The five-membered heteroelement cluster THF·Cl
2
In(O
t
Bu)
3
Sn reacts with the sodium stannate [Na(O
t
Bu)
3
Sn]
2
to produce either the new oxo-centered alkoxo cluster ClInO[Sn(O
t
Bu)
2
]
3
(
1
) (in low yield) or the heteroleptic alkoxo cluster Sn(O
t
Bu)
3
InCl
3
Na[Sn(O
t
Bu)
2
]
2
(
2
). X-ray diffraction analyses reveal that in compound
1
the 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 Sn
3
In pyramid, the edges of which are all saturated by bridging tert-butoxy groups. The indium atom has a further chloride ligand. Compound
2
has two trigonal bipyramids as building blocks which are fused together at a six coordinate indium atom. One of the bipyramids is of the type SnO
3
In with tert-butyl groups on the oxygen atoms, while the other has the composition InCl
3
Na with chlorine atoms connecting the two metals. The sodium atom in
2
has further contacts to two plus one alkoxide groups which are part of a[Sn(O
t
Bu)
2
]
2
dimer disposing of a Sn
2
O
2
central cycle. The hetero element cluster in
2
thus combines three closed entities and its skeleton SnO
3
InCl
3
NaO
2
Sn
2
O
2
consists of three different metallic and two different non-metallic elements.