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The reactions of Ag2C2 and the corresponding silver perfluoro-dicarboxylates result in the formation of three new double and triple salts, Ag2C2·3AgO2CCF2CF2CO2Ag·7H2O (1), 2Ag2C2·6AgO2CCF2CF2CO2Ag·AgNO3·12H2O (2) and Ag2C2·4AgO2CCF2CF2CF2CO2Ag·17.5H2O (3), which have been structurally characterized by single crystal X-ray analysis. Their structures contain silver cages of various shapes: crown in 1, pentagonal bipyramid together with monocapped pentagonal bipyramid in 2, and square antiprism in 3, each containing an encapsulated acetylide dianion. Except for the pentagonal bipyramid, the other three silver cages are unprecedented. Compound 2 provides a unique example in which two kinds of silver polyhedra with different numbers of vertices (C2@Ag7 and C2@Ag8) co-exist in the crystal structure.
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