LiGaH4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent H(2) and four equivalent H(1) atoms to form LiH6 pentagonal pyramids that share corners with four equivalent Ga(1)H4 tetrahedra, edges with two equivalent Li(1)H6 pentagonal pyramids, and  an edgeedge with one Ga(1)H4 tetrahedra. Ga(1) is bonded to two equivalent H(1) and two equivalent H(2) atoms to form GaH4 tetrahedra that share corners with four equivalent Li(1)H6 pentagonal pyramids and  an edgeedge with one Li(1)H6 pentagonal pyramid. There are two inequivalent H sites. In the first H site, H(1) is bonded in a T-shaped geometry to two equivalent Li(1) and one Ga(1) atom. In the second H site, H(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Ga(1) atom.
LiGaH4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent H(2) and four equivalent H(1) atoms to form LiH6 pentagonal pyramids that share corners with four equivalent Ga(1)H4 tetrahedra, edges with two equivalent Li(1)H6 pentagonal pyramids, and  an edgeedge with one Ga(1)H4 tetrahedra. Both Li(1)-H(2) bond lengths are 1.93 Å. There are two shorter (1.94 Å) and two longer (2.12 Å) Li(1)-H(1) bond lengths. Ga(1) is bonded to two equivalent H(1) and two equivalent H(2) atoms to form GaH4 tetrahedra that share corners with four equivalent Li(1)H6 pentagonal pyramids and  an edgeedge with one Li(1)H6 pentagonal pyramid. Both Ga(1)-H(1) bond lengths are 1.60 Å. Both Ga(1)-H(2) bond lengths are 1.57 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a T-shaped geometry to two equivalent Li(1) and one Ga(1) atom. In the second H site, H(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Ga(1) atom.