Xenon-nitrogen bonded compounds

The crystal structure of xenon(II) fluoride imidodisulfuryl fluoride has been determined at −55°C from three-dimensional X-ray data. The compound crystallizes in the monoclinic system, space group P21/a, with four molecules in a unit cell of dimensions a=11.827(4), b=6.828(2) and c=9.467(3) Ā. The structure was refined by least-squares and Fourier methods to a final R factor of 0.023 for 1721 non-zero reflections. The structure analysis has established the existence of discrete FXeN(SO2F)2 molecules and shows that FXeN(SO2F)2 is XeN bonded. The xenon atom is approximately linearly coordinated by the nitrogen atom of the imidodisulfuryl fluoride group and a fluorine atom. The angle F-Xe-N is 178.1(1)°, and the interatomic distances are Xe-N = 2.200(3) and Xe-F=1.967(3) Ā. Raman spectral data and assignments are also presented for 15N-enriched FXeN(SO2F)2, HN(SO2F)2 and Cs+N(SO2F)2−. Solution 15N, 129Xe and 19F N.M.R. studies of 15N-enriched FXeN(SO2F)2 and Xe[N(SO2F)2]2 demonstrate that these compounds are also XeN bonded in solution. The first examples of a directly bonded 129Xe15N coupling are also reported.The new xenon compound [(CF3SO2)2N]2Xe has also been obtained in high yield by a novel route employing the reaction of the trimethylsilyl derivative of HN(SO2CF3)2 with XeF2. Although quite stable, Xe[N(SO2CF3)2]2 exhibits a decomposition route in stark contrast to the related compound Xe[N(SO2F)2]2 forming Xe, C2F6, CF3N(SO2CF3)2 and CF3SO2NSO2.