Abstract
We obtained previously unknown K 3{Li[IrO 4]} in the form of dark-red elongated single crystals, by heating well-ground mixtures of Li 2IrO 3 and KO 0.51 (molar proportions Ir:K, 1.00:3.76) in an “Ag cylinder” (at 1073 K for 71 days). K 3{Li[IrO 4]} crystallizes as mC36 in the space group C2/ c, with a = 1067.29(9) pm, b = 986.36(8) pm, c = 587.70(5) pm and β = 103.938(8)°; Z = 4. Refinement of the structure with 949 reflections ( F 0 > 3 σ( F 0)) from 1032 independent reflections (merged from 4137 I 0( hkl)) gave R = 0.0351 and R w = 0.0378. The structure is characterized by Vierer single chains ∞ 1[(O 2 2 LiO 2IrO 2 2 ) 2] isolated from one another. Their arrangement corresponds to the configuration of a densest packing of “tree-trunks”. The effective coordination numbers, mean fictive ionic radii and the Madelung part of the lattice energy, as well as the charge distribution are calculated and discussed.
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