Cs2LiInCl6 is (Cubic) Perovskite-derived structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent Cl(1) and nine equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra, corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Li(1)Cl6 octahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Cs(2)Cl12 cuboctahedra,  a faceface with one In(1)Cl6 octahedra, faces with three equivalent Li(1)Cl6 octahedra, and faces with three equivalent In(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 14°. In the second Cs site, Cs(2) is bonded to three equivalent Cl(2) and nine equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, corners with three equivalent In(2)Cl6 octahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with four equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent In(1)Cl6 octahedra, and faces with four equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 16°. Li(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent In(1)Cl6 octahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Cs(2)Cl12 cuboctahedra, and  a faceface with one In(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent In sites. In the first In site, In(1) is bonded to six equivalent Cl(1) atoms to form InCl6 octahedra that share corners with six equivalent Li(1)Cl6 octahedra, faces with two equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Cs(2)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles are 3°. In the second In site, In(2) is bonded to six equivalent Cl(2) atoms to form InCl6 octahedra that share corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Li(1)Cl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted linear geometry to one Cs(1), three equivalent Cs(2), one Li(1), and one In(1) atom. In the second Cl site, Cl(2) is bonded to one Cs(2), three equivalent Cs(1), one Li(1), and one In(2) atom to form a mixture of distorted edge, corner, and face-sharing ClCs4LiIn octahedra. The corner-sharing octahedral tilt angles range from 0-60°.
Cs2LiInCl6 is (Cubic) Perovskite-derived structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent Cl(1) and nine equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra, corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Li(1)Cl6 octahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Cs(2)Cl12 cuboctahedra,  a faceface with one In(1)Cl6 octahedra, faces with three equivalent Li(1)Cl6 octahedra, and faces with three equivalent In(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 14°. All Cs(1)-Cl(1) bond lengths are 3.74 Å. There are six shorter (3.67 Å) and three longer (3.74 Å) Cs(1)-Cl(2) bond lengths. In the second Cs site, Cs(2) is bonded to three equivalent Cl(2) and nine equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, corners with three equivalent In(2)Cl6 octahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with four equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent In(1)Cl6 octahedra, and faces with four equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 16°. All Cs(2)-Cl(2) bond lengths are 3.70 Å. There are six shorter (3.67 Å) and three longer (3.73 Å) Cs(2)-Cl(1) bond lengths. Li(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent In(1)Cl6 octahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Cs(2)Cl12 cuboctahedra, and  a faceface with one In(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 3°. All Li(1)-Cl(1) bond lengths are 2.57 Å. All Li(1)-Cl(2) bond lengths are 2.62 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to six equivalent Cl(1) atoms to form InCl6 octahedra that share corners with six equivalent Li(1)Cl6 octahedra, faces with two equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Cs(2)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles are 3°. All In(1)-Cl(1) bond lengths are 2.53 Å. In the second In site, In(2) is bonded to six equivalent Cl(2) atoms to form InCl6 octahedra that share corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Li(1)Cl6 octahedra. All In(2)-Cl(2) bond lengths are 2.53 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted linear geometry to one Cs(1), three equivalent Cs(2), one Li(1), and one In(1) atom. In the second Cl site, Cl(2) is bonded to one Cs(2), three equivalent Cs(1), one Li(1), and one In(2) atom to form a mixture of distorted edge, corner, and face-sharing ClCs4LiIn octahedra. The corner-sharing octahedral tilt angles range from 0-60°.