Li3LaGa8 crystallizes in the orthorhombic Pmmm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Ga(2), two equivalent Ga(4), four equivalent Ga(1), and four equivalent Ga(3) atoms to form distorted LiGa12 cuboctahedra that share edges with four equivalent Li(1)Ga12 cuboctahedra, edges with four equivalent Li(2)Ga12 cuboctahedra, edges with four equivalent La(1)Ga12 cuboctahedra, faces with two equivalent Li(2)Ga12 cuboctahedra, faces with two equivalent La(1)Ga12 cuboctahedra, and faces with four equivalent Li(1)Ga12 cuboctahedra. In the second Li site, Li(2) is bonded to four equivalent Ga(3) and eight equivalent Ga(2) atoms to form a mixture of face and edge-sharing LiGa12 cuboctahedra. La(1) is bonded to four equivalent Ga(1) and eight equivalent Ga(4) atoms to form LaGa12 cuboctahedra that share edges with four equivalent La(1)Ga12 cuboctahedra, edges with eight equivalent Li(1)Ga12 cuboctahedra, faces with four equivalent Li(1)Ga12 cuboctahedra, and faces with four equivalent La(1)Ga12 cuboctahedra. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 9-coordinate geometry to four equivalent Li(1), two equivalent La(1), one Ga(3), and two equivalent Ga(4) atoms. In the second Ga site, Ga(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), four equivalent Li(2), one Ga(2), and two equivalent Ga(3) atoms. In the third Ga site, Ga(3) is bonded in a 9-coordinate geometry to two equivalent Li(2), four equivalent Li(1), one Ga(1), and two equivalent Ga(2) atoms. In the fourth Ga site, Ga(4) is bonded in a 9-coordinate geometry to two equivalent Li(1), four equivalent La(1), one Ga(4), and two equivalent Ga(1) atoms.
Li3LaGa8 crystallizes in the orthorhombic Pmmm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Ga(2), two equivalent Ga(4), four equivalent Ga(1), and four equivalent Ga(3) atoms to form distorted LiGa12 cuboctahedra that share edges with four equivalent Li(1)Ga12 cuboctahedra, edges with four equivalent Li(2)Ga12 cuboctahedra, edges with four equivalent La(1)Ga12 cuboctahedra, faces with two equivalent Li(2)Ga12 cuboctahedra, faces with two equivalent La(1)Ga12 cuboctahedra, and faces with four equivalent Li(1)Ga12 cuboctahedra. Both Li(1)-Ga(2) bond lengths are 3.22 Å. Both Li(1)-Ga(4) bond lengths are 2.95 Å. All Li(1)-Ga(1) bond lengths are 3.04 Å. All Li(1)-Ga(3) bond lengths are 3.22 Å. In the second Li site, Li(2) is bonded to four equivalent Ga(3) and eight equivalent Ga(2) atoms to form a mixture of face and edge-sharing LiGa12 cuboctahedra. All Li(2)-Ga(3) bond lengths are 3.03 Å. All Li(2)-Ga(2) bond lengths are 3.12 Å. La(1) is bonded to four equivalent Ga(1) and eight equivalent Ga(4) atoms to form LaGa12 cuboctahedra that share edges with four equivalent La(1)Ga12 cuboctahedra, edges with eight equivalent Li(1)Ga12 cuboctahedra, faces with four equivalent Li(1)Ga12 cuboctahedra, and faces with four equivalent La(1)Ga12 cuboctahedra. All La(1)-Ga(1) bond lengths are 3.23 Å. All La(1)-Ga(4) bond lengths are 3.17 Å. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 9-coordinate geometry to four equivalent Li(1), two equivalent La(1), one Ga(3), and two equivalent Ga(4) atoms. The Ga(1)-Ga(3) bond length is 2.47 Å. Both Ga(1)-Ga(4) bond lengths are 2.59 Å. In the second Ga site, Ga(2) is bonded in a 9-coordinate geometry to two equivalent Li(1), four equivalent Li(2), one Ga(2), and two equivalent Ga(3) atoms. The Ga(2)-Ga(2) bond length is 2.46 Å. Both Ga(2)-Ga(3) bond lengths are 2.53 Å. In the third Ga site, Ga(3) is bonded in a 9-coordinate geometry to two equivalent Li(2), four equivalent Li(1), one Ga(1), and two equivalent Ga(2) atoms. In the fourth Ga site, Ga(4) is bonded in a 9-coordinate geometry to two equivalent Li(1), four equivalent La(1), one Ga(4), and two equivalent Ga(1) atoms. The Ga(4)-Ga(4) bond length is 2.70 Å.