Eight cyclopropane derivatives (Δ − R) have been modeled, with R = −H, −CH3, −NH2, −C ≡ CH, −C ≡ CCH3, −OH, −F and −C ≡ N. All geometries have been fully optimized at the MP2/ AUG-cc-pVTZ level of calculations. Natural bond orbital analyses reveal extra p character (spλ, λ > 3) in the C-C bonds of the cyclopropyl rings. The banana-like σ CC bonds in the rings are described in detail. Alkene-like complexes between Δ − R molecules and hydrogen fluoride are identified. These weakly bonded complexes are formed through unconventional hydrogen bond interactions between the hydrogen atom in the HF molecule and the carbon–carbon bonds in the cyclopropane ring. A topological analysis of the electronic charge density and its Laplacian has been used to characterize the interactions. The possible relevance of such complexes in the modeling of substrate–receptor interactions in some anti-AIDS drugs is discussed.