The reactions between compounds of the type MAF(6) (M = alkali metal; A = P, As, V, Ru, Ir, Sb, Nb, Ta) and xenon difluoride were studied in anhydrous hydrogen fluoride solvent. The coordination products [M(XeF2)(n)]AsF6 were only observed in the case of LiAF(6) (A = P, As, Ru, Ir), and the crystal structure of [Li(XeF2)(3)]AsF6 was determined (monoclinic space group P2(i) with a = 6.901(9) angstrom, b = 13.19(2) angstrom, c = 6.91(1) angstrom, beta = 91.84(2)degrees, and Z = 2). The coordination sphere of lithium is comprised of six F atoms. The compound series was also characterized by Raman spectroscopy.