This Article describes the synthesis and crystallographic investigation of a silver complex of a modified adenine derivative bearing a nitrile pendant at the N9 position. All three adenine ring nitrogen atoms coordinated to silver ions, while the fourth coordination was achieved at the nitrile functionality, thus resulting in the formation of silver-mediated interconnected trimeric, pentameric, and hexameric metallacyclic rings and helical signatures in two orthogonal directions. © 2010 American Chemical Society.