V3As2 crystallizes in the tetragonal P4/m space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to two equivalent V(5), one As(1), and four equivalent As(2) atoms to form distorted VV2As5 square pyramids that share corners with four equivalent V(3)As6 octahedra, corners with two equivalent V(1)V2As5 square pyramids, corners with four equivalent V(2)As5 square pyramids, edges with two equivalent V(5)V8As4 cuboctahedra,  an edgeedge with one V(3)As6 octahedra, edges with two equivalent V(2)As5 square pyramids, edges with five equivalent V(1)V2As5 square pyramids,  a faceface with one V(3)As6 octahedra, and faces with four equivalent V(1)V2As5 square pyramids. The corner-sharing octahedral tilt angles range from 22-55°. In the second V site, V(2) is bonded to one As(2) and four equivalent As(1) atoms to form distorted VAs5 square pyramids that share  a cornercorner with one V(5)V8As4 cuboctahedra, corners with two equivalent V(3)As6 octahedra, corners with four equivalent V(2)As5 square pyramids, corners with four equivalent V(1)V2As5 square pyramids, edges with two equivalent V(3)As6 octahedra, edges with two equivalent V(1)V2As5 square pyramids, and edges with four equivalent V(2)As5 square pyramids. The corner-sharing octahedral tilt angles are 45°. In the third V site, V(3) is bonded to two equivalent As(1) and four equivalent As(2) atoms to form VAs6 octahedra that share corners with four equivalent V(5)V8As4 cuboctahedra, corners with four equivalent V(2)As5 square pyramids, corners with eight equivalent V(1)V2As5 square pyramids, edges with two equivalent V(3)As6 octahedra, edges with two equivalent V(1)V2As5 square pyramids, edges with four equivalent V(2)As5 square pyramids, and faces with two equivalent V(1)V2As5 square pyramids. In the fourth V site, V(4) is bonded in a distorted square co-planar geometry to four equivalent As(1) atoms. In the fifth V site, V(5) is bonded to eight equivalent V(1) and four equivalent As(2) atoms to form distorted VV8As4 cuboctahedra that share corners with eight equivalent V(3)As6 octahedra, corners with four equivalent V(2)As5 square pyramids, edges with eight equivalent V(1)V2As5 square pyramids, and faces with two equivalent V(5)V8As4 cuboctahedra. The corner-sharing octahedral tilt angles are 43°. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 7-coordinate geometry to one V(1), one V(3), one V(4), and four equivalent V(2) atoms. In the second As site, As(2) is bonded in a 8-coordinate geometry to one V(2), one V(5), two equivalent V(3), and four equivalent V(1) atoms.
V3As2 crystallizes in the tetragonal P4/m space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to two equivalent V(5), one As(1), and four equivalent As(2) atoms to form distorted VV2As5 square pyramids that share corners with four equivalent V(3)As6 octahedra, corners with two equivalent V(1)V2As5 square pyramids, corners with four equivalent V(2)As5 square pyramids, edges with two equivalent V(5)V8As4 cuboctahedra,  an edgeedge with one V(3)As6 octahedra, edges with two equivalent V(2)As5 square pyramids, edges with five equivalent V(1)V2As5 square pyramids,  a faceface with one V(3)As6 octahedra, and faces with four equivalent V(1)V2As5 square pyramids. The corner-sharing octahedral tilt angles range from 22-55°. Both V(1)-V(5) bond lengths are 2.71 Å. The V(1)-As(1) bond length is 2.45 Å. There are two shorter (2.53 Å) and two longer (2.59 Å) V(1)-As(2) bond lengths. In the second V site, V(2) is bonded to one As(2) and four equivalent As(1) atoms to form distorted VAs5 square pyramids that share  a cornercorner with one V(5)V8As4 cuboctahedra, corners with two equivalent V(3)As6 octahedra, corners with four equivalent V(2)As5 square pyramids, corners with four equivalent V(1)V2As5 square pyramids, edges with two equivalent V(3)As6 octahedra, edges with two equivalent V(1)V2As5 square pyramids, and edges with four equivalent V(2)As5 square pyramids. The corner-sharing octahedral tilt angles are 45°. The V(2)-As(2) bond length is 2.55 Å. There are two shorter (2.49 Å) and two longer (2.50 Å) V(2)-As(1) bond lengths. In the third V site, V(3) is bonded to two equivalent As(1) and four equivalent As(2) atoms to form VAs6 octahedra that share corners with four equivalent V(5)V8As4 cuboctahedra, corners with four equivalent V(2)As5 square pyramids, corners with eight equivalent V(1)V2As5 square pyramids, edges with two equivalent V(3)As6 octahedra, edges with two equivalent V(1)V2As5 square pyramids, edges with four equivalent V(2)As5 square pyramids, and faces with two equivalent V(1)V2As5 square pyramids. Both V(3)-As(1) bond lengths are 2.49 Å. All V(3)-As(2) bond lengths are 2.69 Å. In the fourth V site, V(4) is bonded in a distorted square co-planar geometry to four equivalent As(1) atoms. All V(4)-As(1) bond lengths are 2.57 Å. In the fifth V site, V(5) is bonded to eight equivalent V(1) and four equivalent As(2) atoms to form distorted VV8As4 cuboctahedra that share corners with eight equivalent V(3)As6 octahedra, corners with four equivalent V(2)As5 square pyramids, edges with eight equivalent V(1)V2As5 square pyramids, and faces with two equivalent V(5)V8As4 cuboctahedra. The corner-sharing octahedral tilt angles are 43°. All V(5)-As(2) bond lengths are 2.74 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 7-coordinate geometry to one V(1), one V(3), one V(4), and four equivalent V(2) atoms. In the second As site, As(2) is bonded in a 8-coordinate geometry to one V(2), one V(5), two equivalent V(3), and four equivalent V(1) atoms.