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Mixed distannoxane dimers [ClR2SnOSnR'2Cl]2 were synthesized by the reaction of R2SnO (R = Bu, Pr) and R2SnCl2 (R = Me, Ph, Cy, Oct). The crystal structures of compound 1 and 5 show they are ladder-type dimers that contain a central planar Sn2O2 four-membered ring. Both endo- and exo-Sn atoms are five-coordinate.