Ba3(LiSb)4 crystallizes in the orthorhombic Immm space group. Li(1) is bonded to three equivalent Ba(1), one Sb(2), and three equivalent Sb(1) atoms to form distorted LiBa3Sb4 tetrahedra that share  a cornercorner with one Ba(2)Sb6 octahedra, corners with five equivalent Li(1)Ba3Sb4 tetrahedra, edges with two equivalent Ba(2)Sb6 octahedra, edges with six equivalent Li(1)Ba3Sb4 tetrahedra, and faces with four equivalent Li(1)Ba3Sb4 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 Sb(1), and four equivalent Sb(2) atoms. In the second Ba site, Ba(2) is bonded to two equivalent Sb(1) and four equivalent Sb(2) atoms to form BaSb6 octahedra that share corners with four equivalent Li(1)Ba3Sb4 tetrahedra, edges with two equivalent Ba(2)Sb6 octahedra, and edges with eight equivalent Li(1)Ba3Sb4 tetrahedra. There are two inequivalent Sb sites. In the first Sb site, Sb(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 Sb site, Sb(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), two equivalent Ba(2), four equivalent Ba(1), and one Sb(2) atom.
Ba3(LiSb)4 crystallizes in the orthorhombic Immm space group. Li(1) is bonded to three equivalent Ba(1), one Sb(2), and three equivalent Sb(1) atoms to form distorted LiBa3Sb4 tetrahedra that share  a cornercorner with one Ba(2)Sb6 octahedra, corners with five equivalent Li(1)Ba3Sb4 tetrahedra, edges with two equivalent Ba(2)Sb6 octahedra, edges with six equivalent Li(1)Ba3Sb4 tetrahedra, and faces with four equivalent Li(1)Ba3Sb4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. All Li(1)-Ba(1) bond lengths are 3.52 Å. The Li(1)-Sb(2) bond length is 3.06 Å. There are two shorter (2.99 Å) and one longer (3.00 Å) Li(1)-Sb(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 Sb(1), and four equivalent Sb(2) atoms. Both Ba(1)-Sb(1) bond lengths are 3.60 Å. All Ba(1)-Sb(2) bond lengths are 3.63 Å. In the second Ba site, Ba(2) is bonded to two equivalent Sb(1) and four equivalent Sb(2) atoms to form BaSb6 octahedra that share corners with four equivalent Li(1)Ba3Sb4 tetrahedra, edges with two equivalent Ba(2)Sb6 octahedra, and edges with eight equivalent Li(1)Ba3Sb4 tetrahedra. Both Ba(2)-Sb(1) bond lengths are 3.54 Å. All Ba(2)-Sb(2) bond lengths are 3.50 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(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 Sb site, Sb(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), two equivalent Ba(2), four equivalent Ba(1), and one Sb(2) atom. The Sb(2)-Sb(2) bond length is 2.84 Å.