Abstract
Multiple techniques have been used to delineate the self‐assembly of a bis(pyrrole) Schiff base derivative (compound 4, C~16~H~14~N~4~), which forms an unusual dimer through complementary NH⋅⋅⋅NC hydrogen bonds between twisted, C~2~‐symmetric monomer units. The asymmetric unit of the crystal structure comprises one and a half dimer units, with one dimer exhibiting approximate D~2~ point‐group symmetry and the other exact D~2~ symmetry (space group C__2/c). The dimers pack into columns whose axes are collinear with the a axis of the unit cell. The columns assemble into discrete layers with two distinct types of hydrogen‐sized voids residing between the layers. Despite the promising architecture of the voids within the lattice of 4, the absence of genuine channels to interconnect the voids precludes the uptake of hydrogen gas, even at elevated pressures (10 bar). AM1 calculations of the structure of dimeric 4 indicate that self‐recognition through hydrogen bonding depends primarily on favorable electrostatic interactions. The potential‐energy surface for monomeric 4 mapped by counter‐rotation of an adjacent pair of CC‐NC torsion angles indicates that the X‐ray structures of the four monomeric units are global minima with highly nonplanar conformations that are preorganized for self‐recognition by hydrogen bonding. The in vacuo enthalpy of association for the dimer was calculated to be significantly exergonic (Δ__G~asso__c__~=−21.9 kJ mol^−1^, 298 K) and in excellent agreement with that determined by ^1^H NMR spectroscopy in CDCl~3~ (Δ__G__~assoc~=−16.6(4) kJ mol^−1^, 298 K). Using population and bond order analyses, in conjunction with the conformation dependence of the frontier MO energies, we have been able to show that π‐electron delocalization is only marginally diminished in the nonplanar conformers of 4 and that the electronic structures of the constituent monomers of the dimer are well mixed.