LiInI4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one I(1), one I(4), two equivalent I(2), and two equivalent I(3) atoms to form LiI6 octahedra that share corners with two equivalent Li(1)I6 octahedra, corners with two equivalent In(1)I4 tetrahedra,  an edgeedge with one Li(1)I6 octahedra, and edges with two equivalent In(1)I4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. In(1) is bonded to one I(1), one I(2), one I(3), and one I(4) atom to form InI4 tetrahedra that share corners with two equivalent Li(1)I6 octahedra and edges with two equivalent Li(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 61-64°. There are four inequivalent I sites. In the first I site, I(1) is bonded in an L-shaped geometry to one Li(1) and one In(1) atom. In the second I site, I(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one In(1) atom. In the third I site, I(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one In(1) atom. In the fourth I site, I(4) is bonded in a bent 120 degrees geometry to one Li(1) and one In(1) atom.
LiInI4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one I(1), one I(4), two equivalent I(2), and two equivalent I(3) atoms to form LiI6 octahedra that share corners with two equivalent Li(1)I6 octahedra, corners with two equivalent In(1)I4 tetrahedra,  an edgeedge with one Li(1)I6 octahedra, and edges with two equivalent In(1)I4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. The Li(1)-I(1) bond length is 2.90 Å. The Li(1)-I(4) bond length is 2.98 Å. There is one shorter (3.09 Å) and one longer (3.11 Å) Li(1)-I(2) bond length. There is one shorter (3.16 Å) and one longer (3.19 Å) Li(1)-I(3) bond length. In(1) is bonded to one I(1), one I(2), one I(3), and one I(4) atom to form InI4 tetrahedra that share corners with two equivalent Li(1)I6 octahedra and edges with two equivalent Li(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 61-64°. The In(1)-I(1) bond length is 2.73 Å. The In(1)-I(2) bond length is 2.77 Å. The In(1)-I(3) bond length is 2.76 Å. The In(1)-I(4) bond length is 2.72 Å. There are four inequivalent I sites. In the first I site, I(1) is bonded in an L-shaped geometry to one Li(1) and one In(1) atom. In the second I site, I(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one In(1) atom. In the third I site, I(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one In(1) atom. In the fourth I site, I(4) is bonded in a bent 120 degrees geometry to one Li(1) and one In(1) atom.