Ag4Se(O2I)2 crystallizes in the orthorhombic Pna2_1 space group. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one I(2), and two equivalent I(1) atoms. In the second Ag site, Ag(2) is bonded in a 2-coordinate geometry to two equivalent O(1), two equivalent I(1), and two equivalent I(2) atoms. In the third Ag site, Ag(3) is bonded in a 5-coordinate geometry to one O(3), one O(4), one I(2), and two equivalent I(1) atoms. In the fourth Ag site, Ag(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one I(1), and two equivalent I(2) atoms. Se(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(3) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(3), and one Se(1) atom. In the second O site, O(4) is bonded in a 2-coordinate geometry to one Ag(1), one Ag(3), and one Se(1) atom. In the third O site, O(1) is bonded to one Ag(4), two equivalent Ag(2), and one Se(1) atom to form distorted corner-sharing OAg3Se tetrahedra. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(4), and one Se(1) atom. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 7-coordinate geometry to one Ag(4), two equivalent Ag(1), two equivalent Ag(2), and two equivalent Ag(3) atoms. In the second I site, I(2) is bonded in a 6-coordinate geometry to one Ag(1), one Ag(3), two equivalent Ag(2), and two equivalent Ag(4) atoms.
Ag4Se(O2I)2 crystallizes in the orthorhombic Pna2_1 space group. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one I(2), and two equivalent I(1) atoms. The Ag(1)-O(2) bond length is 2.38 Å. The Ag(1)-O(3) bond length is 2.50 Å. The Ag(1)-O(4) bond length is 2.39 Å. The Ag(1)-I(2) bond length is 2.90 Å. There is one shorter (3.45 Å) and one longer (3.46 Å) Ag(1)-I(1) bond length. In the second Ag site, Ag(2) is bonded in a 2-coordinate geometry to two equivalent O(1), two equivalent I(1), and two equivalent I(2) atoms. There is one shorter (2.45 Å) and one longer (2.47 Å) Ag(2)-O(1) bond length. There is one shorter (3.02 Å) and one longer (3.18 Å) Ag(2)-I(1) bond length. There is one shorter (3.06 Å) and one longer (3.41 Å) Ag(2)-I(2) bond length. In the third Ag site, Ag(3) is bonded in a 5-coordinate geometry to one O(3), one O(4), one I(2), and two equivalent I(1) atoms. The Ag(3)-O(3) bond length is 2.51 Å. The Ag(3)-O(4) bond length is 2.80 Å. The Ag(3)-I(2) bond length is 2.88 Å. There is one shorter (2.89 Å) and one longer (2.91 Å) Ag(3)-I(1) bond length. In the fourth Ag site, Ag(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one I(1), and two equivalent I(2) atoms. The Ag(4)-O(1) bond length is 2.44 Å. The Ag(4)-O(2) bond length is 2.42 Å. The Ag(4)-I(1) bond length is 3.05 Å. There is one shorter (2.94 Å) and one longer (3.18 Å) Ag(4)-I(2) bond length. Se(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Se(1)-O(1) bond length is 1.72 Å. The Se(1)-O(2) bond length is 1.69 Å. The Se(1)-O(3) bond length is 1.68 Å. The Se(1)-O(4) bond length is 1.68 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(3), and one Se(1) atom. In the second O site, O(4) is bonded in a 2-coordinate geometry to one Ag(1), one Ag(3), and one Se(1) atom. In the third O site, O(1) is bonded to one Ag(4), two equivalent Ag(2), and one Se(1) atom to form distorted corner-sharing OAg3Se tetrahedra. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(4), and one Se(1) atom. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 7-coordinate geometry to one Ag(4), two equivalent Ag(1), two equivalent Ag(2), and two equivalent Ag(3) atoms. In the second I site, I(2) is bonded in a 6-coordinate geometry to one Ag(1), one Ag(3), two equivalent Ag(2), and two equivalent Ag(4) atoms.