LiBi3(O2Br)2 crystallizes in the orthorhombic Amm2 space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and two equivalent Br(1) atoms. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent Br(1), and two equivalent Br(2) atoms. In the third Bi site, Bi(3) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent Br(1), and two equivalent Br(2) atoms. O(1) is bonded to one Li(1), one Bi(1), one Bi(2), and one Bi(3) atom to form a mixture of distorted edge and corner-sharing OLiBi3 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 6-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms. In the second Br site, Br(2) is bonded in a 4-coordinate geometry to two equivalent Bi(2) and two equivalent Bi(3) atoms.
LiBi3(O2Br)2 crystallizes in the orthorhombic Amm2 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 2.07 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and two equivalent Br(1) atoms. All Bi(1)-O(1) bond lengths are 2.27 Å. Both Bi(1)-Br(1) bond lengths are 3.47 Å. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent Br(1), and two equivalent Br(2) atoms. All Bi(2)-O(1) bond lengths are 2.28 Å. Both Bi(2)-Br(1) bond lengths are 3.43 Å. Both Bi(2)-Br(2) bond lengths are 3.36 Å. In the third Bi site, Bi(3) is bonded in a 4-coordinate geometry to four equivalent O(1), two equivalent Br(1), and two equivalent Br(2) atoms. All Bi(3)-O(1) bond lengths are 2.29 Å. Both Bi(3)-Br(1) bond lengths are 3.41 Å. Both Bi(3)-Br(2) bond lengths are 3.34 Å. O(1) is bonded to one Li(1), one Bi(1), one Bi(2), and one Bi(3) atom to form a mixture of distorted edge and corner-sharing OLiBi3 tetrahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 6-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms. In the second Br site, Br(2) is bonded in a 4-coordinate geometry to two equivalent Bi(2) and two equivalent Bi(3) atoms.