DNA can adopt noncanonical structures that have important biological functions while also providing structural diversity for applications in nanotechnology. Here, the crystal structures of two oligonucleotides composed of d(CGA) triplet repeats in the parallel‐stranded duplex form are described. The structure determination of four unique d(CGA)‐based parallel‐stranded duplexes across two crystal structures has allowed the structural parameters of d(CGA) triplets in the parallel‐stranded duplex form to be characterized and established. These results show that d(CGA) units are highly uniform, but that each strand in the duplex is structurally unique and has a distinct role in accommodating structural asymmetries induced by the C–CH+ base pair.
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