This Communication describes structures of a family of silver-adenine (purine) metallaquartets that occur in a four-stranded coordination motif, bearing a close resemblance to nucleic acid quadruplexes. Using modified purine frameworks, it is further demonstrated that subtle variations in nucleobase heterocycle are tolerable and a metallaquartet is obtained irrespective of the substitution, thus suggesting a high-propensity silver-adenine interaction to achieve quartet structures. All of the solid-state structures studied were orthorhombic, belonging to the Fdd2 space group. © 2007 American Chemical Society.