Pb2PO4I crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms. In the second Pb site, Pb(2) is bonded in a 3-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent I(1) atoms. P(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Pb(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Pb(2), two equivalent Pb(1), and one P(1) atom. I(1) is bonded in a 3-coordinate geometry to three equivalent Pb(2) atoms.
Pb2PO4I crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms. The Pb(1)-O(1) bond length is 2.59 Å. The Pb(1)-O(3) bond length is 2.69 Å. There is one shorter (2.45 Å) and one longer (2.70 Å) Pb(1)-O(2) bond length. There is one shorter (2.49 Å) and one longer (2.83 Å) Pb(1)-O(4) bond length. In the second Pb site, Pb(2) is bonded in a 3-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent I(1) atoms. The Pb(2)-O(1) bond length is 2.44 Å. The Pb(2)-O(3) bond length is 2.40 Å. The Pb(2)-O(4) bond length is 2.56 Å. There are a spread of Pb(2)-I(1) bond distances ranging from 3.30-3.51 Å. P(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.55 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Pb(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Pb(2), two equivalent Pb(1), and one P(1) atom. I(1) is bonded in a 3-coordinate geometry to three equivalent Pb(2) atoms.