The syntheses of triorganotin(IV) derivatives of 2,4,6-tris(trifluoromethyl)benzene R(3)SnC(6)H(2)(CF3)(3) [R = CH3 (1), n-C4H9 (2) and C6H5 (3)] and 1,4-bis(hexafluoroisopropoxy)tetrafluorobenzene [R(3)SnOC(CF3)(2)]2C6F4[R = CH3 (4) and C6H5 (5)] are achieved metathetically by reacting the corresponding triorganotin chlorides with Li[2,4,6-(CF3)(3)C6H2] or [LiOC(CF3)(2)]2C6F4 in diethyl ether/hexane. The solid state structures of compounds 3 and 4 are investigated by single crystal X-ray analysis. Crystals of 3 belong to the orthorhombic space group Pna2(1); fw = 631.3, a = 13.882 (3) Angstrom, b = 21.031 (4) Angstrom, c = 8.324 (2) Angstrom, V = 2430.2 (9) Angstrom(3), Z = 4. Compound 4 crystallizes in a monoclinic system having space group P2(1)/n; fw = 807.7, a = 7.109 (2) Angstrom, b = 16.767 (3) Angstrom, c = 11.370 (2) Angstrom, beta = 101.33 (3)degrees, V = 1328.8 (5) Angstrom(3), Z = 2. The structures are solved by using the direct method and the final refinement by full matrix least square procedures converged at R = 0.034 and R(w) = 0.040 for 3; and R = 0.077 and R(w) = 0.073 for 4 by using 2175 and 1230 refections, respectively, with F > 3 sigma(F). While the solid state structures of 3 and 4 show evidence of Sn-F contacts which are less than the Sn-F van der Waals distance of 3.64 Angstrom, variable temperature F-19 NMR studies of both 1 and 3 in CDCl3/toluene-d(8) show no evidence for Sn-F bonding interactions. The Sn-119 NMR spectrum for 1 in toluene-d(8) is also indicative of four coordinate tin. Intermolecular Sn-F interaction of the trimethyltin moiety in 4 with a fluorine atom of the CF3 group of a neighboring molecule results in flattening of the CH3-Sn-CH3 angle (average = 115.2 degrees) and sheet polymer formation in the solid state.