Ag2S2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(3) atoms to form distorted AgO6 pentagonal pyramids that share corners with three equivalent Ag(2)O6 octahedra, corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra,  an edgeedge with one Ag(2)O6 octahedra, and  an edgeedge with one Ag(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 63-71°. In the second Ag site, Ag(2) is bonded to one O(1), one O(5), one O(6), one O(7), and two equivalent O(2) atoms to form distorted AgO6 octahedra that share corners with three equivalent Ag(1)O6 pentagonal pyramids, corners with three equivalent S(1)O4 tetrahedra, corners with three equivalent S(2)O4 tetrahedra,  an edgeedge with one Ag(2)O6 octahedra, and  an edgeedge with one Ag(1)O6 pentagonal pyramid. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with three equivalent Ag(2)O6 octahedra, corners with four equivalent Ag(1)O6 pentagonal pyramids, and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-56°. In the second S site, S(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form SO4 tetrahedra that share corners with three equivalent Ag(2)O6 octahedra, corners with two equivalent Ag(1)O6 pentagonal pyramids, and  a cornercorner with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-58°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ag(1), two equivalent Ag(2), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Ag(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one S(1) and one S(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Ag(2) and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom.
Ag2S2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(3) atoms to form distorted AgO6 pentagonal pyramids that share corners with three equivalent Ag(2)O6 octahedra, corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra,  an edgeedge with one Ag(2)O6 octahedra, and  an edgeedge with one Ag(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 63-71°. The Ag(1)-O(1) bond length is 2.64 Å. The Ag(1)-O(2) bond length is 2.59 Å. The Ag(1)-O(6) bond length is 2.54 Å. The Ag(1)-O(7) bond length is 2.44 Å. There is one shorter (2.52 Å) and one longer (2.53 Å) Ag(1)-O(3) bond length. In the second Ag site, Ag(2) is bonded to one O(1), one O(5), one O(6), one O(7), and two equivalent O(2) atoms to form distorted AgO6 octahedra that share corners with three equivalent Ag(1)O6 pentagonal pyramids, corners with three equivalent S(1)O4 tetrahedra, corners with three equivalent S(2)O4 tetrahedra,  an edgeedge with one Ag(2)O6 octahedra, and  an edgeedge with one Ag(1)O6 pentagonal pyramid. The Ag(2)-O(1) bond length is 2.48 Å. The Ag(2)-O(5) bond length is 2.49 Å. The Ag(2)-O(6) bond length is 2.44 Å. The Ag(2)-O(7) bond length is 2.51 Å. There is one shorter (2.52 Å) and one longer (2.54 Å) Ag(2)-O(2) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with three equivalent Ag(2)O6 octahedra, corners with four equivalent Ag(1)O6 pentagonal pyramids, and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-56°. The S(1)-O(1) bond length is 1.45 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(3) bond length is 1.44 Å. The S(1)-O(4) bond length is 1.62 Å. In the second S site, S(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form SO4 tetrahedra that share corners with three equivalent Ag(2)O6 octahedra, corners with two equivalent Ag(1)O6 pentagonal pyramids, and  a cornercorner with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-58°. The S(2)-O(4) bond length is 1.66 Å. The S(2)-O(5) bond length is 1.44 Å. The S(2)-O(6) bond length is 1.45 Å. The S(2)-O(7) bond length is 1.45 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ag(1), two equivalent Ag(2), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Ag(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one S(1) and one S(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Ag(2) and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom.