AgTl(PO3)2 crystallizes in the monoclinic P2_1/c space group. Ag(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(5) atoms to form distorted AgO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ag(1)O5 trigonal bipyramid. Tl(1) is bonded in a 4-coordinate geometry to one O(3), one O(5), and two equivalent O(2) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with three equivalent Ag(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent Ag(1)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted single-bond geometry to two equivalent Ag(1), one Tl(1), and one P(1) atom. In the second O site, O(6) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1) and one P(2) atom. In the fourth O site, O(2) is bonded in a distorted single-bond geometry to one Ag(1), two equivalent Tl(1), and one P(1) atom. In the fifth O site, O(3) is bonded in a 2-coordinate geometry to one Ag(1), one Tl(1), and one P(2) atom. In the sixth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.
AgTl(PO3)2 crystallizes in the monoclinic P2_1/c space group. Ag(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(5) atoms to form distorted AgO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ag(1)O5 trigonal bipyramid. The Ag(1)-O(1) bond length is 2.47 Å. The Ag(1)-O(2) bond length is 2.48 Å. The Ag(1)-O(3) bond length is 2.37 Å. There is one shorter (2.57 Å) and one longer (2.63 Å) Ag(1)-O(5) bond length. Tl(1) is bonded in a 4-coordinate geometry to one O(3), one O(5), and two equivalent O(2) atoms. The Tl(1)-O(3) bond length is 2.86 Å. The Tl(1)-O(5) bond length is 2.87 Å. There is one shorter (2.83 Å) and one longer (2.92 Å) Tl(1)-O(2) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with three equivalent Ag(1)O5 trigonal bipyramids. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.62 Å. The P(1)-O(5) bond length is 1.50 Å. The P(1)-O(6) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent Ag(1)O5 trigonal bipyramids. The P(2)-O(1) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.63 Å. The P(2)-O(6) bond length is 1.63 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted single-bond geometry to two equivalent Ag(1), one Tl(1), and one P(1) atom. In the second O site, O(6) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1) and one P(2) atom. In the fourth O site, O(2) is bonded in a distorted single-bond geometry to one Ag(1), two equivalent Tl(1), and one P(1) atom. In the fifth O site, O(3) is bonded in a 2-coordinate geometry to one Ag(1), one Tl(1), and one P(2) atom. In the sixth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.