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Computational methods were used to calculate the crystal lattice energy reflecting global interactions, predominantly long-range electrostatic interactions between ions, as well as the energy of selected specific local C–H···O, C–H···π and π···π interactions found in synthesized 7-(diethylamino)-2-(2-oxo-2H-chromen-3-yl)chromenium perchlorate, the structure of which was determined by X-ray crystallography. Local interactions occurring between specific sites of molecules, amounting to a few tens of kJ mol−1, most likely account for the mutual arrangement of molecular ions, whereas global ones, exceeding half-a-thousand kJ mol−1, are responsible for the thermodynamic stability of the compound investigated in the crystalline solid phase, whose potential applications are briefly outlined.

Global and local interactions in the structure of crystalline 7-(diethylamino)-2-(2-oxo-2H-chromen-3-yl)chromenium perchlorate