Three distannoxane dimers [(PhCH 2) 2(Cl)SnOSn(X)(CH 2Ph) 2] 2 (X=Cl, OMe, OEt) were prepared by the hydrolytic reaction of (PhCH 2) 2SnCl 2 with sodium alkoxides. The compounds are assigned tetranuclear distannoxane structures in solid state, which contain the so called ladder arrangement with a central planar Sn 2O 2 four membered ring. The endo and exo cyclic Sn atoms are both five coordinate, and have distorted trigonal bipyramidal geometries. A variety of hydrolyses of (PhCH 2) 2SnCl 2 were performed and these dimers were characterized by IR, 1H NMR spectroscopy and X ray diffraction analysis. Three distannoxane dimers [(PhCH2) 2 (Cl) SnOSn (X) (CH2Ph) 2] 2 (X = Cl, OMe, OEt) were prepared by the hydrolytic reaction of (PhCH2) 2SnCl2 with sodium alkoxides. compounds are assigned tetranuclear distannoxane structures in solid state, which contain the so called ladder arrangement with a central planar Sn 2O 2 four membered ring. The endo and exo cyclic Sn atoms are both five coordinate, and have distorted trigonal bipyramidal geometries. A variety of The hydrolyses of (PhCH 2) 2SnCl 2 were performed and these dimers were characterized by IR, 1H NMR spectroscopy and X ray diffraction analysis.