Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Der strukturdirigierende Einfluß von α, ω-Alkandiammoniumionen auf die Bildung von Cyanocupraten(I)

The Structure-directing Influence of α, ω-Alkanediammonium Ions on the Formation of Cyanocuprates(I) The alkane-1, n-diammonium-hexacyanotetracuprates(I) (n = 2 - 4) [NH₃(CH₂)₂NH₃][Cu₄(CN)₆]·2H₂O ( 1 ), [NH₃(CH₂)₃NH₃][Cu₄(CN)₆]·H₂O ( 2 ) and [NH₃(CH₂)₄NH₃][Cu₄(CN)₆]·2H₂O ( 3 ) and the pentane-1, 5-diammonium-tetradecacyanooctacuprate(I) [NH₃(CH₂)₅NH₃]₃[Cu₈(CN)₁₄]·3H₂O ( 4 ) were obtained by hydrothermal reaction of ethane-1, 2-diamine, propane-1, 3-diamine, butane-1, 4-diamine and pentane-1, 5-diamine with CuCN, NaCN and formic acid. In the crystal structures of compounds 1 - 3 anionic layers of connected (CuCN)₆-rings which vary in conformation are piled up containing rigid all-anti α, ω-alkanediammonium ions as spacers. The dications and water molecules are linked to chains by hydrogen bridges, penetrating the anionic layers in a needle-like fashion. In contrast the deformable dications [NH₃(CH₂)₅NH₃]²⁺ in 4 are integrated in cavities of a three-dimensional cyanocuprate(I). Crystal structure data: 1 , monoclinic, P2₁/c, a = 6.982(3) Å, b = 8.579(4) Å, c = 13.054(6) Å, β = 92.806(10)°, V = 780.9(6) ų, Z = 2, d_c = 2.145 gcm^-1, R₁ = 0.094; 2 , orthorhombic, C222₁, a = 8.715(2) Å, b = 14.764(3) Å, c = 12.411(2) Å, V = 1596.7(5) ų, Z = 4, d_c = 2.098 gcm^-1, R₁ = 0.026; 3 , orthorhombic, Pnn2, a = 7.276(2) Å, b = 8.612(2) Å, c = 14.731(3) Å, V = 923.1(3) ų, Z = 2, d_c = 1.916 gcm^-1, R₁ = 0.036; 4 , triclinic, P1, a = 8.113(5) Å, b = 11.068(5) Å, c = 13.689(5) Å, α = 91.270(5)°, β = 99.718(5)°, γ = 103.994(5)°, V = 1173.1(10) ų, Z = 1, d_c = 1.746 gcm^-1, R₁ = 0.057.     

Konformation und Vernetzung von (CuCN)6‐Ringen in polymeren Cyanocupraten(I) [Cu2(CN)3—] (n = 2, 3)

Conformation and Cross Linking of (CuCN)₆‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu₂(CN)₃^—] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu₂(CN)₃] · H₂O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu₂(CN)₃] · H₂O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH₂(Me)₂]equation/tex2gif-stack-11.gif[Cu₂(CN)₃] ( 3 ), [NH₂(iPr)₂]equation/tex2gif-stack-12.gif[Cu₂(CN)₃] ( 4 ), [NH₂(Pr)₂]equation/tex2gif-stack-13.gif[Cu₂(CN)₃] ( 5 ) and [NH₂(secBu)₂]equation/tex2gif-stack-14.gif[Cu₂(CN)₃] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)₆‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P2₁/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)ų, Z = 4, d_c = 2.728 gcm^—1, R₁ = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)ų, Z = 8, d_c = 2.937 gcm^—1, R₁ = 0.028; 3 , orthorhombic, Pna2₁, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)ų, Z = 4, d_c = 2.023 gcm^—1, R₁ = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)ų, Z = 8, d_c = 1.702 gcm^—1, R₁ = 0.022; 5 , monoclinic, P2₁/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)ų, Z = 4, d_c = 1.598 gcm^—1, R₁ = 0.039; 6 , monoclinic, P2₁/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)ų, Z = 8, d_c = 1.525 gcm^—1, R₁ = 0.070.     

γ-Cyanooxazolines: an interesting synthon from oxazoline cyanocuprate addition to conjugated cyanoalkenes

The oxazoline cyanocuprates addition to conjugated cyanoalkenes, was shown to be an efficient method for the synthesis of a variety of γ-cyanooxazolines, interesting intermediates with different, but convertible, functions in a symmetrical position.     

Diastereoselective synthesis of α,β-unsaturated systems

Functionalized Z-vinylic tellurides were used in substitution reactions with lower order cyanocuprates leading to α,β-unsaturated ketones and esters in good yields. In the case of acyclic tellurides, the product was obtained in high diastereoselectivity. The control of the stereoselectivity was achieved by simple change of the reaction temperature.     

The Crystal Structures of a Lower Order and a “Higher Order” Cyanocuprate: [tBuCu(CN)Li(OEt2)2]∞ and [tBuCutBu{Li(thf)(pmdeta)}2CN]

Different types of bonding are present in cyanocuprates 1 and 2 , whose crystal structures could be determined (the drawings below show the important structural characteristics). Accordingly, 1 is a lower order cyanocuprate of the type RCu(CN)Li, whereas 2 , which is of the type R₂Cu(CN)Li₂, does not exist as a “higher order” cyanocuprate with Cu–CN bonds, but rather as a cyano-Gilman cuprate.