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Stolze, Karoline
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article
Bridging Nonaselenium Ring in [Se9(IrBr3)2], and Three Modifications of the Mononuclear Complex [IrBr3(SeBr2)3]
Abstract
<p>The reaction of iridium powder with an excess of selenium and SeBr<sub>4</sub> yielded lustrous, vermillion crystals of the mononuclear iridium complex [IrBr<sub>3</sub>(SeBr<sub>2</sub>)<sub>3</sub>]. The transition metal is coordinated octahedrally by three SeBr<sub>2</sub> and three bromide ligands with facial or meridional configuration. Three different modifications were obtained under similar conditions: a-fac-IrBr<sub>3</sub>(SeBr<sub>2</sub>)<sub>3</sub>, space group P{1}, with a = 789.4(1) pm, b = 830.4(1) pm, c = 1334.4(1) pm, α = 81.634(5)°, β = 84.948(5)°, γ = 67.616(4)°; m-fac-IrBr<sub>3</sub>(SeBr<sub>2</sub>)<sub>3</sub>, space group P2<sub>1</sub>/n, with a = 1205.3(1) pm, b = 962.4(1) pm, c = 1383.9(1) pm, β = 91.114(3)°; mer-IrBr<sub>3</sub>(SeBr<sub>2</sub>)<sub>3</sub>, space group P2<sub>1</sub>/n with a = 859.7(1) pm, b = 1284.3(1) pm, c = 1437.5(1) pm, β = 94.427(3)°. A lower bromine content in the starting composition resulted in shiny, deep-red crystals of [Se<sub>9</sub>(IrBr<sub>3</sub>)<sub>2</sub>]. X-ray diffraction on a single-crystal revealed a tetragonal lattice (space group I4<sub>1</sub>/a) with a = 1245.4(1) pm and c = 2486.8(1) pm at 296(1) K. In the [Se<sub>9</sub>(IrBr<sub>3</sub>)<sub>2</sub>] complex, a crown-shaped uncharged Se<sub>9</sub> ring coordinates two iridium(III) cations as a bridging bis-tridentate ligand. Three terminal bromide ions complete the distorted octahedral coordination of each transition metal atom.</p>