Complexes formed by the reactions of fluorinated and non-fluorinated organonitriles with [Zn(SO2)2][AsF6]2:: A structural study

[Zn(SO2)(2)][AsF6](2) (1) has been prepared from zinc metal and AsF5 in liquid sulfur dioxide, and crystallized from sulfur dioxide giving crystals of [Zn(SO2)(4)(AsF6)(2)] (1a). The compound 1 forms the homoleptic complexes [Zn(NCR)(6)](ASF(6))(2) (R: CH3 (2a), C6H5 (3a), C6F5 (3b)) with the corresponding nitriles. In these complexes, the metal center is octahedrally surrounded by six ligands (average Zn-N 2.13 angstrom). Reaction of 1 with the weaker ligand F3CCN results in dicoordination at the metal center complemented by a two-dimensional polymeric network (2b) containing bridging AsF6- anions. [Zn(SO2)(4)(AsF6)(2)] (1a): monoclinic, P2(1)/c, a= 8.5176(8) angstrom, b = 13.5787(14) angstrom, c = 14.7661(15) angstrom, beta = 99.296(2)degrees; [Zn(NCCH3)(6)] [AsF6](2) (2a): rhombohedral, R-3, a=11.2225(8) angstrom, b = 11.2225(8) angstrom, c = 16.9393(14) angstrom; [Zn(NCCF3)(2)][mu-FAsF5)(2)((2b): monoclinic, P2(1)/c, a = 11.226(3) angstrom, b = 6.6147(19) angstrom, c = 10.460(3) angstrom, beta = 104.028(5)degrees; [Zn(NCC6H5)(6)] [AsF6](2) (3a): monoclinic, P2(1)/n, a = 13.7968(10) angstrom, b = 19.8861(15) angstrom, c = 16.1692(12) angstrom, beta = 91.563(2)degrees; [Zn(NCC6F5)(6)] [AsF6](2)center dot 2SO(2) (3b): monoclinic, P2(1)/n, a = 10.8448(9) angstrom, b = 154456(13) angstrom, c = 17.5206(15) angstrom, beta = 104.158(1)degrees.