LiBi3(O2I)2 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent I(1), and two equivalent I(2) atoms. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent I(1), and two equivalent I(2) atoms. O(1) is bonded to one Li(1), one Bi(1), and two equivalent Bi(2) atoms to form a mixture of distorted corner and edge-sharing OLiBi3 tetrahedra. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms. In the second I site, I(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms.
LiBi3(O2I)2 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. All Li(1)-O(1) bond lengths are 2.11 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent I(1), and two equivalent I(2) atoms. All Bi(1)-O(1) bond lengths are 2.30 Å. Both Bi(1)-I(1) bond lengths are 3.51 Å. Both Bi(1)-I(2) bond lengths are 3.57 Å. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent I(1), and two equivalent I(2) atoms. All Bi(2)-O(1) bond lengths are 2.28 Å. There is one shorter (3.58 Å) and one longer (3.66 Å) Bi(2)-I(1) bond length. Both Bi(2)-I(2) bond lengths are 3.62 Å. O(1) is bonded to one Li(1), one Bi(1), and two equivalent Bi(2) atoms to form a mixture of distorted corner and edge-sharing OLiBi3 tetrahedra. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms. In the second I site, I(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms.