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Journal Article

Selenium-Rich Octanuclear Iridium Clusters with Mixed-Valent Selenium Ligands in the Densest Known Packing of Ellipsoids

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Ruck,  Michael
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Stolze, K., Günther, A., Hoffmann, H. C., & Ruck, M. (2014). Selenium-Rich Octanuclear Iridium Clusters with Mixed-Valent Selenium Ligands in the Densest Known Packing of Ellipsoids. Zeitschrift für anorganische und allgemeine Chemie, 640(5), 719-723. doi:10.1002/zaac.201300581.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0019-16BD-B
Abstract
Dark-red air-stable crystals of Ir(8)Se(28)Br(14<bold>)2</bold>H2O were obtained by reacting iridium in an excess of selenium and selenium tetrabromide at 300 degrees C for one week. The crystal structure is monoclinic (space group P2(1)/n) with a = 1274.66(3) pm, b = 1211.48(3) pm, c = 1743.82(4) pm, and = 91.227(1)degrees at 296(1) K. The structure consists of uncharged clusters Ir8Se28Br14 = (Ir3+)(8)(Se-2(2-))(Se-4(2-))(6)(SeBr2)(2)(Br-)(10) with two water molecules attached to each of them. Selenium adopts three different oxidation states, -I in the diselenide dumbbell, -I and +/- 0 in the tetraselenide chains, and +II in the SeBr2 units. The iridium(III) cations are coordinated octahedrally by selenium atoms and bromide ions. The octahedra share common vertices, while the oligoselenide anions provide high intra-cluster connectivity: (6)-(2) in the case of Se-2(2-) and (4)-(3) for Se-4(2-). In parts the cluster resembles a cut-out of the rhombohedral Ir3Se8 framework structure. The ellipsoidal clusters form an excellent approximation of the mathematically predicted densest known packing of ellipsoids, featuring the coordination number of 14.