A series of novel tin chlorides RnSnCl4−n and respective hydrides RnSnH4−n were synthesized displaying a range of substituted phenyl residues, as well as naphthyl moieties (R = Ph, o-tolyl, 2,4-xylyl, 2,6-xylyl, p-biphenyl, 1-naphthyl, 2-naphthyl). These compounds were characterized using 1H, 13C and 119Sn NMR spectroscopy. In addition, X-ray diffraction was employed to elucidate the molecular structure of all solid aryltin chlorides (8–10, 14, 15). In each case, the tin is in a distorted tetrahedral environment. All naphthyl containing derivatives exhibit displaced π–π stacking. DFT calculations were carried out to compare experimental NMR data with calculated 13C and 119Sn shifts, as well as 13C–119Sn coupling constants.