Unidirectional Molecular Stacking of Tribenzotriquinacenes in the Solid State: A Combined X‐ray and Theoretical Study

A combined X‐ray diffraction and theoretical study of the solid‐state molecular and crystal structures of tribenzotriquinacene (TBTQ, 2 ) and its centro‐methyl derivative ( 3 ) is presented. The molecular structure of the parent hydrocarbon displays C_3v symmetry and the three indane wings adopt mutually orthogonal orientations, similar to the case in its previously reported methyl derivative ( 3 ). Also similarly to the latter structure, the bowl‐shaped molecules of compound 2 form infinite molecular stacks with perfectly axial, face‐to‐back (convex–concave) packing and with parallel and unidirectional orientation of the stacks. The experimentally determined intra‐stack molecular distance is 4.75 Å for compound 2 and 5.95 Å for compound 3 . Whereas the molecules of compound 2 show a slight alternating rotation (±6°) about the common axis of each stack, those of compound 3 show perfect translational symmetry within the stacks. We used dispersion‐corrected density functional theory to compute the crystal structures of tribenzotriquinacenes 2 and 3 . The London dispersion correction was crucial for obtaining an accurate description of the crystallization of both analyzed systems and the calculated results agreed excellently with the experimental measurements. We also obtained reasonable sublimation energies for both compounds. In addition, the geometries and dimerization energies of oligomeric stacks of compound 2 were computed and showed smooth convergence to the properties of the infinite polymeric stack.