Na5Al3H14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent H(1) atoms. In the second Na site, Na(2) is bonded to two equivalent H(2) and four equivalent H(1) atoms to form distorted NaH6 octahedra that share corners with two equivalent Na(2)H6 octahedra, corners with two equivalent Al(1)H6 octahedra, corners with four equivalent Al(2)H6 octahedra, and edges with four equivalent Na(2)H6 octahedra. The corner-sharing octahedral tilt angles range from 38-71°. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent H(2) and four equivalent H(3) atoms to form AlH6 octahedra that share corners with four equivalent Al(2)H6 octahedra and corners with eight equivalent Na(2)H6 octahedra. The corner-sharing octahedral tilt angles range from 33-71°. In the second Al site, Al(2) is bonded to two equivalent H(3) and four equivalent H(1) atoms to form AlH6 octahedra that share corners with two equivalent Al(1)H6 octahedra and corners with eight equivalent Na(2)H6 octahedra. The corner-sharing octahedral tilt angles range from 33-69°. There are three inequivalent H sites. In the first H site, H(2) is bonded in a 5-coordinate geometry to four equivalent Na(2) and one Al(1) atom. In the second H site, H(3) is bonded in a bent 150 degrees geometry to one Al(1) and one Al(2) atom. In the third H site, H(1) is bonded to one Na(1), two equivalent Na(2), and one Al(2) atom to form a mixture of distorted edge and corner-sharing HNa3Al trigonal pyramids.
Na5Al3H14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent H(1) atoms. All Na(1)-H(1) bond lengths are 2.47 Å. In the second Na site, Na(2) is bonded to two equivalent H(2) and four equivalent H(1) atoms to form distorted NaH6 octahedra that share corners with two equivalent Na(2)H6 octahedra, corners with two equivalent Al(1)H6 octahedra, corners with four equivalent Al(2)H6 octahedra, and edges with four equivalent Na(2)H6 octahedra. The corner-sharing octahedral tilt angles range from 38-71°. Both Na(2)-H(2) bond lengths are 2.52 Å. There are two shorter (2.19 Å) and two longer (2.23 Å) Na(2)-H(1) bond lengths. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent H(2) and four equivalent H(3) atoms to form AlH6 octahedra that share corners with four equivalent Al(2)H6 octahedra and corners with eight equivalent Na(2)H6 octahedra. The corner-sharing octahedral tilt angles range from 33-71°. Both Al(1)-H(2) bond lengths are 1.74 Å. All Al(1)-H(3) bond lengths are 1.73 Å. In the second Al site, Al(2) is bonded to two equivalent H(3) and four equivalent H(1) atoms to form AlH6 octahedra that share corners with two equivalent Al(1)H6 octahedra and corners with eight equivalent Na(2)H6 octahedra. The corner-sharing octahedral tilt angles range from 33-69°. Both Al(2)-H(3) bond lengths are 1.76 Å. All Al(2)-H(1) bond lengths are 1.72 Å. There are three inequivalent H sites. In the first H site, H(2) is bonded in a 5-coordinate geometry to four equivalent Na(2) and one Al(1) atom. In the second H site, H(3) is bonded in a bent 150 degrees geometry to one Al(1) and one Al(2) atom. In the third H site, H(1) is bonded to one Na(1), two equivalent Na(2), and one Al(2) atom to form a mixture of distorted edge and corner-sharing HNa3Al trigonal pyramids.