BaLi4 crystallizes in the hexagonal P6_3/mmc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Li(3) and six equivalent Li(4) atoms to form face-sharing LiLi12 cuboctahedra. In the second Li site, Li(2) is bonded in a 10-coordinate geometry to one Li(2), three equivalent Li(4), and six equivalent Ba(1) atoms. In the third Li site, Li(3) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Li(3), six equivalent Li(4), and two equivalent Ba(1) atoms. In the fourth Li site, Li(4) is bonded in a 12-coordinate geometry to one Li(1), one Li(2), three equivalent Li(3), three equivalent Li(4), and four equivalent Ba(1) atoms. Ba(1) is bonded in a 18-coordinate geometry to two equivalent Li(3), four equivalent Li(2), eight equivalent Li(4), and four equivalent Ba(1) atoms.
BaLi4 crystallizes in the hexagonal P6_3/mmc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Li(3) and six equivalent Li(4) atoms to form face-sharing LiLi12 cuboctahedra. All Li(1)-Li(3) bond lengths are 2.91 Å. All Li(1)-Li(4) bond lengths are 3.13 Å. In the second Li site, Li(2) is bonded in a 10-coordinate geometry to one Li(2), three equivalent Li(4), and six equivalent Ba(1) atoms. The Li(2)-Li(2) bond length is 2.94 Å. All Li(2)-Li(4) bond lengths are 3.20 Å. There are three shorter (3.95 Å) and three longer (3.96 Å) Li(2)-Ba(1) bond lengths. In the third Li site, Li(3) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Li(3), six equivalent Li(4), and two equivalent Ba(1) atoms. Both Li(3)-Li(3) bond lengths are 3.24 Å. There are two shorter (3.07 Å) and four longer (3.14 Å) Li(3)-Li(4) bond lengths. Both Li(3)-Ba(1) bond lengths are 3.83 Å. In the fourth Li site, Li(4) is bonded in a 12-coordinate geometry to one Li(1), one Li(2), three equivalent Li(3), three equivalent Li(4), and four equivalent Ba(1) atoms. There is one shorter (3.25 Å) and two longer (3.30 Å) Li(4)-Li(4) bond lengths. There are two shorter (3.82 Å) and two longer (4.08 Å) Li(4)-Ba(1) bond lengths. Ba(1) is bonded in a 18-coordinate geometry to two equivalent Li(3), four equivalent Li(2), eight equivalent Li(4), and four equivalent Ba(1) atoms. There are two shorter (4.51 Å) and two longer (4.57 Å) Ba(1)-Ba(1) bond lengths.