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The crystal structure of {[Cu2Br3]n[Cu(H-Leof)2]· 2H2O} (1) comprises of [Cu(H-Leof)2] + cations, [Cu2Br3]nanions and lattice water molecules. And anion is a 1-D chain formed through alternative Cu-Br dimer and triangular geometry. CCDC: 274841.