The influence of intermolecular interactions on the Mossbauer quadrupole splitting (Delta) of Sn-119 was investigated in detail by density functional theory (DFT) calculations. Six organotin(IV) complexes [Me2Sn(acac)(2) (1), Ph3SnCl (2), Me3Sn-succinimide (3), Me3Sn-phthalimide (4), Me3SnCl (5), and cHex(3)SnCl (6)] of known solid-state structures and quadrupole splittings were selected. Theoretical Delta values were calculated for both fully optimized geometries and experimental solid-state structures of different size, and the results were compared to the experimental Delta values. Compared to a synthetic procedure described in the literature for compound 4, a more convenient synthesis is reported here. The experimental Delta of this compound has also been redetermined at 80 K. For compounds with negligible intermolecular interactions in the solid state, calculated Delta values obtained did not vary significantly. In contrast, the calculated Delta values turned out to be very sensitive to the size of the supramolecular moiety considered in the crystal lattice. The crystal structure of compound 2 shows no significant intermolecular interactions; however, the calculated and the experimental Delta values remained very different, even when the supramolecular moiety considered was extended. Distortion of the coordination sphere of tin in the molecule of 2 toward a trigonal bipyramidal geometry was considered, and a possible weak intermolecular Sn center dot center dot center dot Cl interaction was included in the model. Steps of the distortion followed the new structure correlation function, which was found for the R3SnCl (R = alkyl, aryl) compounds. The experimental Delta value could be approached by this method. These results suggest that compound 2 is involved in some unexpected intermolecular interaction at 80 K.