Li5B4 crystallizes in the trigonal R3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one B(2) and four equivalent B(1) atoms. In the second Li site, Li(2) is bonded in a single-bond geometry to one B(2) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to six equivalent B(1) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded to two equivalent Li(3), four equivalent Li(1), and one B(2) atom to form a mixture of distorted edge, face, and corner-sharing BLi6B pentagonal bipyramids. In the second B site, B(2) is bonded in a 7-coordinate geometry to one Li(2), three equivalent Li(1), and three equivalent B(1) atoms.
Li5B4 crystallizes in the trigonal R3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one B(2) and four equivalent B(1) atoms. The Li(1)-B(2) bond length is 2.38 Å. There are two shorter (2.39 Å) and two longer (2.52 Å) Li(1)-B(1) bond lengths. In the second Li site, Li(2) is bonded in a single-bond geometry to one B(2) atom. The Li(2)-B(2) bond length is 2.16 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to six equivalent B(1) atoms. There are three shorter (2.40 Å) and three longer (2.56 Å) Li(3)-B(1) bond lengths. There are two inequivalent B sites. In the first B site, B(1) is bonded to two equivalent Li(3), four equivalent Li(1), and one B(2) atom to form a mixture of distorted edge, face, and corner-sharing BLi6B pentagonal bipyramids. The B(1)-B(2) bond length is 1.62 Å. In the second B site, B(2) is bonded in a 7-coordinate geometry to one Li(2), three equivalent Li(1), and three equivalent B(1) atoms.