Ag2As2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 2-coordinate geometry to one O(3), one O(7), and two equivalent O(6) atoms. In the second Ag site, Ag(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing AsO4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-62°. In the second As site, As(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form AsO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra and  an edgeedge with one As(2)O6 octahedra. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 120 degrees geometry to one As(1) and one As(2) atom. In the second O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Ag(1) and one As(1) atom. In the third O site, O(7) is bonded in a bent 120 degrees geometry to one Ag(1) and one As(1) atom. In the fourth O site, O(1) is bonded in a distorted T-shaped geometry to one Ag(2) and two equivalent As(2) atoms. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ag(2) and one As(2) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Ag(1), two equivalent Ag(2), and one As(2) atom. In the seventh O site, O(4) is bonded in a bent 120 degrees geometry to one As(1) and one As(2) atom.
Ag2As2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 2-coordinate geometry to one O(3), one O(7), and two equivalent O(6) atoms. The Ag(1)-O(3) bond length is 2.71 Å. The Ag(1)-O(7) bond length is 2.13 Å. There is one shorter (2.12 Å) and one longer (2.67 Å) Ag(1)-O(6) bond length. In the second Ag site, Ag(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Ag(2)-O(1) bond length is 2.22 Å. The Ag(2)-O(2) bond length is 2.07 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Ag(2)-O(3) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing AsO4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-62°. The As(1)-O(4) bond length is 1.76 Å. The As(1)-O(5) bond length is 1.75 Å. The As(1)-O(6) bond length is 1.71 Å. The As(1)-O(7) bond length is 1.72 Å. In the second As site, As(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form AsO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra and  an edgeedge with one As(2)O6 octahedra. The As(2)-O(2) bond length is 1.75 Å. The As(2)-O(3) bond length is 1.86 Å. The As(2)-O(4) bond length is 1.91 Å. The As(2)-O(5) bond length is 1.96 Å. There is one shorter (1.88 Å) and one longer (1.95 Å) As(2)-O(1) bond length. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 120 degrees geometry to one As(1) and one As(2) atom. In the second O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Ag(1) and one As(1) atom. In the third O site, O(7) is bonded in a bent 120 degrees geometry to one Ag(1) and one As(1) atom. In the fourth O site, O(1) is bonded in a distorted T-shaped geometry to one Ag(2) and two equivalent As(2) atoms. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ag(2) and one As(2) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Ag(1), two equivalent Ag(2), and one As(2) atom. In the seventh O site, O(4) is bonded in a bent 120 degrees geometry to one As(1) and one As(2) atom.