Polynuclear clusters and noncovalent interactions play an important role in determining the structure, properties, and reactivity of organic and organometallic species. In this report crystallization of newly prepared copper(II) tetranuclear clusters [Cu4X6O(NCNMe2)4] (X = Cl 1, Br 2) and their adducts from toluene and styrene solutions afforded crystalline substances: 1·4PhMe, 1·4PhCH=CH2, 2·4PhMe, and 2·4PhCH=CH2, which were characterized by physicochemical methods including XRD, IR and AAS. Inspection of the X-ray structures of (1−2)·4(arene) and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unreported π-hole···arene interactions involving the cyanamide ligands.