VCr3As4 is Modderite-derived structured and crystallizes in the monoclinic Pm space group. V(1) is bonded to one As(1), one As(2), two equivalent As(3), and two equivalent As(4) atoms to form distorted VAs6 octahedra that share corners with four equivalent Cr(1)As6 octahedra, corners with eight equivalent Cr(3)As6 octahedra, edges with two equivalent V(1)As6 octahedra, edges with four equivalent Cr(2)As6 octahedra, and faces with two equivalent Cr(1)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one As(1), one As(2), two equivalent As(3), and two equivalent As(4) atoms to form distorted CrAs6 octahedra that share corners with four equivalent V(1)As6 octahedra, corners with eight equivalent Cr(2)As6 octahedra, edges with two equivalent Cr(1)As6 octahedra, edges with four equivalent Cr(3)As6 octahedra, and faces with two equivalent V(1)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. In the second Cr site, Cr(2) is bonded to one As(3), one As(4), two equivalent As(1), and two equivalent As(2) atoms to form distorted CrAs6 octahedra that share corners with four equivalent Cr(3)As6 octahedra, corners with eight equivalent Cr(1)As6 octahedra, edges with two equivalent Cr(2)As6 octahedra, edges with four equivalent V(1)As6 octahedra, and faces with two equivalent Cr(3)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. In the third Cr site, Cr(3) is bonded to one As(3), one As(4), two equivalent As(1), and two equivalent As(2) atoms to form distorted CrAs6 octahedra that share corners with four equivalent Cr(2)As6 octahedra, corners with eight equivalent V(1)As6 octahedra, edges with two equivalent Cr(3)As6 octahedra, edges with four equivalent Cr(1)As6 octahedra, and faces with two equivalent Cr(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 6-coordinate geometry to one V(1), one Cr(1), two equivalent Cr(2), and two equivalent Cr(3) atoms. In the second As site, As(2) is bonded in a 6-coordinate geometry to one V(1), one Cr(1), two equivalent Cr(2), and two equivalent Cr(3) atoms. In the third As site, As(3) is bonded in a 6-coordinate geometry to two equivalent V(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the fourth As site, As(4) is bonded in a 6-coordinate geometry to two equivalent V(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms.
VCr3As4 is Modderite-derived structured and crystallizes in the monoclinic Pm space group. V(1) is bonded to one As(1), one As(2), two equivalent As(3), and two equivalent As(4) atoms to form distorted VAs6 octahedra that share corners with four equivalent Cr(1)As6 octahedra, corners with eight equivalent Cr(3)As6 octahedra, edges with two equivalent V(1)As6 octahedra, edges with four equivalent Cr(2)As6 octahedra, and faces with two equivalent Cr(1)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. The V(1)-As(1) bond length is 2.59 Å. The V(1)-As(2) bond length is 2.48 Å. Both V(1)-As(3) bond lengths are 2.54 Å. Both V(1)-As(4) bond lengths are 2.55 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one As(1), one As(2), two equivalent As(3), and two equivalent As(4) atoms to form distorted CrAs6 octahedra that share corners with four equivalent V(1)As6 octahedra, corners with eight equivalent Cr(2)As6 octahedra, edges with two equivalent Cr(1)As6 octahedra, edges with four equivalent Cr(3)As6 octahedra, and faces with two equivalent V(1)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. The Cr(1)-As(1) bond length is 2.52 Å. The Cr(1)-As(2) bond length is 2.59 Å. Both Cr(1)-As(3) bond lengths are 2.55 Å. Both Cr(1)-As(4) bond lengths are 2.49 Å. In the second Cr site, Cr(2) is bonded to one As(3), one As(4), two equivalent As(1), and two equivalent As(2) atoms to form distorted CrAs6 octahedra that share corners with four equivalent Cr(3)As6 octahedra, corners with eight equivalent Cr(1)As6 octahedra, edges with two equivalent Cr(2)As6 octahedra, edges with four equivalent V(1)As6 octahedra, and faces with two equivalent Cr(3)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. The Cr(2)-As(3) bond length is 2.63 Å. The Cr(2)-As(4) bond length is 2.42 Å. Both Cr(2)-As(1) bond lengths are 2.54 Å. Both Cr(2)-As(2) bond lengths are 2.50 Å. In the third Cr site, Cr(3) is bonded to one As(3), one As(4), two equivalent As(1), and two equivalent As(2) atoms to form distorted CrAs6 octahedra that share corners with four equivalent Cr(2)As6 octahedra, corners with eight equivalent V(1)As6 octahedra, edges with two equivalent Cr(3)As6 octahedra, edges with four equivalent Cr(1)As6 octahedra, and faces with two equivalent Cr(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. The Cr(3)-As(3) bond length is 2.46 Å. The Cr(3)-As(4) bond length is 2.56 Å. Both Cr(3)-As(1) bond lengths are 2.54 Å. Both Cr(3)-As(2) bond lengths are 2.50 Å. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 6-coordinate geometry to one V(1), one Cr(1), two equivalent Cr(2), and two equivalent Cr(3) atoms. In the second As site, As(2) is bonded in a 6-coordinate geometry to one V(1), one Cr(1), two equivalent Cr(2), and two equivalent Cr(3) atoms. In the third As site, As(3) is bonded in a 6-coordinate geometry to two equivalent V(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the fourth As site, As(4) is bonded in a 6-coordinate geometry to two equivalent V(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms.