Ag4I(PO4) crystallizes in the monoclinic P2_1/m space group. There are five inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 4-coordinate geometry to one O(6), two equivalent O(1), and one I(2) atom. In the second Ag site, Ag(2) is bonded in a distorted bent 120 degrees geometry to one O(4), one O(5), one I(1), and two equivalent I(2) atoms. In the third Ag site, Ag(3) is bonded to one O(2), one O(3), two equivalent O(5), and one I(2) atom to form distorted AgIO4 trigonal pyramids that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. In the fourth Ag site, Ag(4) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(5), and one I(1) atom. In the fifth Ag site, Ag(5) is bonded in a 4-coordinate geometry to one O(6), two equivalent O(1), and one I(1) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(6), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with three equivalent Ag(3)IO4 trigonal pyramids. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share  a cornercorner with one Ag(3)IO4 trigonal pyramid. There are six inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to one Ag(5), two equivalent Ag(1), and one P(1) atom. In the second O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Ag(5), two equivalent Ag(1), and one P(2) atom. In the third O site, O(2) is bonded in a distorted single-bond geometry to one Ag(3), two equivalent Ag(4), and one P(1) atom. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Ag(3), two equivalent Ag(4), and one P(2) atom. In the fifth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Ag(2) and one P(2) atom. In the sixth O site, O(5) is bonded in a 4-coordinate geometry to one Ag(2), one Ag(3), one Ag(4), and one P(1) atom. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 5-coordinate geometry to one Ag(5), two equivalent Ag(2), and two equivalent Ag(4) atoms. In the second I site, I(2) is bonded in a 7-coordinate geometry to one Ag(3), two equivalent Ag(1), and four equivalent Ag(2) atoms.
Ag4I(PO4) crystallizes in the monoclinic P2_1/m space group. There are five inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 4-coordinate geometry to one O(6), two equivalent O(1), and one I(2) atom. The Ag(1)-O(6) bond length is 2.39 Å. There is one shorter (2.38 Å) and one longer (2.44 Å) Ag(1)-O(1) bond length. The Ag(1)-I(2) bond length is 2.75 Å. In the second Ag site, Ag(2) is bonded in a distorted bent 120 degrees geometry to one O(4), one O(5), one I(1), and two equivalent I(2) atoms. The Ag(2)-O(4) bond length is 2.34 Å. The Ag(2)-O(5) bond length is 2.45 Å. The Ag(2)-I(1) bond length is 2.95 Å. There is one shorter (2.99 Å) and one longer (3.32 Å) Ag(2)-I(2) bond length. In the third Ag site, Ag(3) is bonded to one O(2), one O(3), two equivalent O(5), and one I(2) atom to form distorted AgIO4 trigonal pyramids that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The Ag(3)-O(2) bond length is 2.70 Å. The Ag(3)-O(3) bond length is 2.46 Å. Both Ag(3)-O(5) bond lengths are 2.45 Å. The Ag(3)-I(2) bond length is 3.45 Å. In the fourth Ag site, Ag(4) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(5), and one I(1) atom. The Ag(4)-O(2) bond length is 2.45 Å. The Ag(4)-O(3) bond length is 2.36 Å. The Ag(4)-O(5) bond length is 2.43 Å. The Ag(4)-I(1) bond length is 2.85 Å. In the fifth Ag site, Ag(5) is bonded in a 4-coordinate geometry to one O(6), two equivalent O(1), and one I(1) atom. The Ag(5)-O(6) bond length is 2.53 Å. Both Ag(5)-O(1) bond lengths are 2.42 Å. The Ag(5)-I(1) bond length is 2.81 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(6), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with three equivalent Ag(3)IO4 trigonal pyramids. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.57 Å. Both P(1)-O(5) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share  a cornercorner with one Ag(3)IO4 trigonal pyramid. The P(2)-O(3) bond length is 1.58 Å. The P(2)-O(4) bond length is 1.55 Å. Both P(2)-O(1) bond lengths are 1.57 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to one Ag(5), two equivalent Ag(1), and one P(1) atom. In the second O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Ag(5), two equivalent Ag(1), and one P(2) atom. In the third O site, O(2) is bonded in a distorted single-bond geometry to one Ag(3), two equivalent Ag(4), and one P(1) atom. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Ag(3), two equivalent Ag(4), and one P(2) atom. In the fifth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Ag(2) and one P(2) atom. In the sixth O site, O(5) is bonded in a 4-coordinate geometry to one Ag(2), one Ag(3), one Ag(4), and one P(1) atom. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 5-coordinate geometry to one Ag(5), two equivalent Ag(2), and two equivalent Ag(4) atoms. In the second I site, I(2) is bonded in a 7-coordinate geometry to one Ag(3), two equivalent Ag(1), and four equivalent Ag(2) atoms.