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Novel negatively charged cyanocuprate(I) host [Cu4(CN)7]3− built of tetrahedral Cu(I) coordination centers: Crystal structure of [{NH2(CH2CH2)2NCH2CH2NH2}2H][Cu4(CN)7]

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Abstract

The title inclusion compound [{NH2(CH2CH2)2NCH2CH2NH2}2H][Cu4(CN)7] was obtained as single crystals from an aqueous solution containing CuCN, KCN, andN-(2-aminoethyl)piperazine. It crystallizes in the monoclinic space groupP2/n,a = 12.3829(9),b = 8.5970(9),c = 12.6633(7) Å, β = 109.984(5)°,z = 2,R = 0.035 for 2921 independent reflections. The inclusion structure is composed of the hydrogen-bonded dimeric onium guest [{NH2(CH2CH2)2NCH2CH2NH2}2H]3+ and the negatively-charged three-dimensional host [CU4(CN)7]3− in which the CN-bridged framework Cu(I) atoms are all tetrahedral. A polyacene-like one-dimensional array of hexagons cornered by Cu(I) atoms and edged by -CN- linkages is arrayed in parallel to theb axis and stacked approximately along the c axis. The Cu(I) corner shared in the one-dimensional array extends an N-coordinate CN group along the c axis to a pair of unshared Cu(I) corners for which the C end behaves as a bifurcated ligand to build up the three-dimensional host structure. The cavity is composed of two networks of the hexagons at the top and bottom and pillared by six >CN- groups and accommodates a dimeric guest ofN-(2-aminoethyl)piperazinium cations protonated at each 4-N with the cations being hydrogen-bonded to each other through the 2-NH2 groups sharing another H+.

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Authors and Affiliations

  1. Department of Chemistry, School of Science, Kitasato University, Kitasato, Sagamihara, 228, Kanagawa, Japan

    Hidetaka Yuge

  2. Department of Chemistry, College of Arts and Sciences, The University of Tokyo, Komaba, 153, Meguro, Tokyo, Japan

    Toschitake Iwamoto

Authors
  1. Hidetaka Yuge
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  2. Toschitake Iwamoto
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Yuge, H., Iwamoto, T. Novel negatively charged cyanocuprate(I) host [Cu4(CN)7]3− built of tetrahedral Cu(I) coordination centers: Crystal structure of [{NH2(CH2CH2)2NCH2CH2NH2}2H][Cu4(CN)7]. J Incl Phenom Macrocycl Chem 26, 119–126 (1996). https://doi.org/10.1007/BF01029936

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