Ag4P2S7 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(2), one S(4), and two equivalent S(1) atoms to form distorted AgS4 trigonal pyramids that share corners with four equivalent P(1)S4 tetrahedra, corners with five equivalent Ag(2)S4 trigonal pyramids, and  an edgeedge with one Ag(1)S4 trigonal pyramid. In the second Ag site, Ag(2) is bonded to one S(1), one S(4), and two equivalent S(2) atoms to form AgS4 trigonal pyramids that share corners with four equivalent P(1)S4 tetrahedra, corners with two equivalent Ag(2)S4 trigonal pyramids, and corners with five equivalent Ag(1)S4 trigonal pyramids. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share  a cornercorner with one P(1)S4 tetrahedra, corners with four equivalent Ag(1)S4 trigonal pyramids, and corners with four equivalent Ag(2)S4 trigonal pyramids. There are four inequivalent S sites. In the first S site, S(4) is bonded in a trigonal non-coplanar geometry to one Ag(1), one Ag(2), and one P(1) atom. In the second S site, S(1) is bonded to one Ag(2), two equivalent Ag(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing SAg3P trigonal pyramids. In the third S site, S(2) is bonded to one Ag(1), two equivalent Ag(2), and one P(1) atom to form corner-sharing SAg3P tetrahedra. In the fourth S site, S(3) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms.
Ag4P2S7 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(2), one S(4), and two equivalent S(1) atoms to form distorted AgS4 trigonal pyramids that share corners with four equivalent P(1)S4 tetrahedra, corners with five equivalent Ag(2)S4 trigonal pyramids, and  an edgeedge with one Ag(1)S4 trigonal pyramid. The Ag(1)-S(2) bond length is 2.56 Å. The Ag(1)-S(4) bond length is 2.58 Å. There is one shorter (2.59 Å) and one longer (2.96 Å) Ag(1)-S(1) bond length. In the second Ag site, Ag(2) is bonded to one S(1), one S(4), and two equivalent S(2) atoms to form AgS4 trigonal pyramids that share corners with four equivalent P(1)S4 tetrahedra, corners with two equivalent Ag(2)S4 trigonal pyramids, and corners with five equivalent Ag(1)S4 trigonal pyramids. The Ag(2)-S(1) bond length is 2.72 Å. The Ag(2)-S(4) bond length is 2.55 Å. There is one shorter (2.57 Å) and one longer (2.73 Å) Ag(2)-S(2) bond length. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share  a cornercorner with one P(1)S4 tetrahedra, corners with four equivalent Ag(1)S4 trigonal pyramids, and corners with four equivalent Ag(2)S4 trigonal pyramids. The P(1)-S(1) bond length is 2.03 Å. The P(1)-S(2) bond length is 2.08 Å. The P(1)-S(3) bond length is 2.15 Å. The P(1)-S(4) bond length is 2.05 Å. There are four inequivalent S sites. In the first S site, S(4) is bonded in a trigonal non-coplanar geometry to one Ag(1), one Ag(2), and one P(1) atom. In the second S site, S(1) is bonded to one Ag(2), two equivalent Ag(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing SAg3P trigonal pyramids. In the third S site, S(2) is bonded to one Ag(1), two equivalent Ag(2), and one P(1) atom to form corner-sharing SAg3P tetrahedra. In the fourth S site, S(3) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms.