V3As2O9 crystallizes in the monoclinic Cm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-48°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(7) atoms to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-48°. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(6), and two equivalent O(7) atoms to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. There are two inequivalent As sites. In the first As site, As(1) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(6) atoms. In the second As site, As(2) is bonded in a distorted T-shaped geometry to one O(4) and two equivalent O(7) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one As(2) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one As(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one As(2) atom.
V3As2O9 crystallizes in the monoclinic Cm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-48°. The V(1)-O(1) bond length is 1.82 Å. The V(1)-O(3) bond length is 2.04 Å. The V(1)-O(4) bond length is 2.10 Å. The V(1)-O(5) bond length is 1.73 Å. Both V(1)-O(6) bond lengths are 1.99 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(7) atoms to form a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-48°. The V(2)-O(2) bond length is 1.67 Å. The V(2)-O(3) bond length is 2.04 Å. The V(2)-O(4) bond length is 2.12 Å. The V(2)-O(5) bond length is 1.89 Å. Both V(2)-O(7) bond lengths are 1.99 Å. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(6), and two equivalent O(7) atoms to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. The V(3)-O(1) bond length is 1.75 Å. The V(3)-O(2) bond length is 2.06 Å. Both V(3)-O(6) bond lengths are 1.98 Å. Both V(3)-O(7) bond lengths are 1.98 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(6) atoms. The As(1)-O(3) bond length is 1.77 Å. Both As(1)-O(6) bond lengths are 1.81 Å. In the second As site, As(2) is bonded in a distorted T-shaped geometry to one O(4) and two equivalent O(7) atoms. The As(2)-O(4) bond length is 1.76 Å. Both As(2)-O(7) bond lengths are 1.82 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one As(2) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one As(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one As(2) atom.