Na2LiAlH6 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent H(3), three equivalent H(1), and three equivalent H(2) atoms. Li(1) is bonded to two equivalent H(1), two equivalent H(2), and two equivalent H(3) atoms to form LiH6 octahedra that share corners with six equivalent Al(1)H6 octahedra. The corner-sharing octahedral tilt angles range from 20-21°. Al(1) is bonded to two equivalent H(1), two equivalent H(2), and two equivalent H(3) atoms to form AlH6 octahedra that share corners with six equivalent Li(1)H6 octahedra. The corner-sharing octahedral tilt angles range from 20-21°. There are three inequivalent H sites. In the first H site, H(1) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Li(1), and one Al(1) atom. In the second H site, H(2) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Li(1), and one Al(1) atom. In the third H site, H(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), and one Al(1) atom.
Na2LiAlH6 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent H(3), three equivalent H(1), and three equivalent H(2) atoms. There is one shorter (2.29 Å) and one longer (2.42 Å) Na(1)-H(3) bond length. There are a spread of Na(1)-H(1) bond distances ranging from 2.29-2.54 Å. There are a spread of Na(1)-H(2) bond distances ranging from 2.30-2.55 Å. Li(1) is bonded to two equivalent H(1), two equivalent H(2), and two equivalent H(3) atoms to form LiH6 octahedra that share corners with six equivalent Al(1)H6 octahedra. The corner-sharing octahedral tilt angles range from 20-21°. Both Li(1)-H(1) bond lengths are 1.95 Å. Both Li(1)-H(2) bond lengths are 1.95 Å. Both Li(1)-H(3) bond lengths are 1.95 Å. Al(1) is bonded to two equivalent H(1), two equivalent H(2), and two equivalent H(3) atoms to form AlH6 octahedra that share corners with six equivalent Li(1)H6 octahedra. The corner-sharing octahedral tilt angles range from 20-21°. Both Al(1)-H(1) bond lengths are 1.74 Å. Both Al(1)-H(2) bond lengths are 1.74 Å. Both Al(1)-H(3) bond lengths are 1.74 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Li(1), and one Al(1) atom. In the second H site, H(2) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Li(1), and one Al(1) atom. In the third H site, H(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), and one Al(1) atom.