The x-ray structure determination and semiempirical PM3 calculations of 2,4,4,6,6-pentachloro-2-(piperidyl)cyclotri(phosphazene)

Abstract

The structure of 2,4,4,6,6‐pentachloro‐2‐(piperidyl)‐cyclotri(phosphazene) (1) was determined by single‐crystal X‐ray diffraction analysis. Compound 1 crystallizes in the orthorhombic space group Pbea with Z = 8 and unit cell dimensions a = 8.316(2), b = 17.261(3), and c = 22.007(4) Å. The experimentally obtained structural parameters for compound 1 compare well with those calculated at the semiempirical PM3 level of theory. These results give credence to the PM3‐calculated structure of 2,4,4,6,6‐pentaazido‐2‐(piperidyl)cyclotri(phosphazene) (2) for which presently there are no experimental data available. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 283–286, 1997.

The preparation and x-ray structure of [P(C2H5)4]+[N3]? and the attempted preparation of [PH4]+[N3]?

“…The vacuum lines, handling techniques, and spectrometers used in this study have been described elsewhere [4,5,7]. All solvents were commercial materials and were dried and purified by condensation prior to use (CH 2 Cl 2 , Fissons, P 4 O 10 ; THF, Fissons, Na; SO 2 , BOC, CaH 2 ; SO 2 ClF, Aldrich, CaH 2 ; HF, Merck, BiF 5 ).…”

“…Covalently bound group 15 azides can conveniently be prepared from the corresponding halides and either sodium or silver azide [2]. For example, the following compounds were synthesized from the chloride precursors: [PN(N 3 ) 2 ] 3 [1b,3], P 3 N 3 (N 3 ) 5 (NC 5 H 10 ) 1 [4], P 3 N 3 (N 3 ) 4 (NC 5 H 10 ) 2 [5], P 3 N 3 (N 3 ) 3 (NC 5 H 10 ) 3 [5], E(N 3 ) 3 (E ‫ס‬ P, As, Sb, Bi) [2,6a-d], P(N 3 ) 5 [6e], and [PCl 6‫מ‬n …”

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Tetraethylphosphonium azide, [P(C 2 H 5 ) 4 ] ‫ם‬ [N 3 ] ‫מ‬ , was prepared from tetraethyl phosphonium bromide and silver azide. Single crystals of [P(C 2 H 5 ) 4 ] ‫ם‬ [N 3 ] ‫מ‬ were grown from dichloromethane/THF (10:1) solution.

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