It has been shown that diamondoids can interact with DNA by forming relatively strong hydrogen bonds to DNA units, such as nucleobases. For this interaction to occur the diamondoids must be chemically modified in order to provide donor/acceptor groups for the hydrogen bond. We show here that the exact arrangement of an amine-modified adamantane with respect to a neighboring nucleobase has a significant influence on the strength of the hydrogen bond. Whether the diamondoid acts as a hydrogen donor or acceptor in the hydrogen binding to the nucleobase affects the electronic structure and thereby the electronic band-gaps of the diamondoid-nucleobase complex. In a donor arrangement of the diamondoid close to a nucleobase, the interaction energies are weak, but the electronic band-gaps differ significantly. Exactly the opposite trend is observed in an acceptor arrangement of the diamondoid. In each of these cases the frontier orbitals of the diamondoid and the nucleobase play a different role in the binding. The results are discussed in view of a diamondoid-based biosensing device.