The five-membered heteroelement cluster THF·Cl2In(OtBu)3Sn reacts with the sodium stannate [Na(OtBu)3Sn]2to produce either the new oxo-centered alkoxo cluster ClInO[Sn(OtBu)2]3(1) (in low yield) or the heteroleptic alkoxo cluster Sn(OtBu)3InCl3Na[Sn(OtBu)2]2(2). X-ray diffraction analyses reveal that in compound1the polycyclic entity is made of three tin atoms which together with a central oxygen atom form a trigonal, almost planar triangle, perpendicular to which a further indium atom is connected through the oxygen atom. The metal atoms thus are arranged in a Sn3In pyramid, the edges of which are all saturated by bridging tert-butoxy groups. The indium atom has a further chloride ligand. Compound2has two trigonal bipyramids as building blocks which are fused together at a six coordinate indium atom. One of the bipyramids is of the type SnO3In with tert-butyl groups on the oxygen atoms, while the other has the composition InCl3Na with chlorine atoms connecting the two metals. The sodium atom in2has further contacts to two plus one alkoxide groups which are part of a[Sn(OtBu)2]2dimer disposing of a Sn2O2central cycle. The hetero element cluster in2thus combines three closed entities and its skeleton SnO3InCl3NaO2Sn2O2consists of three different metallic and two different non-metallic elements.