Ligand influences on copper cyanide solid-state architecture: Flattened and fused "slinky", corrugated sheet, and ribbon motifs in the copper-cyanide-triazolate-organoamine family

A series of novel composite inorganic-organic materials from the copper-cyanide-triazolate-organoamine system have been isolated and structurally characterized. An unusual interpenetrating layered structure type composed of fused and flattened "slinkies", [Cu₆(CN)₅(trz)] (1) (trz = triazolate, C₂N₃H₂^-), a complex corrugated layer structure, [Cu₅(CN)₃(trz)₂(bpy)] (2), and a series of increasingly intricate one-dimensional ribbons, [Cu₃(CN)₂(trz)(bpy)], [Cu₃(CN)₂(trz)(phen)], and [Cu₄(CN)₃(trz)(phen)] (3-5), have been isolated from hydrothermal media. All trz ligands are deprotonated and participate in μ₃-bridging of Cu sites. An anionic layered compound, [Cu(OH₂)₄]-[Cu₄(CN)₆] (6), composed of {Cu₆(CN)₆} rings with tetraaquacupric dications intercalated into alternate interlamellar spaces, has also been characterized upon the slow evaporation of the mother liquor of 1. The syntheses and structural characterizations of compounds 1-6 by single-crystal X-ray diffraction and FTIR microscopy are discussed in relation to the supramolecular chemistry of other copper cyanide solid-state materials. Crystal data: C₇H₂CU₆N₈ (1), orthorhombic, Pcca, a = 11.108(2) Å, b = 8.886(2) Å, c = 15.397(3) Å, Z = 4; C₃₄H₂₄Cu₁₀N₂₂ (2), triclinic, P1̄, a = 9.1183(5) Å, b = 9.9838(6) Å, c = 12.7545(8) Å, α = 94.206(1)°, β= 90.492(1)°, γ = 112.534(1)°, Z = 1; C₂₈H₂₀Cu₆N₁₄ (3), monoclinic, P2₁/c, a = 9.7582(1) Å, b = 17.1622(2) Å, c = 9.901(1) Å, β = 106.869(1)°, Z = 2; C₁₇H₁₀Cu₄N₈ (4), monoclinic, P2₁/c, a = 11.590(3) Å, b = 20.555(4) Å, c = 16.158(3) Å, β= 103.865(5)°, Z = 8; C₁₆H₁₀Cu₃N₇ (5), triclinic, P1̄, a = 8.542(2) Å, b = 9.802(2) Å, c = 20.439(4) Å, α = 82.468(5)°, β= 83.126(5)°, γ = 79.832(5)°, Z = 4; C₆Cu₅N₆O₄ (6), monoclinic, P2₁,/n, a = 7.466(1) Å, b = 8.952(2) Å, c = 11.116(2) Å, β= 92.816(5)°, Z = 4.