Li5Ga4 crystallizes in the trigonal P-3m1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent Li(3) and four equivalent Ga(1) atoms to form distorted LiLi3Ga4 tetrahedra that share corners with three equivalent Li(1)Li3Ga4 tetrahedra, corners with four equivalent Li(2)Ga4 tetrahedra, corners with six equivalent Ga(2)Li4 tetrahedra, edges with six equivalent Li(1)Li3Ga4 tetrahedra, and faces with three equivalent Li(1)Li3Ga4 tetrahedra. In the second Li site, Li(2) is bonded to one Ga(1) and three equivalent Ga(2) atoms to form distorted LiGa4 tetrahedra that share corners with four equivalent Li(1)Li3Ga4 tetrahedra and corners with six equivalent Li(2)Ga4 tetrahedra. In the third Li site, Li(3) is bonded in a distorted linear geometry to six equivalent Li(1), two equivalent Ga(2), and six equivalent Ga(1) atoms. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 5-coordinate geometry to one Li(2), three equivalent Li(3), and four equivalent Li(1) atoms. In the second Ga site, Ga(2) is bonded to one Li(3) and three equivalent Li(2) atoms to form distorted GaLi4 tetrahedra that share corners with six equivalent Li(1)Li3Ga4 tetrahedra and corners with seven equivalent Ga(2)Li4 tetrahedra.
Li5Ga4 crystallizes in the trigonal P-3m1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent Li(3) and four equivalent Ga(1) atoms to form distorted LiLi3Ga4 tetrahedra that share corners with three equivalent Li(1)Li3Ga4 tetrahedra, corners with four equivalent Li(2)Ga4 tetrahedra, corners with six equivalent Ga(2)Li4 tetrahedra, edges with six equivalent Li(1)Li3Ga4 tetrahedra, and faces with three equivalent Li(1)Li3Ga4 tetrahedra. All Li(1)-Li(3) bond lengths are 2.67 Å. There are three shorter (2.63 Å) and one longer (2.80 Å) Li(1)-Ga(1) bond length. In the second Li site, Li(2) is bonded to one Ga(1) and three equivalent Ga(2) atoms to form distorted LiGa4 tetrahedra that share corners with four equivalent Li(1)Li3Ga4 tetrahedra and corners with six equivalent Li(2)Ga4 tetrahedra. The Li(2)-Ga(1) bond length is 2.72 Å. All Li(2)-Ga(2) bond lengths are 2.66 Å. In the third Li site, Li(3) is bonded in a distorted linear geometry to six equivalent Li(1), two equivalent Ga(2), and six equivalent Ga(1) atoms. Both Li(3)-Ga(2) bond lengths are 2.74 Å. All Li(3)-Ga(1) bond lengths are 3.09 Å. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 5-coordinate geometry to one Li(2), three equivalent Li(3), and four equivalent Li(1) atoms. In the second Ga site, Ga(2) is bonded to one Li(3) and three equivalent Li(2) atoms to form distorted GaLi4 tetrahedra that share corners with six equivalent Li(1)Li3Ga4 tetrahedra and corners with seven equivalent Ga(2)Li4 tetrahedra.