LiGaI3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms to form LiI6 octahedra that share corners with two equivalent Li(1)I6 octahedra, corners with four equivalent Li(2)I6 octahedra, corners with two equivalent Ga(1)GaI3 tetrahedra, and edges with two equivalent Ga(2)GaI3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-46°. In the second Li site, Li(2) is bonded to two equivalent I(1), two equivalent I(2), and two equivalent I(3) atoms to form LiI6 octahedra that share corners with two equivalent Li(2)I6 octahedra, corners with four equivalent Li(1)I6 octahedra, corners with two equivalent Ga(2)GaI3 tetrahedra, and corners with four equivalent Ga(1)GaI3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-50°. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one Ga(2), one I(1), and two equivalent I(3) atoms to form distorted GaGaI3 tetrahedra that share corners with two equivalent Li(1)I6 octahedra and corners with four equivalent Li(2)I6 octahedra. The corner-sharing octahedral tilt angles range from 62-76°. In the second Ga site, Ga(2) is bonded to one Ga(1), one I(4), and two equivalent I(2) atoms to form distorted GaGaI3 tetrahedra that share corners with two equivalent Li(2)I6 octahedra and edges with two equivalent Li(1)I6 octahedra. The corner-sharing octahedral tilt angles are 79°. There are four inequivalent I sites. In the first I site, I(1) is bonded in a trigonal non-coplanar geometry to two equivalent Li(2) and one Ga(1) atom. In the second I site, I(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Ga(2) atom. In the third I site, I(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Ga(1) atom. In the fourth I site, I(4) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Ga(2) atom.
LiGaI3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms to form LiI6 octahedra that share corners with two equivalent Li(1)I6 octahedra, corners with four equivalent Li(2)I6 octahedra, corners with two equivalent Ga(1)GaI3 tetrahedra, and edges with two equivalent Ga(2)GaI3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-46°. Both Li(1)-I(2) bond lengths are 2.94 Å. Both Li(1)-I(3) bond lengths are 3.10 Å. Both Li(1)-I(4) bond lengths are 3.07 Å. In the second Li site, Li(2) is bonded to two equivalent I(1), two equivalent I(2), and two equivalent I(3) atoms to form LiI6 octahedra that share corners with two equivalent Li(2)I6 octahedra, corners with four equivalent Li(1)I6 octahedra, corners with two equivalent Ga(2)GaI3 tetrahedra, and corners with four equivalent Ga(1)GaI3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-50°. Both Li(2)-I(1) bond lengths are 3.17 Å. Both Li(2)-I(2) bond lengths are 3.01 Å. Both Li(2)-I(3) bond lengths are 2.97 Å. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one Ga(2), one I(1), and two equivalent I(3) atoms to form distorted GaGaI3 tetrahedra that share corners with two equivalent Li(1)I6 octahedra and corners with four equivalent Li(2)I6 octahedra. The corner-sharing octahedral tilt angles range from 62-76°. The Ga(1)-Ga(2) bond length is 2.43 Å. The Ga(1)-I(1) bond length is 2.61 Å. Both Ga(1)-I(3) bond lengths are 2.64 Å. In the second Ga site, Ga(2) is bonded to one Ga(1), one I(4), and two equivalent I(2) atoms to form distorted GaGaI3 tetrahedra that share corners with two equivalent Li(2)I6 octahedra and edges with two equivalent Li(1)I6 octahedra. The corner-sharing octahedral tilt angles are 79°. The Ga(2)-I(4) bond length is 2.61 Å. Both Ga(2)-I(2) bond lengths are 2.62 Å. There are four inequivalent I sites. In the first I site, I(1) is bonded in a trigonal non-coplanar geometry to two equivalent Li(2) and one Ga(1) atom. In the second I site, I(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Ga(2) atom. In the third I site, I(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Ga(1) atom. In the fourth I site, I(4) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Ga(2) atom.