VP4 is Sylvanite-derived structured and crystallizes in the monoclinic C2/c space group. V(1) is bonded to two equivalent P(1) and four equivalent P(2) atoms to form VP6 octahedra that share corners with six equivalent P(2)V2P2 tetrahedra and edges with two equivalent V(1)P6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded in a 4-coordinate geometry to one V(1), one P(2), and two equivalent P(1) atoms. In the second P site, P(2) is bonded to two equivalent V(1), one P(1), and one P(2) atom to form distorted PV2P2 tetrahedra that share corners with three equivalent V(1)P6 octahedra, corners with four equivalent P(2)V2P2 tetrahedra, and  an edgeedge with one P(2)V2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 55-62°.
VP4 is Sylvanite-derived structured and crystallizes in the monoclinic C2/c space group. V(1) is bonded to two equivalent P(1) and four equivalent P(2) atoms to form VP6 octahedra that share corners with six equivalent P(2)V2P2 tetrahedra and edges with two equivalent V(1)P6 octahedra. Both V(1)-P(1) bond lengths are 2.38 Å. There are two shorter (2.34 Å) and two longer (2.42 Å) V(1)-P(2) bond lengths. There are two inequivalent P sites. In the first P site, P(1) is bonded in a 4-coordinate geometry to one V(1), one P(2), and two equivalent P(1) atoms. The P(1)-P(2) bond length is 2.24 Å. Both P(1)-P(1) bond lengths are 2.21 Å. In the second P site, P(2) is bonded to two equivalent V(1), one P(1), and one P(2) atom to form distorted PV2P2 tetrahedra that share corners with three equivalent V(1)P6 octahedra, corners with four equivalent P(2)V2P2 tetrahedra, and  an edgeedge with one P(2)V2P2 tetrahedra. The corner-sharing octahedral tilt angles range from 55-62°. The P(2)-P(2) bond length is 2.20 Å.