The condensation reaction of partly substituted spiro-cyclophosphazenic lariat (PNP-pivot) ethers, N3P3[(o-NHPhO)(2)R]Cl-4 (5-8), where R=-CH2CH2-, -CH2CH2CH2-, -CH2CH2OCH2CH2-, and -CH2PhCH2-, with pyrrolidine have been afforded fully substituted pyrrolidino phosphazene derivatives (9-12) (Scheme). There are the first examples of the spiro-cyclophosphazenic lariat (PNP-pivot) ether ligands with N2Ox-(x = 2, 3) donor type containing 11-14 membered macrocycles. The solid state structures of (11 and 12) have been determined by X-ray diffraction techniques. Evidently, in the macrocyclic ring of the compound (11), there are two three-centered (bifurcate) N-(HO)-O-.../N-(HN)-N-... hydrogen bonds, while compound (12) has two intramolecular N-(HO)-O-... bonds. The relative radii of macrocyclic hole sizes of the compounds (11 and 12) are 1.25 and 1.10 angstrom, respectively. The structures of the new compounds (9-12) have also been examined by FTIR, H-1-, C-13-, P-31- NMR, MS and elemental analysis. Compound (11) crystallizes in the Pcab space group with a=9.8474(13), b=18.466(2), c=38.9375(19) angstrom, V=7080.7(14) angstrom(3), Z=8 and D-x=1.317 g cm(-3), while compound (12) crystallizes in P-1 space group with a=9.3724(5), b=11.2613(9), c=20.401(2) angstrom, alpha=93.177(8), beta=102.115(7), gamma=105.360(5)degrees, 17=2016.0(3) angstrom(3), Z=2 and D-x=1.268 g cm(-3). The structures of (11 and 12) consist of nearly planar and non-planar trimeric phosphazene rings with spiro-cyclic bulky N2O3 and N2O2 macrocycles, respectively. (c) 2005 Elsevier B.V. All rights reserved.