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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Synthesis, decomposition studies and crystal structure of a three-dimensional CuCN network structure with protonated
Christopher Koenigsmann1, Leena N Rachid1, Christina M Sheedy1
1Department of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA.
Abstract:
The compound poly[2-hydroxy-N-methylethan-1-aminium [μ3-cyanido-κ3C:C:N-di-μ-cyanido-κ4C:N-dicuprate(I)]], {(C3H10NO)[Cu2(CN)3]}n or [meoenH]Cu2(CN)3, crystallizes in the tetragonal space group P43. The structure consists of a three-dimensional (3D) anionic CuICN network with noncoordinated protonated N-methylethanolamine cations providing charge neutrality. Pairs of cuprophilic Cu atoms are bridged by the C atoms of μ3-cyanide ligands, which link these units into a 43 spiral along the c axis. The spirals are linked together into a 3D anionic network by the two other cyanide groups. The cationic moieties are linked into their own 43 spiral via N-H...O and O-H...O hydrogen bonds, and the cations interact with the 3D network via an unusual pair of N-H...N hydrogen bonds to one of the μ2-cyanide groups. Thermogravimetric analysis indicates an initial loss of the base cation and one cyanide as HCN at temperatures in the range 130-250 °C to form CuCN. We show how loss of a specific cyanide group from the 3D CuCN structure could form the linear CuCN structure. Further heating leaves a residue of elemental copper, isolated as the oxide.
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