Li5GeAs3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one Ge(1), one As(2), and three equivalent As(1) atoms to form distorted LiGeAs4 tetrahedra that share  a cornercorner with one Li(2)Ge2As4 tetrahedra, corners with six equivalent Li(1)GeAs4 tetrahedra,  an edgeedge with one Li(1)GeAs4 tetrahedra, and edges with three equivalent Li(2)Ge2As4 tetrahedra. In the second Li site, Li(2) is bonded to two equivalent Ge(1), two equivalent As(1), and two equivalent As(2) atoms to form distorted LiGe2As4 tetrahedra that share corners with two equivalent Li(1)GeAs4 tetrahedra, corners with four equivalent Li(2)Ge2As4 tetrahedra, and edges with six equivalent Li(1)GeAs4 tetrahedra. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one Ge(1), one As(2), and three equivalent As(1) atoms. Ge(1) is bonded in a 10-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), two equivalent As(1), and two equivalent As(2) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded in a body-centered cubic geometry to one Li(2), three equivalent Li(1), three equivalent Li(3), and one Ge(1) atom. In the second As site, As(2) is bonded in a body-centered cubic geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and two equivalent Ge(1) atoms.
Li5GeAs3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one Ge(1), one As(2), and three equivalent As(1) atoms to form distorted LiGeAs4 tetrahedra that share  a cornercorner with one Li(2)Ge2As4 tetrahedra, corners with six equivalent Li(1)GeAs4 tetrahedra,  an edgeedge with one Li(1)GeAs4 tetrahedra, and edges with three equivalent Li(2)Ge2As4 tetrahedra. The Li(1)-Ge(1) bond length is 3.05 Å. The Li(1)-As(2) bond length is 2.62 Å. There are a spread of Li(1)-As(1) bond distances ranging from 2.62-2.66 Å. In the second Li site, Li(2) is bonded to two equivalent Ge(1), two equivalent As(1), and two equivalent As(2) atoms to form distorted LiGe2As4 tetrahedra that share corners with two equivalent Li(1)GeAs4 tetrahedra, corners with four equivalent Li(2)Ge2As4 tetrahedra, and edges with six equivalent Li(1)GeAs4 tetrahedra. There is one shorter (2.96 Å) and one longer (3.11 Å) Li(2)-Ge(1) bond length. Both Li(2)-As(1) bond lengths are 2.62 Å. Both Li(2)-As(2) bond lengths are 2.64 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one Ge(1), one As(2), and three equivalent As(1) atoms. The Li(3)-Ge(1) bond length is 3.03 Å. The Li(3)-As(2) bond length is 2.60 Å. There are a spread of Li(3)-As(1) bond distances ranging from 2.59-2.76 Å. Ge(1) is bonded in a 10-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), two equivalent As(1), and two equivalent As(2) atoms. Both Ge(1)-As(1) bond lengths are 2.45 Å. Both Ge(1)-As(2) bond lengths are 2.70 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded in a body-centered cubic geometry to one Li(2), three equivalent Li(1), three equivalent Li(3), and one Ge(1) atom. In the second As site, As(2) is bonded in a body-centered cubic geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and two equivalent Ge(1) atoms.