AgP(OF)2 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 O(1), one O(4), and three equivalent O(3) atoms to form distorted AgO5 trigonal bipyramids that share  a cornercorner with one P(3)O2F2 tetrahedra, corners with four equivalent P(1)O2F2 tetrahedra,  a cornercorner with one Ag(2)O5 trigonal bipyramid, corners with two equivalent Ag(1)O5 trigonal bipyramids,  an edgeedge with one Ag(2)O5 trigonal bipyramid, and edges with two equivalent Ag(1)O5 trigonal bipyramids. In the second Ag site, Ag(2) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted AgO5 trigonal bipyramids that share  a cornercorner with one P(1)O2F2 tetrahedra, corners with two equivalent P(2)O2F2 tetrahedra, corners with two equivalent P(3)O2F2 tetrahedra,  a cornercorner with one Ag(1)O5 trigonal bipyramid,  an edgeedge with one Ag(1)O5 trigonal bipyramid, and edges with two equivalent Ag(2)O5 trigonal bipyramids. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one F(2), and one F(3) atom to form PO2F2 tetrahedra that share  a cornercorner with one Ag(2)O5 trigonal bipyramid and corners with four equivalent Ag(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent F(1) atoms to form PO2F2 tetrahedra that share corners with four equivalent Ag(2)O5 trigonal bipyramids. In the third P site, P(3) is bonded to two equivalent O(1) and two equivalent F(4) atoms to form PO2F2 tetrahedra that share corners with two equivalent Ag(1)O5 trigonal bipyramids and corners with four equivalent Ag(2)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1), two equivalent Ag(2), and one P(3) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Ag(2) and one P(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to three equivalent Ag(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(2), and one P(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one P(2) atom. In the second F site, F(2) is bonded in a single-bond geometry to one P(1) atom. In the third F site, F(3) is bonded in a single-bond geometry to one P(1) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to one P(3) atom.
AgP(OF)2 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 O(1), one O(4), and three equivalent O(3) atoms to form distorted AgO5 trigonal bipyramids that share  a cornercorner with one P(3)O2F2 tetrahedra, corners with four equivalent P(1)O2F2 tetrahedra,  a cornercorner with one Ag(2)O5 trigonal bipyramid, corners with two equivalent Ag(1)O5 trigonal bipyramids,  an edgeedge with one Ag(2)O5 trigonal bipyramid, and edges with two equivalent Ag(1)O5 trigonal bipyramids. The Ag(1)-O(1) bond length is 2.55 Å. The Ag(1)-O(4) bond length is 2.32 Å. There are a spread of Ag(1)-O(3) bond distances ranging from 2.40-2.71 Å. In the second Ag site, Ag(2) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted AgO5 trigonal bipyramids that share  a cornercorner with one P(1)O2F2 tetrahedra, corners with two equivalent P(2)O2F2 tetrahedra, corners with two equivalent P(3)O2F2 tetrahedra,  a cornercorner with one Ag(1)O5 trigonal bipyramid,  an edgeedge with one Ag(1)O5 trigonal bipyramid, and edges with two equivalent Ag(2)O5 trigonal bipyramids. The Ag(2)-O(4) bond length is 2.48 Å. There is one shorter (2.53 Å) and one longer (2.76 Å) Ag(2)-O(1) bond length. There is one shorter (2.39 Å) and one longer (2.40 Å) Ag(2)-O(2) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one F(2), and one F(3) atom to form PO2F2 tetrahedra that share  a cornercorner with one Ag(2)O5 trigonal bipyramid and corners with four equivalent Ag(1)O5 trigonal bipyramids. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.50 Å. The P(1)-F(2) bond length is 1.57 Å. The P(1)-F(3) bond length is 1.56 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent F(1) atoms to form PO2F2 tetrahedra that share corners with four equivalent Ag(2)O5 trigonal bipyramids. Both P(2)-O(2) bond lengths are 1.50 Å. Both P(2)-F(1) bond lengths are 1.57 Å. In the third P site, P(3) is bonded to two equivalent O(1) and two equivalent F(4) atoms to form PO2F2 tetrahedra that share corners with two equivalent Ag(1)O5 trigonal bipyramids and corners with four equivalent Ag(2)O5 trigonal bipyramids. Both P(3)-O(1) bond lengths are 1.50 Å. Both P(3)-F(4) bond lengths are 1.58 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1), two equivalent Ag(2), and one P(3) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Ag(2) and one P(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to three equivalent Ag(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(2), and one P(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one P(2) atom. In the second F site, F(2) is bonded in a single-bond geometry to one P(1) atom. In the third F site, F(3) is bonded in a single-bond geometry to one P(1) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to one P(3) atom.