Phosphorus–nitrogen compounds. spiro- and crypta-phosphazene derivatives: synthesis and spectral investigations. Structure of butane-N,N0-bis(1,4-oxybenzyl)-spiro(propane-1,3-diamino) tetrachlorocyclo-2l5, 4l5, 6l5-triphosphazatriene. Part VII

The condensation reactions between trimer, N3P3Cl6, and diamines, 2 and 4 and {1-{N-[1-(2-hydroxynaphthylmethyl)aminomethylidene]}- 2(1H)-naphthalenone, 3, yielded the new spiro-cyclic- (5 and 8) and the novel spiro-phosphazene (7) derivatives, respectively. The fully substituted phosphazene (6) was also obtained from the reaction of 5 with the excess of pyrrolidine. Compounds (4–8) have been characterized by elemental analyses, FTIR, 1H-, 13C-, 31P-NMR, HETCOR, COSY and MS. The structure of crypta-phosphazene, 8, has been examined crystallographically. Compound 8 is the first example of the crypta-phosphazene derivatives. The 31P-NMR spectra of compounds 7 and 8 indicate that, both of the compounds have anisochronism because of the stereogenic centers. The pyramidal geometry of two spiro-cyclic nitrogen atoms in compound 8, gives rise to stereogenic property. The sums of the bond angles around N4 and N5 nitrogens are 350.6(2) and 349.6(3)8, respectively. Compound 8 crystallizes in the triclinic space group P1 with a ¼ 8:798ð3Þ; b ¼ 10:498ð3Þ and c ¼ 15.689(4) A° ; a ¼ 91:35ð2Þ; b ¼ 103:39ð4Þ and g ¼ 102:88ð4Þ8; V ¼ 1369.9(7) A° 3, Z ¼ 2 and Dx ¼ 1:491 g cm23: It consists of a non-centrosymmetric, non-planar phosphazene ring with a bulky dibenzo-diazacrown etheric side group. q 2004 Elsevier B.V. All rights reserved.