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The CsCl/LiCl system has been studied for over a century now. Numerous phases have been predicted – only three have hitherto been found. We present the synthesis and single‐crystal structure of the cesium lithium pentachloride Cs3Li2Cl5, predicted earlier but with a different structure. The anhydrous new phase readily reacts to Cs3LiCl4·4H2O in air. The tetrahydrate can also be obtained through the...
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