Ba3(LiBi)4 crystallizes in the orthorhombic Immm space group. Li(1) is bonded to three equivalent Ba(1), one Bi(2), and three equivalent Bi(1) atoms to form distorted LiBa3Bi4 tetrahedra that share  a cornercorner with one Ba(2)Bi6 octahedra, corners with five equivalent Li(1)Ba3Bi4 tetrahedra, edges with two equivalent Ba(2)Bi6 octahedra, edges with six equivalent Li(1)Ba3Bi4 tetrahedra, and faces with four equivalent Li(1)Ba3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to six equivalent Li(1), two equivalent Bi(1), and four equivalent Bi(2) atoms. In the second Ba site, Ba(2) is bonded to two equivalent Bi(1) and four equivalent Bi(2) atoms to form BaBi6 octahedra that share corners with four equivalent Li(1)Ba3Bi4 tetrahedra, edges with two equivalent Ba(2)Bi6 octahedra, and edges with eight equivalent Li(1)Ba3Bi4 tetrahedra. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to six equivalent Li(1), one Ba(2), and two equivalent Ba(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), two equivalent Ba(2), four equivalent Ba(1), and one Bi(2) atom.
Ba3(LiBi)4 crystallizes in the orthorhombic Immm space group. Li(1) is bonded to three equivalent Ba(1), one Bi(2), and three equivalent Bi(1) atoms to form distorted LiBa3Bi4 tetrahedra that share  a cornercorner with one Ba(2)Bi6 octahedra, corners with five equivalent Li(1)Ba3Bi4 tetrahedra, edges with two equivalent Ba(2)Bi6 octahedra, edges with six equivalent Li(1)Ba3Bi4 tetrahedra, and faces with four equivalent Li(1)Ba3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. There are two shorter (3.60 Å) and one longer (3.61 Å) Li(1)-Ba(1) bond length. The Li(1)-Bi(2) bond length is 3.08 Å. There are two shorter (3.05 Å) and one longer (3.06 Å) Li(1)-Bi(1) bond length. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to six equivalent Li(1), two equivalent Bi(1), and four equivalent Bi(2) atoms. Both Ba(1)-Bi(1) bond lengths are 3.67 Å. All Ba(1)-Bi(2) bond lengths are 3.71 Å. In the second Ba site, Ba(2) is bonded to two equivalent Bi(1) and four equivalent Bi(2) atoms to form BaBi6 octahedra that share corners with four equivalent Li(1)Ba3Bi4 tetrahedra, edges with two equivalent Ba(2)Bi6 octahedra, and edges with eight equivalent Li(1)Ba3Bi4 tetrahedra. Both Ba(2)-Bi(1) bond lengths are 3.60 Å. All Ba(2)-Bi(2) bond lengths are 3.52 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to six equivalent Li(1), one Ba(2), and two equivalent Ba(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), two equivalent Ba(2), four equivalent Ba(1), and one Bi(2) atom. The Bi(2)-Bi(2) bond length is 3.02 Å.