RbVP2S7 crystallizes in the monoclinic C2 space group. Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. V(1) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form VS6 octahedra that share corners with two equivalent P(1)S4 tetrahedra and edges with two equivalent P(1)S4 tetrahedra. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one P(1)S4 tetrahedra, and  an edgeedge with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 62°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to two equivalent Rb(1) and two equivalent P(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Rb(1), one V(1), and one P(1) atom. In the third S site, S(3) is bonded in a distorted L-shaped geometry to one Rb(1), one V(1), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted L-shaped geometry to one Rb(1), one V(1), and one P(1) atom.
RbVP2S7 crystallizes in the monoclinic C2 space group. Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. Both Rb(1)-S(1) bond lengths are 3.63 Å. Both Rb(1)-S(2) bond lengths are 3.56 Å. Both Rb(1)-S(3) bond lengths are 3.76 Å. Both Rb(1)-S(4) bond lengths are 3.74 Å. V(1) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form VS6 octahedra that share corners with two equivalent P(1)S4 tetrahedra and edges with two equivalent P(1)S4 tetrahedra. Both V(1)-S(2) bond lengths are 2.48 Å. Both V(1)-S(3) bond lengths are 2.47 Å. Both V(1)-S(4) bond lengths are 2.41 Å. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one P(1)S4 tetrahedra, and  an edgeedge with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 62°. The P(1)-S(1) bond length is 2.16 Å. The P(1)-S(2) bond length is 2.03 Å. The P(1)-S(3) bond length is 2.03 Å. The P(1)-S(4) bond length is 2.05 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to two equivalent Rb(1) and two equivalent P(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Rb(1), one V(1), and one P(1) atom. In the third S site, S(3) is bonded in a distorted L-shaped geometry to one Rb(1), one V(1), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted L-shaped geometry to one Rb(1), one V(1), and one P(1) atom.