The hexaazaphenalenyl anion (HAP, 3(-)), a highly symmetric heterocyclic pi system, has been synthesized and characterized. The crystal structures of its potassium salt K+(.)3(-) and copper complex Cu(2+)center dot(NH3)(4)center dot(3(-))(2) show pi-pi stacking and radially extended hydrogen bonds as well as coordination bonds constructed by the HAP anion. These in-plane and out-of-plane strong interactions demonstrate the multiple-networking ability of the HAP anion.