Compound 1 was obtained in good yield following a copper-catalysed Ullman coupling between the previously reported dimethyl 2,5-bis((4-(tert-butyl)phenyl)amino)terephthalate and methyl 2-iodobenzoate. Quantitative saponification yielded the key intermediate 2, which then underwent a four-fold intramolecular Friedel-Crafts acylation of the in situ-prepared acyl chloride derivative in the presence of the Lewis acid AlCl3 to afford a mixture of two isomers, Sym-DiDiKTa and Asym-DiDiKTa, in 36% and 5% yield, respectively, after isolation by column chromatography. The compounds were further purified by gradient-temperature vacuum sublimation and their structure and purity were confirmed by a combination of NMR spectroscopy, high-resolution mass spectrometry, melting point determination and HPLC and elemental analyses. packing. In the case of Sym-DiDiKTa, adjacent molecules are partially superimposed, forming π-stacked chain along the c-axis with the molecules stacked in a slipped manner (Figure and). In contrast, for Asym-DiDiKTa, adjacent molecules display a greater degree of overlap and more π-stacking (Figure ), resulting in symmetric pairs of adjacent molecules with the tert-butyl groups pointing in the opposite direction (Figure ). Additional π-stacking interactions link these to form π-stacked chains along the a-axis. The distance between the central ring (e) between two nearest molecules is 9.1422(9) Å for Sym-DiDiKTa, whereas for Asym-DiDiKTa it is only 3.4699(17) Å. We also obtained single crystals of Sym-DiDiKTa from slow evaporation of a CH2Cl2:MeOH solution (8:2 ratio). Under these conditions, the crystal structure is comprised π-stacked columns of molecules along the crystallographic aaxis (Figures and), with greater superimposition than in the previous case (distance between the central rings (e) of 3.8500(2) Å). This is achieved with the aid of MeOH molecules forming both strong and weak hydrogen bonds between and within the columns.