Five new derivatives of the polycyclic alumosiloxalic [Ph2SiO]8[Al(O)OH]4have 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, [Ph2SiO]8[Al(O)OH]2[AlO2]M (M=Ge, Sn), and those with complete substitution of the protic hydrogen atoms by metal atoms like [Ph2SiO]8[AlO2]4M2(M= Sn, Pb). Always one element of the series Ge, Sn, Ph is missing in the two types of compounds. Crystal structure analyses of [Ph2SiO]8[Al(O)OH]2[AlO2]2M∙2 C4H8O2(M= Ge (1), Sn (2a)), [Ph2SiO]8[Al(O)OH]2[AlO2]2Sn∙2THF(2b) and [Ph2SiO]8[AlO2]4M2(M= Sn (3) Pb (4)) have been performed elucidating either polycyclic basket-type (1, 2a, 2b) or closed polyhedral structures (3, 4).