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The X-ray structures of a high temperature  α -phase (monoclinic,  P 2 1 / c ,  Z  = 24) and a low temperature  β -phase (orthorhombic,  Pbca ,  Z  = 8) of trichlorophosphazo- N -sulfurylchloride Cl 3 PNSO 2 Cl were determined at 173 K and 150 K, respectively. Both modifications are composed of isolated molecules arranged in layers with no strong intermolecular interactions with numerous Cl … O intermolecular interactions. The molecules in both modifications are fairly eclipsed along the P … S direction, the largest deviation from an ideal position being −17.4(2)° and 22.7(3)°. The bond lengths and angles of all molecules are equal within 4 σ  limits with an exception of P–Cl bonds.

Crystal structures of α and β modifications of trichlorophosphazo- N -sulfurylchloride Cl 3 PNSO 2 Cl