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.