V5As3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one As(1) and four equivalent As(2) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to two equivalent As(1) and four equivalent As(2) atoms. In the third V site, V(3) is bonded to one As(1) and four equivalent As(2) atoms to form distorted edge-sharing VAs5 square pyramids. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to two equivalent As(1) and three equivalent As(2) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one V(1), one V(3), two equivalent V(2), and four equivalent V(4) atoms. In the second As site, As(2) is bonded in a 9-coordinate geometry to two equivalent V(1), two equivalent V(2), two equivalent V(3), and three equivalent V(4) atoms.
V5As3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one As(1) and four equivalent As(2) atoms. The V(1)-As(1) bond length is 2.49 Å. There are two shorter (2.56 Å) and two longer (2.66 Å) V(1)-As(2) bond lengths. In the second V site, V(2) is bonded in a 6-coordinate geometry to two equivalent As(1) and four equivalent As(2) atoms. There is one shorter (2.55 Å) and one longer (2.68 Å) V(2)-As(1) bond length. There are two shorter (2.58 Å) and two longer (2.61 Å) V(2)-As(2) bond lengths. In the third V site, V(3) is bonded to one As(1) and four equivalent As(2) atoms to form distorted edge-sharing VAs5 square pyramids. The V(3)-As(1) bond length is 2.52 Å. There are two shorter (2.53 Å) and two longer (2.54 Å) V(3)-As(2) bond lengths. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to two equivalent As(1) and three equivalent As(2) atoms. There is one shorter (2.49 Å) and one longer (2.53 Å) V(4)-As(1) bond length. There are a spread of V(4)-As(2) bond distances ranging from 2.54-2.76 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one V(1), one V(3), two equivalent V(2), and four equivalent V(4) atoms. In the second As site, As(2) is bonded in a 9-coordinate geometry to two equivalent V(1), two equivalent V(2), two equivalent V(3), and three equivalent V(4) atoms.