Crystal Structure of 8,8-dichloro-1,2,10,11,13,14-hexahydro-6.LAMBDA.5,8.LAMBDA.5, 10.LAMBDA.5-6,10-nitrilo[1,3,5,7,2,4,6]tetraazatriphosphonino-bis[1,3,2]oxazaphosphorine

Abstract

is known as a "standard" compound in the field of phosphazene chemistry, which has potential use in the syntheses of many small organocyclophosphazene derivatives. 1 In the reactions of N3P3Cl6 with N2O2-donor type tetradentate ligands, two kinds of products, e.g. spiro-ansa-spiro and spiro-bino-spiro, are expected to be formed. However, only the spiro-ansa-spiro architecture has been isolated. The title molecule was prepared from the reaction of N,N′bis(2-hydroxyethyl)ethylenediamine (5.00 g, 33.8 mmol), N3P3Cl6 (5.88 g, 16.9 mmol) and K2CO3 (18.65 g, 135.1 mmol) in dry THF (250 ml) by vigorous stirring; argon was passed over the reaction mixture for 2 days. The solvent was evaporated and the residue was chromatographed [eluent CH3CN-benzene (2:1), silica-gel (100 g)] and then crystallized from a CH3CN-benzene (2:1) mixture (yield 2.48 g, 47%, m.p. 528 K). The X-ray analysis results are given in Tables 1-3. The H atoms were located in a difference synthesis and refined isotropically. The title molecule is on a crystallographic mirror plane that passes through N2, P1, Cl1, and Cl2; therefore, only half of this molecule is independent. The C3 atom was disordered. The occupancies of the disordered C3A and C3B atoms were fixed at 0.5. The title molecule was also analysed to resolve the disorder in lower symmetry space group Pna21 by removing the mirror symmetry in the molecule, but was not successful. In the title molecule (Fig. 2) the rings, A(P1/N1/P2/N2/ P2 i /N1 i) and B(N2/P2/N3/C3a/C3b i /N3 i /P2 i), are not planar with total puckering amplitudes 2 of QT = 0.431(4) and 0.839(4)Å, respectively [symmetry code (i): x, 1.5-y, z]. The fivemembered ring C(P2/O1/C1/C2/N3) has a twisted conformation with ϕ2 =-80.8(5)˚. The bicyclic system is made up of rings A and B in a sofa conformation (Fig. 3a). Each ring is V-shaped. Regarding the disordered structure of the N-CC -N chain, the sums of the bond angles around the N3 atom [335.4(4) and 356.0(3)˚] show a change in the hybridization of atom N3 from x77

Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene Derivatives

“…The fully substituted spiro-ansa-spiro-phosphazenes 14 and 16 were obtained by the reaction of 11 with an excess of pyrrolidine and DASD, respectively, in dry THF. Compounds 10 and 11 are the first examples of the ansa structure having an ethane-1,2-diamine precursor in contrast to the expectation of spiro structure, and their structures have previously been confirmed by X-ray crystallography. 8b,8c Interestingly, the P−N bonds of the seven membered ansa rings of 10 and 11 have cis configurations. Two P atoms of the ansa ring in 10 and 11 are stereogenic because they have four different substituents.…”

“…Synthesis. Spiro-ansa-spiro-phosphazene 10 has been prepared by means of the reaction of N 3 P 3 Cl 6 with aminopodand 1 8b. The fully substituted spiro-ansa-spiro-phosphazenes 14 and 16 were obtained by the reaction of 11 with an excess of pyrrolidine and DASD, respectively, in dry THF.…”

“…The preparation and crystallographic data of 8,8-dichloro-1,2,10,11,13,14-hexahydro-6λ 5 ,8λ 5 ,10λ 5 -6,10-nitrilo[1,3,5,7,2,4,6]tetrazatriphosphonino-bis[1,3,2]oxazaphosphorine ( 10 ) were published before 8b. The MS, IR, and 1 H, 13 C, and 31 P NMR data of 10 will be discussed in this paper.…”

“…13 C NMR (400 MHz, CDCl 3 ): δ 24.7 ( 3 J PC = 4.2 Hz, N−CH 2 − C H 2 ), 47.3 ( 2 J PC = 3.7 Hz, N− C H 2 ), 47.9 (Ar− C H 2 −N), 118.7 ( 3 J PC = 8.3 Hz, C 5 ), 123.7 ( 3 J PC = 7.3 Hz, C 1 ), 124.3 ( C 3 ), 126.6 ( C 4 ), 129.1 ( C 2 ), 149.9 ( 2 J PC = 8.5 Hz, C 6 ). The second product is 13 8a…”

“…In recent years, two interesting papers about the reactions of bifunctional reagents with fluoro- and chlorophosphazenes have appeared in the literature, and it has been reported that, in these reactions, ansa-, spiro-, ansa-spiro-, and bis(ansa-substituted)-cyclophosphazenes have been isolated . Our group has recently synthesized four novel families of partially substituted phosphazene derivatives with N 2 O x ( x =2,3) donor-type crown ethers, bulky difunctional aminopodands, and tetrafunctional aminopodands, namely, spiro-crypta, spiro-crown (PNP-lariat), spiro-ansa-spiro-, and spiro-bino-spiro-phosphazenes. Another area of interest is the ring-opening polymerization leading to the preparation of different polyphosphazene types, cyclolinear or cyclomatrix polymers …”