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Reaction of N 3 P 3 Cl 6 with spermidine and spermine in protic solvents such as CHCl 3 proceeds cleanly to yield the SPIRANSA, N 3 P 3 Cl 3 [HN(CH 2 ) 3 N(CH 2 ) 4 NH], and the DISPIRANSA, N 3 P 3 Cl 2 [HN(CH 2 ) 3 N(CH 2 ) 4 N(CH 2 ) 3 NH], derivatives, respectively. These two chemicals crystallize in orthorhombic systems. SPIRANSA: Pbcn, a = 20.206(3), b = 18.107(3), c = 9.944(2)A, V = 3638 A 3 , Z = 8, D X = 1.56(1) Mg m −3 , R = 0.067 for 2880 unique reflections and 226 variable parameters. DISPIRANSA: Pmn 2 1 , a = 13.653(6), b = 8.467(5), c = 7.297(2)A, V = 843.5 A 3 , Z = 2, D X = 1.73(1) Mg m −3 , R = 0.045 for 736 unique reflections and 117 variable parameters. These two structures exhibit spermidino and spermino ligands grafted on the N 3 P 3 ring in a merged bicyclic SPIRANSA (i.e. a fusion of one SPIRO loop and of an ANSA arch) and a merged tricyclic DISPIRANSA (i.e. a fusion of two SPIRO loops and of an ANSA arch) configurations, respectively.