Four simultaneously different bridging coordination modes were characterized in a new 2D manganese-azide system, giving a proof of the extraordinary versatility of this ligand and the influence of the counterion in the final topology.
A new topology of a Mn(II) azide only 2D system exhibiting dicubane subunits and four different azide bridging modes is reported.
► A new 2D Mn(II) azide only topology is reported. ► Four different azide bridging modes are simultaneously present. ► The [Mn2(N3)5]− anionic layers are built up by defective dicubane subunits. ► The title compound shows overall antiferromagnetic behavior.