RbVSe2 crystallizes in the orthorhombic Fddd space group. Rb(1) is bonded in a 8-coordinate geometry to eight equivalent Se(1) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent Se(1) atoms to form edge-sharing VSe4 tetrahedra. In the second V site, V(2) is bonded to four equivalent Se(1) atoms to form edge-sharing VSe4 tetrahedra. Se(1) is bonded in a 6-coordinate geometry to four equivalent Rb(1), one V(1), and one V(2) atom.
RbVSe2 crystallizes in the orthorhombic Fddd space group. Rb(1) is bonded in a 8-coordinate geometry to eight equivalent Se(1) atoms. There are a spread of Rb(1)-Se(1) bond distances ranging from 3.67-3.73 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent Se(1) atoms to form edge-sharing VSe4 tetrahedra. All V(1)-Se(1) bond lengths are 2.41 Å. In the second V site, V(2) is bonded to four equivalent Se(1) atoms to form edge-sharing VSe4 tetrahedra. All V(2)-Se(1) bond lengths are 2.42 Å. Se(1) is bonded in a 6-coordinate geometry to four equivalent Rb(1), one V(1), and one V(2) atom.