The heteropolyanions [Bi 2 W 22 O 74 (OH) 2 ] 12-(1) and [X 2 W 20 M 2 O 70 (H 2 O) 6 ] (14-2n)-(X ) Sb 3+ , Bi 3+ ; M n+ ) Fe 3+ , Co 2+ , Zn 2+ ) (2-7) have been synthesized as alkali metal and ammonium salts, respectively, and characterized by elemental analysis, infrared spectroscopy, and X-ray crystallography. These tungsto bismutates and antimonates reveal one common feature: the trivacant -B-XW 9 O 33 Keggin fragment as the structural building unit. Formally, the unit can be derived from the Keggin structure by removing one trimetalate fragment, W 3 O 13 , and a 60°rotation of one of the remaining W 3 O 13 subunits around the X-O W3X bond vector (the subscript indicates the element(s) bonded). The unshared pair of electrons of the respective central, pyramidally coordinated heteroatom Sb III or Bi III prevents formation of the complete spherical structure. In the presented heteropolyanions 1-7, two -B-XW 9 O 33 units are connected by two WO 2 groups. Further stabilization of this hitherto unknown bis-decatungsto ion [X 2 W 20 O 70 ] 14-is reached either by addition of two formal fac-WO 3 anti-Lipscomb's rule units to give the bis-undecatungsto bismutate [Bi 2 W 22 O 74 (OH) 2 ] 12-(1) or by addition of two M n+ (H 2 O) 3 groups (M n+ ) Fe 3+ , Co 2+ , Zn 2+ ) forming the large, transition-metal-substituted heteropolyanion clusters [X 2 W 20 M 2 O 70 (H 2 O) 6 ] (14-2n)-(X ) Sb 3+ , Bi 3+ ; M n+ ) Fe 3+ , Co 2+ , Zn 2+ ) (2-7).

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