Pb3I2O2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a distorted L-shaped geometry to two equivalent O(1), one I(1), and three equivalent I(2) atoms. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to four equivalent O(1) atoms. In the third Pb site, Pb(3) is bonded in a distorted L-shaped geometry to two equivalent O(1) and one I(1) atom. O(1) is bonded to one Pb(1), one Pb(3), and two equivalent Pb(2) atoms to form a mixture of edge and corner-sharing OPb4 tetrahedra. There are two inequivalent I sites. In the first I site, I(1) is bonded in a water-like geometry to one Pb(1) and one Pb(3) atom. In the second I site, I(2) is bonded in a distorted trigonal planar geometry to three equivalent Pb(1) atoms.
Pb3I2O2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a distorted L-shaped geometry to two equivalent O(1), one I(1), and three equivalent I(2) atoms. Both Pb(1)-O(1) bond lengths are 2.30 Å. The Pb(1)-I(1) bond length is 3.39 Å. There is one shorter (3.22 Å) and two longer (3.53 Å) Pb(1)-I(2) bond lengths. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to four equivalent O(1) atoms. There are two shorter (2.42 Å) and two longer (2.45 Å) Pb(2)-O(1) bond lengths. In the third Pb site, Pb(3) is bonded in a distorted L-shaped geometry to two equivalent O(1) and one I(1) atom. Both Pb(3)-O(1) bond lengths are 2.24 Å. The Pb(3)-I(1) bond length is 3.21 Å. O(1) is bonded to one Pb(1), one Pb(3), and two equivalent Pb(2) atoms to form a mixture of edge and corner-sharing OPb4 tetrahedra. There are two inequivalent I sites. In the first I site, I(1) is bonded in a water-like geometry to one Pb(1) and one Pb(3) atom. In the second I site, I(2) is bonded in a distorted trigonal planar geometry to three equivalent Pb(1) atoms.