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Ba(AlTe2)2 crystallizes in the tetragonal I422 space group. The structure is three-dimensional. Ba2+ is bonded in a 8-coordinate geometry to eight equivalent Te2- atoms. All Ba–Te bond lengths are 3.65 Å. Al3+ is bonded to four equivalent Te2- atoms to form edge-sharing AlTe4 tetrahedra. All Al–Te bond lengths are 2.66 Å. Te2- is bonded in a 4-coordinate geometry to two equivalent Ba2+ and two equivalent Al3+ atoms.
Ba(AlTe2)2 crystallizes in the tetragonal P4/nbm space group. The structure is three-dimensional. Ba2+ is bonded in a 8-coordinate geometry to eight equivalent Te2- atoms. All Ba–Te bond lengths are 3.66 Å. There are two inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to four equivalent Te2- atoms to form edge-sharing AlTe4 tetrahedra. All Al–Te bond lengths are 2.66 Å. In the second Al3+ site, Al3+ is bonded to four equivalent Te2- atoms to form edge-sharing AlTe4 tetrahedra. All Al–Te bond lengths are 2.66 Å. Te2- is bonded to two equivalent Ba2+ and two Al3+ atoms to form a mixture of distorted corner and edge-sharing TeBa2Al2 trigonal pyramids.