Hydrolysis reactions of di-and trinuclear organotin halides yielded large novel cage compounds containing SnÀ OÀ Sn bridges. The molecular structures of two octanuclear tetraorganodistannoxanes showing double-ladder motifs, viz., [{Me 3 SiCH 2 (Cl)SnCH 2 YCH 2 Sn(OH)CH 2 SiMe 3 } 2 (μ-O) 2 ] 2 [1, Y = p-(Me) 2 SiC 6 H 4 -C 6 H 4 Si(Me) 2 ] and [{Me 3 SiCH 2 (I) SnCH 2 YCH 2 Sn(OH)CH 2 SiMe 3 } 2 (μ-O) 2 ] 2 •0.48 I 2 [2•0.48 I 2 , Y = p-(Me) 2 SiC 6 H 4 -C 6 H 4 Si(Me) 2 ], and the hexanuclear cage-compound 1,3,6-C 6 H 3 (p-C 6 H 4 Si(Me) 2 CH 2 Sn(R) 2 OSn (R) 2 CH 2 Si(Me) 2 C 6 H 4 -p) 3 C 6 H 3 -1,3,6 (3, R = CH 2 SiMe 3 ) are reported. Of these, the co-crystal 2•0.48 I 2 exhibits the largest spacing of 16.7 Å reported to date for distannoxane-based double ladders. DFT calculations for the hexanuclear cage and a related octanuclear congener accompany the experimental work.