A family of tetradentate ligands,[N, N′-bis (pyridine-2-yl)] ethane-1, 2-diamine (L1),[N, N′- bis (pyridine-2-yl)] propane-1, 3-diamine (L2) and [N, N′-bis (pyridine-2-yl)] butane-1, 4- diamine (L3) has been prepared. These ligands differ only in the number of CH2 groups separating two pyridyl/imine moieties, however, in reactions with MnII and N− 3 salts, they produce structurally very diverse solids;[Mn2 (L1) 3 (N3)] n (ClO4) 3n (1),[Mn2 (L2) 2 (N3) ...