V3(AsO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with three equivalent As(1)O5 trigonal bipyramids,  a cornercorner with one As(2)O4 trigonal pyramid, and  an edgeedge with one As(2)O4 trigonal pyramid. In the second V site, V(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(5), and two equivalent O(7) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(8) atom to form AsO5 trigonal bipyramids that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one As(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-39°. In the second As site, As(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form distorted AsO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one As(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 45°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one As(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one As(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one As(1) and one As(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one As(2) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one As(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one As(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one As(1) atom.
V3(AsO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with three equivalent As(1)O5 trigonal bipyramids,  a cornercorner with one As(2)O4 trigonal pyramid, and  an edgeedge with one As(2)O4 trigonal pyramid. The V(1)-O(1) bond length is 1.85 Å. The V(1)-O(2) bond length is 2.09 Å. The V(1)-O(4) bond length is 1.73 Å. The V(1)-O(5) bond length is 2.23 Å. The V(1)-O(7) bond length is 2.09 Å. The V(1)-O(8) bond length is 1.80 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(5), and two equivalent O(7) atoms. Both V(2)-O(2) bond lengths are 2.38 Å. Both V(2)-O(5) bond lengths are 2.07 Å. Both V(2)-O(7) bond lengths are 1.96 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(8) atom to form AsO5 trigonal bipyramids that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one As(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-39°. The As(1)-O(1) bond length is 1.76 Å. The As(1)-O(3) bond length is 2.05 Å. The As(1)-O(4) bond length is 1.91 Å. The As(1)-O(6) bond length is 1.66 Å. The As(1)-O(8) bond length is 1.79 Å. In the second As site, As(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form distorted AsO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one As(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 45°. The As(2)-O(2) bond length is 1.73 Å. The As(2)-O(3) bond length is 1.70 Å. The As(2)-O(5) bond length is 1.75 Å. The As(2)-O(7) bond length is 1.82 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one As(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one As(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one As(1) and one As(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one As(2) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one As(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one As(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one As(1) atom.