The compounds Sn(CH(2)CH(2)CO(2)Me)(2)(C3S5) 1 (R = Me or Pr-1) and [Q][Sn(CH(2)CH(2)CO(2)Me)(C3S5)(2)] 2 (Q = NEt(4) or 1,4-dimethylpyridinium; C3S5 = 4,5-disulfanyl-1,3-dithiole-2-thionate) have been prepared and characterised by solution and solid-state NMR spectroscopy. A crystal structure determination of 1 (R = Me) revealed it to be a monomeric six-co-ordinate, distorted-octahedral complex with chelating MeO(2)CCH(2)CH(2) groups and trans-carbon atoms [Sn-O(C) 2.629(7) Angstrom]. The MeO(2)CCH(2)CH(2) group in 2, both in solution and in the crystal, is monodentate: the tin centres in the anions of both complexes 2 were shown to have structures closer to rectangular pyramids than to trigonal bipyramids. There were, however, slight differences in the solid-state structures of the anions, particularly in regard to the separations of the Sn and carbonyl oxygen atoms; Sn ... O intramolecular distances are 4.84(1) and 3.371(4) Angstrom in 2 (Q = NEt(4)) and 2 (Q = 1,4-dimethylpyridinium) respectively. There were also differences in the packing of the anions.