Metal(II) hexafluorophosphates(V) (M = Sr, Pb) containing XeF(2)-coordinated metal ions [M(XeF(2))(3)](PF(6))(2), [Pb(3)(XeF(2))(11)](PF(6))(6), and [Sr(3)(XeF(2))(10)](PF(6))(6).

From the system MF(2)/PF(5)/XeF(2)/anhydrous hydrogen fluoride (aHF), four compounds Sr(XeF(2))(3)(2), Pb(XeF(2))(3)(2), Sr(3)(XeF(2))(10)(6), and Pb(3)(XeF(2))(11)(6) were isolated and characterized by Raman spectroscopy and X-ray single-crystal diffraction. The M(XeF(2))(3)(2) (M = Sr, Pb) compounds are isostructural with the previously reported Sr(XeF(2))(3)(2). The structure of Sr(3)(XeF(2))(10)(6) (space group C2/c; a = 11.778(6) Angstrom, b = 12.497(6) Angstrom, c = 34.60(2) Angstrom, beta = 95.574(4) degrees, V = 5069(4) Angstrom(3), Z = 4) contains two crystallographically independent metal centers with a coordination number of 10 and rather unusual coordination spheres in the shape of tetracapped trigonal prisms. The bridging XeF(2) molecules and one bridging PF(6)- anion, which connect the metal centers, form complicated 3D structures. The structure of Pb(3)(XeF(2))(11)(6) (space group C2/m; a = 13.01(3) Angstrom, b = 11.437(4) Angstrom, c = 18.487(7) Angstrom, beta = 104.374(9) degrees, V = 2665(6) Angstrom(3), Z = 2) consists of a 3D network of the general formula {Pb(3)(XeF(2))(10)(6)}n and a noncoordinated XeF(2) molecule fixed in the crystal structure only by weak electrostatic interactions. This structure also contains two crystallographically independent Pb atoms. One of them possesses a unique homoleptic environment built up by eight F atoms from eight XeF(2) molecules in the shape of a cube, whereas the second Pb atom with a coordination number of 9 adopts the shape of a tricapped trigonal prism common for lead compounds. Pb(3)(XeF(2))(11)(6) and Sr(3)(XeF(2))(10)(6) are formed when an excess of XeF(2) is used during the process of the crystallization of M(XeF(2))(3)(2) from their aHF solutions.