Ni3Al2 crystallizes in the tetragonal P4/mmm space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to four equivalent Ni(4) and four equivalent Al(1) atoms. In the second Ni site, Ni(2) is bonded in a body-centered cubic geometry to four equivalent Al(1) and four equivalent Al(2) atoms. In the third Ni site, Ni(3) is bonded in a body-centered cubic geometry to eight equivalent Al(2) atoms. In the fourth Ni site, Ni(4) is bonded in a 10-coordinate geometry to eight equivalent Ni(1) and two equivalent Al(1) atoms. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded in a 9-coordinate geometry to one Ni(4), four equivalent Ni(1), and four equivalent Ni(2) atoms. In the second Al site, Al(2) is bonded in a body-centered cubic geometry to four equivalent Ni(2) and four equivalent Ni(3) atoms.
Ni3Al2 crystallizes in the tetragonal P4/mmm space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to four equivalent Ni(4) and four equivalent Al(1) atoms. All Ni(1)-Ni(4) bond lengths are 2.43 Å. All Ni(1)-Al(1) bond lengths are 2.42 Å. In the second Ni site, Ni(2) is bonded in a body-centered cubic geometry to four equivalent Al(1) and four equivalent Al(2) atoms. All Ni(2)-Al(1) bond lengths are 2.49 Å. All Ni(2)-Al(2) bond lengths are 2.48 Å. In the third Ni site, Ni(3) is bonded in a body-centered cubic geometry to eight equivalent Al(2) atoms. All Ni(3)-Al(2) bond lengths are 2.48 Å. In the fourth Ni site, Ni(4) is bonded in a 10-coordinate geometry to eight equivalent Ni(1) and two equivalent Al(1) atoms. Both Ni(4)-Al(1) bond lengths are 2.66 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded in a 9-coordinate geometry to one Ni(4), four equivalent Ni(1), and four equivalent Ni(2) atoms. In the second Al site, Al(2) is bonded in a body-centered cubic geometry to four equivalent Ni(2) and four equivalent Ni(3) atoms.