The reaction of spermidine with 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene produces a mixture of products of which one of the fractions is a spiro-cis-ansa derivative, namely 12-chloro-14,14-diphenyl-2,6,11,13,15,16-hexaaza-1,12-diphosphatricyclo[10.3.1.0(1,6)]hexadeca-12,14-diene, C19H26ClN6P3. Recrystallization of this fraction from different solvents results in the formation of two different crystalline forms. The rod morphology formed in dichloromethane-n-hexane (1:1) produces a triclinic structure with three molecules in the asymmetric unit. These three molecules adopt different conformations as a result of two NH groups flipping in an ansa-bridged ring system. The plate morphology crystals, grown in dichloromethane-n-hexane-ethyl acetate (1:1:1), produce a C-centred monoclinic structure that adopts a conformation that is essentially the same as one of the forms in the triclinic structure.