Cr2As6O19 crystallizes in the orthorhombic Pmmn space group. Cr(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent As(2)O4 tetrahedra and corners with four equivalent As(1)O4 tetrahedra. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form AsO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second As site, As(2) is bonded to one O(4), one O(7), and two equivalent O(3) atoms to form AsO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a bent 120 degrees geometry to two equivalent As(2) atoms. In the second O site, O(5) is bonded in a bent 120 degrees geometry to one Cr(1) and one As(1) atom. In the third O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent As(1) atoms. In the fourth O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent As(1) atoms. In the fifth O site, O(7) is bonded in a single-bond geometry to one As(2) atom. In the sixth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one As(1) atom. In the seventh O site, O(3) is bonded in a bent 120 degrees geometry to one Cr(1) and one As(2) atom.
Cr2As6O19 crystallizes in the orthorhombic Pmmn space group. Cr(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent As(2)O4 tetrahedra and corners with four equivalent As(1)O4 tetrahedra. Both Cr(1)-O(2) bond lengths are 1.99 Å. Both Cr(1)-O(3) bond lengths are 1.98 Å. Both Cr(1)-O(5) bond lengths are 2.00 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form AsO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-53°. The As(1)-O(1) bond length is 1.78 Å. The As(1)-O(2) bond length is 1.68 Å. The As(1)-O(5) bond length is 1.68 Å. The As(1)-O(6) bond length is 1.78 Å. In the second As site, As(2) is bonded to one O(4), one O(7), and two equivalent O(3) atoms to form AsO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. The As(2)-O(4) bond length is 1.78 Å. The As(2)-O(7) bond length is 1.73 Å. Both As(2)-O(3) bond lengths are 1.72 Å. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a bent 120 degrees geometry to two equivalent As(2) atoms. In the second O site, O(5) is bonded in a bent 120 degrees geometry to one Cr(1) and one As(1) atom. In the third O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent As(1) atoms. In the fourth O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent As(1) atoms. In the fifth O site, O(7) is bonded in a single-bond geometry to one As(2) atom. In the sixth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one As(1) atom. In the seventh O site, O(3) is bonded in a bent 120 degrees geometry to one Cr(1) and one As(2) atom.