LiBH4 crystallizes in the hexagonal P6_3mc space group. Li(1) is bonded to one H(1) and six equivalent H(2) atoms to form LiH7 hexagonal pyramids that share corners with six equivalent Li(1)H7 hexagonal pyramids,  a cornercorner with one B(1)H4 tetrahedra, and edges with three equivalent B(1)H4 tetrahedra. B(1) is bonded to one H(1) and three equivalent H(2) atoms to form BH4 tetrahedra that share  a cornercorner with one Li(1)H7 hexagonal pyramid and edges with three equivalent Li(1)H7 hexagonal pyramids. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one Li(1) and one B(1) atom. In the second H site, H(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one B(1) atom.
LiBH4 crystallizes in the hexagonal P6_3mc space group. Li(1) is bonded to one H(1) and six equivalent H(2) atoms to form LiH7 hexagonal pyramids that share corners with six equivalent Li(1)H7 hexagonal pyramids,  a cornercorner with one B(1)H4 tetrahedra, and edges with three equivalent B(1)H4 tetrahedra. The Li(1)-H(1) bond length is 1.91 Å. All Li(1)-H(2) bond lengths are 2.11 Å. B(1) is bonded to one H(1) and three equivalent H(2) atoms to form BH4 tetrahedra that share  a cornercorner with one Li(1)H7 hexagonal pyramid and edges with three equivalent Li(1)H7 hexagonal pyramids. The B(1)-H(1) bond length is 1.22 Å. All B(1)-H(2) bond lengths are 1.22 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one Li(1) and one B(1) atom. In the second H site, H(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one B(1) atom.