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Reactions of CuI with N-methylpyrazinium iodide, (pyr)I, N-methyl-4,4′-bipyridinium iodide, (bp4)I and N-methyl-2,2′-bipyridinium iodide, (bp2)I, in organic solvents led to three novel types of copper(I) complexes of stoichiometries (pyr)Cu 2 I 3 , (bp4)Cu 3 I 4  and (bp2)Cu 2 I 3 . In all of them the cations are n-σ-bonded to copper(I) through donation of their unshared electron pairs. (pyr)Cu 2 I 3  crystallizes with an ionic structure (trigonal, R 3 c, hexagonal axes a = 3053(2), c = 671.9(3) pm, Z = 18). Polymeric cations  ∞  1 [((pyr)CuI 3/3 ) 3 ] 3+  and anions  ∞  1 [CuI 4/2 ]-form parallel rod packings. The structure motif of the cations can be described as a columnar part of the β-CuI structure in which the copper and iodine atoms are also arranged to Cu 3 I 3  rings.

zeitschrift für naturforschung b

Synthese und Strukturuntersuchungen von Iodocupraten(I) / Synthesis and Structure Investigations of Iodocuprates(I): XIV. Iodocuprate(I) mit n-σ-gebundenen Kationen [1]/ XIV. Iodocuprates(I) with n-σ-Bonded Cations [1]