V4As3 crystallizes in the monoclinic C2/m space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to one As(2), two equivalent As(1), and two equivalent As(3) atoms to form distorted VAs5 square pyramids that share corners with six equivalent V(2)As6 octahedra, corners with six equivalent V(3)As5 square pyramids, edges with two equivalent V(4)As6 octahedra, edges with two equivalent V(1)As5 square pyramids, edges with two equivalent V(3)As5 square pyramids, and  a faceface with one V(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. In the second V site, V(2) is bonded to one As(3), two equivalent As(1), and three equivalent As(2) atoms to form distorted VAs6 octahedra that share corners with four equivalent V(4)As6 octahedra, corners with two equivalent V(3)As5 square pyramids, corners with six equivalent V(1)As5 square pyramids, edges with four equivalent V(2)As6 octahedra, edges with three equivalent V(3)As5 square pyramids,  a faceface with one V(4)As6 octahedra, and  a faceface with one V(1)As5 square pyramid. The corner-sharing octahedral tilt angles range from 50-51°. In the third V site, V(3) is bonded to two equivalent As(3) and three equivalent As(1) atoms to form distorted VAs5 square pyramids that share corners with two equivalent V(2)As6 octahedra, corners with two equivalent V(4)As6 octahedra, corners with six equivalent V(1)As5 square pyramids, edges with three equivalent V(2)As6 octahedra, edges with two equivalent V(1)As5 square pyramids, and edges with four equivalent V(3)As5 square pyramids. The corner-sharing octahedral tilt angles range from 21-46°. In the fourth V site, V(4) is bonded to two equivalent As(3) and four equivalent As(2) atoms to form VAs6 octahedra that share corners with eight equivalent V(2)As6 octahedra, corners with four equivalent V(3)As5 square pyramids, edges with two equivalent V(4)As6 octahedra, edges with four equivalent V(1)As5 square pyramids, and faces with two equivalent V(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the fifth V site, V(5) is bonded in a distorted square co-planar geometry to two equivalent As(1) and two equivalent As(3) atoms. There are three inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one V(5), two equivalent V(1), two equivalent V(2), and three equivalent V(3) atoms. In the second As site, As(2) is bonded to one V(1), two equivalent V(4), and three equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing AsV6 pentagonal pyramids. In the third As site, As(3) is bonded in a 7-coordinate geometry to one V(2), one V(4), one V(5), two equivalent V(1), and two equivalent V(3) atoms.
V4As3 crystallizes in the monoclinic C2/m space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to one As(2), two equivalent As(1), and two equivalent As(3) atoms to form distorted VAs5 square pyramids that share corners with six equivalent V(2)As6 octahedra, corners with six equivalent V(3)As5 square pyramids, edges with two equivalent V(4)As6 octahedra, edges with two equivalent V(1)As5 square pyramids, edges with two equivalent V(3)As5 square pyramids, and  a faceface with one V(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. The V(1)-As(2) bond length is 2.54 Å. Both V(1)-As(1) bond lengths are 2.55 Å. Both V(1)-As(3) bond lengths are 2.51 Å. In the second V site, V(2) is bonded to one As(3), two equivalent As(1), and three equivalent As(2) atoms to form distorted VAs6 octahedra that share corners with four equivalent V(4)As6 octahedra, corners with two equivalent V(3)As5 square pyramids, corners with six equivalent V(1)As5 square pyramids, edges with four equivalent V(2)As6 octahedra, edges with three equivalent V(3)As5 square pyramids,  a faceface with one V(4)As6 octahedra, and  a faceface with one V(1)As5 square pyramid. The corner-sharing octahedral tilt angles range from 50-51°. The V(2)-As(3) bond length is 2.47 Å. Both V(2)-As(1) bond lengths are 2.58 Å. There are two shorter (2.56 Å) and one longer (2.64 Å) V(2)-As(2) bond length. In the third V site, V(3) is bonded to two equivalent As(3) and three equivalent As(1) atoms to form distorted VAs5 square pyramids that share corners with two equivalent V(2)As6 octahedra, corners with two equivalent V(4)As6 octahedra, corners with six equivalent V(1)As5 square pyramids, edges with three equivalent V(2)As6 octahedra, edges with two equivalent V(1)As5 square pyramids, and edges with four equivalent V(3)As5 square pyramids. The corner-sharing octahedral tilt angles range from 21-46°. Both V(3)-As(3) bond lengths are 2.51 Å. There is one shorter (2.54 Å) and two longer (2.58 Å) V(3)-As(1) bond lengths. In the fourth V site, V(4) is bonded to two equivalent As(3) and four equivalent As(2) atoms to form VAs6 octahedra that share corners with eight equivalent V(2)As6 octahedra, corners with four equivalent V(3)As5 square pyramids, edges with two equivalent V(4)As6 octahedra, edges with four equivalent V(1)As5 square pyramids, and faces with two equivalent V(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. Both V(4)-As(3) bond lengths are 2.50 Å. All V(4)-As(2) bond lengths are 2.61 Å. In the fifth V site, V(5) is bonded in a distorted square co-planar geometry to two equivalent As(1) and two equivalent As(3) atoms. Both V(5)-As(1) bond lengths are 2.62 Å. Both V(5)-As(3) bond lengths are 2.56 Å. There are three inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one V(5), two equivalent V(1), two equivalent V(2), and three equivalent V(3) atoms. In the second As site, As(2) is bonded to one V(1), two equivalent V(4), and three equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing AsV6 pentagonal pyramids. In the third As site, As(3) is bonded in a 7-coordinate geometry to one V(2), one V(4), one V(5), two equivalent V(1), and two equivalent V(3) atoms.