Amino alcohols are important ligands for the asymmetric catalytic hydroamination of aminoallenes to form chiral pyrrolidines. Herein, we report the crystal structures of two chiral amino alcohols, D-N-(2-Adamantyl)phenylglycinol and L-N-(2-Adamantyl)diphenylphenylalinol, that function as ligands within transition metal complexes that catalyze the hydroamination of aminoallenes. Both molecules crystallize in the noncentrosymmetric orthorhombic space group P2(1)2(1)2(1). Inter-and intramolecular hydrogen bonding plays an important role in stabilizing each alcohol in the solid state in the absence of a transition metal. The presence of these hydrogen bonds has been verified by single crystal X-ray diffraction and their overall strength determined by computational methods.