Solid-state stability of Z′ < 1 and Z′ = 2 polymorphs of N,N,N′,N′-tetrabenzylethylenediamine: a combined experimental and theoretical study

Abstract

The synthesis and structural analysis by means of single crystal X-ray diffraction (SC-XRD) and DFT calculations, of two additional new polymorphs of the flexible organic molecule N,N,N′,N′-tetrabenzylethylenediamine (L) which is used as first sphere ligand in outer sphere adducts are reported. Slow crystallization of L in the solution-state yields two polymorphs (L_α-phase and L_β-phase) with Z′ = 0.5, while fast crystallization by rapid cooling from solution and directly from melt, allows a third, less stable polymorph with Z′ = 2 (L_γ-phase). The latter structure can be seen as a low-density metastable phase obtained by trapping L molecules after they reached high mobility by thermal treatment (i.e., high energy state). The three L polymorphs have been also studied using quantum mechanical (QM) calculations specific for the solid state by comparing the sublimation energy for each polymorph, and by comparing the experimental X-ray structures against the optimized structures from DFT, showing that L_β-phase is the most stable and L_γ-phase is the least stable phase. The high Z′ structure can be considered as a “crystal on the way” of a more stable form. These results provide insights about crystallization mechanisms and polymorphism in organic crystals. The potential use of conformational polymorphs of flexible ligands to prepare second sphere adducts with marked polymorphism is commented.