Squeezing the [Cu-OH...H2O-Cu]3+ bridge by cryptate encapsulation

Treatment of cryptand L(1) with Cu(II) generates a H3O2(-)-bridged dicopper(II) cryptate, 2, where the guest anion has responded to steric constraint by a significant shortening of the O-O distance to 2.325(9) A; computational optimization at the B3LYP/6-31(d) level suggests that the bridging O-H...O H-bond is bent (approximately 157 degrees) but that the barrier to interchange of the bridging H atom is low (<4 kJ mol(-1)). This cryptate, rather than the [Cu2L(1)muCN]3+ species recently claimed to derive from cleavage of the C-C bond of the solvent, is the product of acetonitrile recrystallization of the initially formed reaction product, 1.