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Updated: May 28, 2025
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Published on: February 11, 2012
Synthesis and Crystal Structure of Zn3(OAc)8[EMIM]2, a Novel Ionic Compound with Isolated Homoleptic Trinuclear Metal
Przemyslaw Dera1, Edward Bruffey2, Natalia Majewska1,3
1Hawai'i Institute of Geophysics and Planetology, University of Hawai'i at Ma̅noa, 1680 East West Road, Post 602, Honolulu, Hawaii 96822, United States.
Abstract:
We synthesized and characterized a novel anhydrous zinc(II) aceto 1-ethyl-3-methylimidazolium (EMIM) coordination compound with the simplified empirical formula Zn3(OAc)8[EMIM]2. The title compound is structurally related to recently reported Mn4(OAc)10[EMIM]2, and Fe4(OAc)10[EMIM]2. While in the other two ionic salts metal cations were organized in infinite chains of corner-sharing octahedra, Zn2+ in Zn3(OAc)8[EMIM]2 assumes two different coordination environments, including Zn(OAc)6 octahedra and Zn(OAc)4 tetrahedral sites, linked together by carboxylate oxygen-sharing to form isolated [Zn3(OAc)8]2- trinuclear linear clusters. The homoleptic trinuclear cluster configuration of zinc is important because it provides a distinct coordination environment that can influence the cluster's electronic and structural properties, offering unique opportunities for designing novel materials with specific characteristics. This configuration is unique as it avoids the presence of water in the coordination shell, which can alter the behavior of the cluster, thus enabling more controlled and predictable interactions in various applications, including catalysis. Similar to the Mn and Fe compounds, in the title compound, the EMIM+ moieties do not interact directly with the Zn2+ and contribute to the structure framework of the compound through hydrogen bonds with the acetate anions. Two different polymorphs of Zn3(OAc)8[EMIM]2 were crystallized and characterized, one with monoclinic symmetry (α-phase) and one with triclinic symmetry (β-phase). The α-phase has a melting temperature of 80 °C, while the β-phase melts at ∼81 °C, thus both can be considered as metal-containing ionic liquids. Both forms of the Zn3(OAc)8[EMIM]2 compound are porous and plausibly capable of accommodating other types of molecules.
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