Experimental and theoretical study of thymine and cytosine derivatives: the crucial role of weak noncovalent interactions

In this paper we report the synthesis of N1-hexylthymine (1), N1-hexylcytosine (2), N1-hexylcytosine hydrobromide (3) and [(N1-hexylcytosinium)·(N1-hexylcytosine)]2·[Cl2Hg(μ-Cl)2HgCl2] (4) (the hemiprotonated form of the N1-hexylcytosine forming a CHC+ pair with carbonyl-amino symmetric and N3–N3 recognitions) and X-ray characterization of compounds 1, 3 and 4. In the solid state, N1-hexylthymine 1 follows exactly the same behaviour as N1-hexyluracil. In addition to strong hydrogen bonding interactions, various weak forces, i.e. C–H/π, carbonyl–carbonyl (CO⋯CO) and anion–π interactions (between the bromide and N1 of cytosine in 3), play a key role in stabilizing the 3D architectures of the compounds. The theoretical calculations allow estimation of the strength of these contacts and how they influence each other.

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