Interaction of hexachlorocyclodiphosph(V)azanes, (I a−h ) with 5,5 indigodisulfonic acid disodium salt (II) furnished the expected cyclodiphosph(V)azanes of the type (H 2 L 1 -H 2 L 8 ). The coordinating behavior of H 2 L 1 , where H 2 L 1 is 1M = Mn(II) and Co(II) (x = 2, n = 6, z = 1); M = Ni(II) (x = 2, n = 6, z = 1.5); M = Cu(II) (x = 2, n = 2, z = nil); M = Fe(III) (x = 4, n = 4, z = 4) and (L 1 ) = the deprotonated form of cyclodiphosphazane ligand. The molar conductance data show that all complexes are non-electrolytes. The spectral data and magnetic susceptibility measurements revealed that the ligand behaves as a dibasic tetradentate ligand coordinated to the metal ions through heterocyclic nitrogen and carbonyl oxygen atoms in an octahedral and square planar manner. Some ligand field parameters (Dq, B, and β), in addition to ligand field stabilization energy (LFSE), were calculated. The thermal behavior of these complexes is studied using TG technique and the different dynamic parameters are calculated applying Coats-Redfern equation. Antimicrobial activities have been studied using the agar-disc diffusion technique, and the higher antimicrobial activity has been observed for the iron (III) complex compared to the other metal complexes.