Rb3LiTbV2O8 crystallizes in the trigonal P3m1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one O(1) and six equivalent O(4) atoms to form distorted RbO7 hexagonal pyramids that share corners with six equivalent Rb(1)O7 hexagonal pyramids,  a cornercorner with one V(1)O4 tetrahedra, and edges with three equivalent Tb(1)O6 octahedra. In the second Rb site, Rb(2) is bonded in a distorted single-bond geometry to one O(2) atom. In the third Rb site, Rb(3) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent O(3) atoms. Li(1) is bonded in a 3-coordinate geometry to three equivalent O(4) atoms. Tb(1) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form TbO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra and edges with three equivalent Rb(1)O7 hexagonal pyramids. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1) and three equivalent O(3) atoms to form VO4 tetrahedra that share  a cornercorner with one Rb(1)O7 hexagonal pyramid and corners with three equivalent Tb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 21°. In the second V site, V(2) is bonded in a 4-coordinate geometry to one O(2) and three equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Rb(1), three equivalent Rb(3), and one V(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Rb(2), three equivalent Rb(3), and one V(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Rb(3), one Tb(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Rb(1), one Li(1), one Tb(1), and one V(2) atom.
Rb3LiTbV2O8 crystallizes in the trigonal P3m1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one O(1) and six equivalent O(4) atoms to form distorted RbO7 hexagonal pyramids that share corners with six equivalent Rb(1)O7 hexagonal pyramids,  a cornercorner with one V(1)O4 tetrahedra, and edges with three equivalent Tb(1)O6 octahedra. The Rb(1)-O(1) bond length is 3.44 Å. All Rb(1)-O(4) bond lengths are 3.06 Å. In the second Rb site, Rb(2) is bonded in a distorted single-bond geometry to one O(2) atom. The Rb(2)-O(2) bond length is 2.50 Å. In the third Rb site, Rb(3) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent O(3) atoms. All Rb(3)-O(1) bond lengths are 3.53 Å. All Rb(3)-O(2) bond lengths are 3.51 Å. All Rb(3)-O(3) bond lengths are 3.53 Å. Li(1) is bonded in a 3-coordinate geometry to three equivalent O(4) atoms. All Li(1)-O(4) bond lengths are 2.08 Å. Tb(1) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form TbO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra and edges with three equivalent Rb(1)O7 hexagonal pyramids. All Tb(1)-O(3) bond lengths are 2.34 Å. All Tb(1)-O(4) bond lengths are 2.24 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1) and three equivalent O(3) atoms to form VO4 tetrahedra that share  a cornercorner with one Rb(1)O7 hexagonal pyramid and corners with three equivalent Tb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 21°. The V(1)-O(1) bond length is 1.71 Å. All V(1)-O(3) bond lengths are 1.76 Å. In the second V site, V(2) is bonded in a 4-coordinate geometry to one O(2) and three equivalent O(4) atoms. The V(2)-O(2) bond length is 1.73 Å. All V(2)-O(4) bond lengths are 1.85 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Rb(1), three equivalent Rb(3), and one V(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Rb(2), three equivalent Rb(3), and one V(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Rb(3), one Tb(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Rb(1), one Li(1), one Tb(1), and one V(2) atom.