site, V(2) is bonded to six equivalent I(1) atoms to form face-sharing VI6 octahedra. There are three shorter (2.84 Å) and three longer (2.86 Å) V(2)-I(1) bond lengths. There are two inequivalent I sites. In the first I site, I(1) is bonded to three equivalent Rb(1) and two equivalent V(2) atoms to form a mixture of distorted edge, face, and corner-sharing IRb3V2 square pyramids. In the second I site, I(2) is bonded to three equivalent Rb(1) and two equivalent V(1) atoms to form a mixture of distorted edge, face, and corner-sharing IRb3V2 square pyramids.