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Reaction of A 2 CO 3  with Sn and Se in an H 2 O/CH 3 OH mixture at 115 - 130°C affords the isotypic lamellar selenidostannates A 2 Sn 4 Se 9 -H 2 O 1 (A = Rb) and 2 (A = Cs). The polyanions  2  ∞ [Sn 4 Se 9  2- ] exhibit Sn 4 Se 5  es molecular building units, in which two adjacent Sn(IV) atoms of an Sn 4 Se 4  8-membered ring are bridged by an additional Se atom. These units connect through (SnSe) 2  4-membered rings to afford a 4 4  anionic net with 16-membered cavities. Cs 2 Sn 2 Se 6  (3) may be prepared by methanolothermal reaction of Cs 2 CO 3  with SnSe and Se at 130°C and contains porous  2  ∞ [SnTSe 2-  ] sheets in which  1  ∞ [SnSe 3  2-  ] ribbons are linked through Se-Se bonds. The resulting 4 4  net displays 14-membered pores in which the Cs cations reside.

Solventothermal Synthesis of the Lamellar Selenidostannates(IV) A 2 Sn 4 Se 9 · H 2 O (A = Rb, Cs) and Cs 2 Sn 2 Se 6