Five new derivatives of the polycyclic alumosiloxalic [Ph
2
SiO]
8
[Al(O)OH]
4
have been synthesized by replacement of the protic hydrogen atoms on the hydroxy-groups attached to the aluminium atoms by the divalent group 14 elements germanium, till and lead. The compounds can be divided in those with one metal atom per alumosiloxane moiety, [Ph
2
SiO]
8
[Al(O)OH]
2
[AlO
2
]M (M=Ge, Sn), and those with complete substitution of the protic hydrogen atoms by metal atoms like [Ph
2
SiO]
8
[AlO
2
]
4
M
2
(M= Sn, Pb). Always one element of the series Ge, Sn, Ph is missing in the two types of compounds. Crystal structure analyses of [Ph
2
SiO]
8
[Al(O)OH]
2
[AlO
2
]
2
M∙2 C
4
H
8
O
2
(M= Ge (1), Sn (2a)), [Ph
2
SiO]
8
[Al(O)OH]
2
[AlO
2
]
2
Sn∙2THF(2b) and [Ph
2
SiO]
8
[AlO
2
]
4
M
2
(M= Sn (3) Pb (4)) have been performed elucidating either polycyclic basket-type (1, 2a, 2b) or closed polyhedral structures (3, 4).