Supramolecular approach to crystallization of polynuclear chromium(III) aqua hydroxo complexes: synthesis and crystal structures of complexes [Cr2(OH)2(H2O)8]4+ and [Cr4(OH)6(H2O)12]6+ with cucurbit[n]uril (n = 7, 8)

Abstract

Supramolecular compounds of the compositions {[Cr2(OH)2(H2O)8](C42H42N28O14)2}-(NO3)4·18.75H2O (1) and {[Cr4(OH)6(H2O)12](C48H48N32O16)3(NO3)6·55H2O (2) were synthesized from aqueous solutions of chromium(III) nitrate and the macrocyclic cavitand cucurbit[n]uril (C6n H6n N4n O2n , where n = 7 or 8, respectively). According to the X-ray diffraction study, the polynuclear chromium aqua complexes are disposed in cavities formed by the cucurbit[n]uril molecules and are linked to these molecules through hydrogen bonds between the hydroxo and aqua ligands of the polycations and the portal oxygen atoms of the macrocycles. Compound 1 is the first example of supramolecular compounds of cucurbit[7]uril with metal aqua complexes. The isolation of the supramolecular adduct with cucurbit[8]uril 2 in the single-crystalline state allows the determination of the structure of the tetranuclear chromium aqua complex having an adamantane-like structure, [Cr4(μ2-OH)6(H2O)12]6+, which has been previously unknown in the solid state.