Three types of ladder-like organostannoxanes, [C 5 H 4 N( p -CO 2 )] 2 [Bu 2 Sn] 4 ( μ 3 -O) 2 ( μ 2 -OH) 2 ( 1 ), [Ph 2 CHCO 2 ] 4 [Bu 2 Sn] 4 ( μ 3 -O) 2 ( 2 ), and [( p -NH 2 )-C 6 H 4 -CO 2 ] 2 [Bu 2 Sn] 4 ( μ 3 -O) 2 ( μ 2 -OH) 2 ( 3 ), have been synthesized and characterized using elemental analyses, Fourier-transform infrared spectroscopy, nuclear magnetic resonance ( 1 H, 13 C) experiments, and, for 1 and 2 , single-crystal X-ray diffraction analysis. X-Ray diffraction discloses that complexes adopt tetranuclear tin( iv ) ladder-like structures containing two ( 1 ) or four ( 2 ) deprotonated ligands. The essential difference between their molecular structures is that in 2 there are four carboxylate ligands, while in 1 and 3 there are two. The crystal structure of 1 reveals them to be a tetranuclear structure containing a three-rung-staircase Sn 4 O 4 core. The Sn 4 O 4 cluster consists of a ladder of four Sn 2 O 2 units. For 2 , the structure is a tetranuclear centrosymmetric dimer of an oxoditin unit having a central four-member ring. In this complex, the central Sn 2 O 2 core is fused with two four-member and two six-member rings. In the structures, there are two types of tin ions arranged in distorted trigonal bipyramid geometry or octahedron geometry. A series of O–H⋯N, C–H⋯O, and C–H⋯π intermolecular hydrogen bonds in these complexes play an important function in the supramolecular, or two-dimensional network structures are formed by these interactions.