LiIn(CN2)2 crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form LiN6 octahedra that share edges with two equivalent Li(1)N6 octahedra and edges with four equivalent In(1)N6 octahedra. In(1) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form InN6 octahedra that share edges with two equivalent In(1)N6 octahedra and edges with four equivalent Li(1)N6 octahedra. C(1) is bonded in a linear geometry to one N(1) and one N(2) atom. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Li(1), one In(1), and one C(1) atom to form distorted NLi2InC tetrahedra that share corners with three equivalent N(1)Li2InC tetrahedra, corners with seven equivalent N(2)LiIn2C trigonal pyramids, edges with two equivalent N(1)Li2InC tetrahedra, and  an edgeedge with one N(2)LiIn2C trigonal pyramid. In the second N site, N(2) is bonded to one Li(1), two equivalent In(1), and one C(1) atom to form distorted NLiIn2C trigonal pyramids that share corners with seven equivalent N(1)Li2InC tetrahedra, corners with three equivalent N(2)LiIn2C trigonal pyramids,  an edgeedge with one N(1)Li2InC tetrahedra, and edges with two equivalent N(2)LiIn2C trigonal pyramids.
LiIn(CN2)2 crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form LiN6 octahedra that share edges with two equivalent Li(1)N6 octahedra and edges with four equivalent In(1)N6 octahedra. Both Li(1)-N(2) bond lengths are 2.56 Å. There are two shorter (2.25 Å) and two longer (2.33 Å) Li(1)-N(1) bond lengths. In(1) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form InN6 octahedra that share edges with two equivalent In(1)N6 octahedra and edges with four equivalent Li(1)N6 octahedra. Both In(1)-N(1) bond lengths are 2.24 Å. There are two shorter (2.26 Å) and two longer (2.28 Å) In(1)-N(2) bond lengths. C(1) is bonded in a linear geometry to one N(1) and one N(2) atom. The C(1)-N(1) bond length is 1.22 Å. The C(1)-N(2) bond length is 1.25 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Li(1), one In(1), and one C(1) atom to form distorted NLi2InC tetrahedra that share corners with three equivalent N(1)Li2InC tetrahedra, corners with seven equivalent N(2)LiIn2C trigonal pyramids, edges with two equivalent N(1)Li2InC tetrahedra, and  an edgeedge with one N(2)LiIn2C trigonal pyramid. In the second N site, N(2) is bonded to one Li(1), two equivalent In(1), and one C(1) atom to form distorted NLiIn2C trigonal pyramids that share corners with seven equivalent N(1)Li2InC tetrahedra, corners with three equivalent N(2)LiIn2C trigonal pyramids,  an edgeedge with one N(1)Li2InC tetrahedra, and edges with two equivalent N(2)LiIn2C trigonal pyramids.