The reactions of the ligands 2,6-diacetylpyridine bis(S-methyldithiocarbazate)] (H 2 dapmdtc) and 2,6-diacetylpyridine bis(S-benzyldithiocarbazate)] (H 2 dapbdtc) with R 4-m SnCl m (R = Me, n Bu, Ph; and m=2) led to the formation of six seven-coordinate diorganotin(IV) complexes, which were studied by microanalysis, i.r., n.m.r ( 1 H, 119 Sn) and Mo¨ssbauer spectroscopies. The X-ray structures determination of complexes [Me 2 Sn(dapmdtc)], [Me 2 Sn(dapbdtc)] and [Ph 2 Sn(dapbdtc)] revealed the presence of neutral seven-coordinated complexes. The structures consist of monomeric units in which the Sn(IV) atom exhibits distorted pentagonal bipyramidal (PBP) geometry, with the S,N,N,N,S-donor systems of the ligands lying in the equatorial plane and organic groups in the apical positions. A correlation between Mo¨ssbauer and X-ray data based on the point-charge model is discussed.