X-ray crystallography shows that AgN3 is a coordination polymer with square planar Ag+ coordinated by four azide ligands. Correspondingly, each end of each azide ligand is connected to a pair of Ag+ centers. The structure consists of two-dimensional AgN3 layers stacked one on top of the other, with weaker Ag–N bonds between layers. The coordination of Ag+ can alternatively be described as highly distorted 4 + 2 octahedral, the two more distant nitrogen atoms being part of the layers above and below.