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) A, b = 11.4269(16) A, c = 13.4055(12) A, α = 72.211(10)°, β = 72.150(9)°, γ = 81.777(11)°, V = 1557.3(3) A3, and Z = 2. 2c crystallizes in a monclinic space group, P21/n, with a = 12.433(3) A, b = 20.484(4) A, c = 12.645(3) A, β = 92.81(2)°, V = 1557.3(3) A3, and Z = 4. The cycloalkylamino-substituted polyphosphazenes contain a small amount of residual chlorine atoms. These have high glass transition temperatures.