Quaternary Selenidogermanates(IV) A3[AgGe4Se10]·2H2O and A2[MnGe4Se10]·3H2O (A = Rb, Cs) with Open Framework Structures

Abstract
Hydrothermal reaction of Ge and Se with Ag(CH3COO) in the presence of alkali metal carbonates affords the open framework selenidogermanates(IV) A3[AgGe4Se10]·2H2O (A = Rb, Cs), 1 and 2, which contain corner linked adamantane-like Ge4Se10 cages and AgSe4 tetrahedra. The analogous reaction with Mn(CH3COO)2 yields the isostructural tetragonal compounds A2[MnGe4Se10]·3H2O (A = Rb, Cs), 3 and 4. The cations are sited at a general position in the channels of the silver bridged anionic framework of 1 and 2 and exhibit a disordered pattern of occupation (s.o.f. = 0.75) with one of the two crystallographically independent water oxygen atoms O(2) (s.o.f. = 0.25). In contrast, the Rb+ cations in 3 are disordered over all three cation/oxygen sites, and the cation/water occupation pattern is fully reversed for the larger Cs+ cations in 4 in comparison to 1 and 2.

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