NV3P crystallizes in the orthorhombic Cmcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 4-coordinate geometry to two equivalent P(1) and two equivalent N(1) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to three equivalent P(1) and two equivalent N(1) atoms. P(1) is bonded in a 8-coordinate geometry to two equivalent V(1) and six equivalent V(2) atoms. N(1) is bonded to two equivalent V(1) and four equivalent V(2) atoms to form a mixture of corner and edge-sharing NV6 octahedra. The corner-sharing octahedral tilt angles are 39°.
NV3P crystallizes in the orthorhombic Cmcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 4-coordinate geometry to two equivalent P(1) and two equivalent N(1) atoms. Both V(1)-P(1) bond lengths are 2.34 Å. Both V(1)-N(1) bond lengths are 1.95 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to three equivalent P(1) and two equivalent N(1) atoms. There are two shorter (2.41 Å) and one longer (2.47 Å) V(2)-P(1) bond length. Both V(2)-N(1) bond lengths are 2.06 Å. P(1) is bonded in a 8-coordinate geometry to two equivalent V(1) and six equivalent V(2) atoms. N(1) is bonded to two equivalent V(1) and four equivalent V(2) atoms to form a mixture of corner and edge-sharing NV6 octahedra. The corner-sharing octahedral tilt angles are 39°.