In this study, the crystal structures of the dispiroansa spermine derivatives of cyclotriphosphazene are characterised for the first time. The reaction of spiro-, gem-disubstituted cyclotriphosphazene derivatives, N(3)P(3)Cl(4)R(2) [R = NHPh, (HN(CH(2))(3)NH)(0.5), (OCH(2)C(CH(3))(2)CH(2)O)(0.5)], (1-3), with spermine (4), in aprotic solvents such as CH(2)Cl(2) results in a series of dispirobino spermine derivatives of cyclotriphosphazene (5a, 6a, 7), namely spermine bridged compounds. Whereas, in protic solvents such as CHCl(3) give, dispiroansa derivatives (8-10) namely tetracyclic cyclotriphosphazene. The new series of dispirobino and dispiroansa spermine derivatives of cyclotriphosphazene (5a, 6a, 7-10) have been characterised by elemental analysis, mass spectrometry, X-ray (for 5a, 8,10) and (1)H, (31)P NMR spectroscopies. (C) 2009 Elsevier Ltd. All rights reserved.