Cycloalkylaminocyclo- and Polyphosphazenes: X-ray Crystal Structures of gem-Tetrakis(cyclohexylamino)dichlorocyclotriphosphazene and Octakis(cyclopropylamino)cyclotetraphosphazene

The reactions of chlorocyclophosphazenes N₃P₃Cl₆ (1) and N₄P₄Cl₈ (2) and polydichlorophosphazene (3) with cyclohexylamine, cyclopentylamine, and cyclopropylamine have been studied. The major product with 1 is the geminal tetrakis derivative N₃P₃Cl₂(NHR)₄, while 2 gives the completely substituted derivative, N₄P₄(NHR)₈. X-ray crystal structure determinations of N₃P₃Cl₂(NHC₆H₁₁) ₄ (1a) and N₄P₄(NHC₃H₅)₈ (2c) have been carried out. 1a crystallizes in a triclinic space group, P1, with a = 11.2330(13) Å, b = 11.4269(16) Å, c = 13.4055(12) Å, α = 72.211(10)°, β= 72.150(9)°, γ = 81.777(11)°, V = 1557.3(3) A°³, and Z = 2. 2c crystallizes in a monclinic space group, P2₁/n, with a = 12.433(3) Å, b = 20.484(4) Å, c = 12.645(3) Å, β = 92.81(2)°, V = 1557.3(3) A°³, and Z = 4. The cycloalkylamino-substituted polyphosphazenes contain a small amount of residual chlorine atoms. These have high glass transition temperatures.