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", [Cu-6(CN)(5)(trz)] (1) (trz = triazolate, C2N3H2-), a complex corrugated layer structure, [Cu-5(CN)(3)(trz)(2)(bpy)] (2), and a series of increasingly intricate one-dimensional ribbons, [Cu-3(CN)(2)(trz)(bpy)], [Cu-3(CN)(2)(trz)(phen)], and [Cu-4(CN)(3)(trz)(phen)] (3-5), have been isolated from hydrothermal media. All trz ligands are deprotonated and participate in mu(3)-bridging of Cu sites. An anionic layered compound, [Cu(OH2)(4)][Cu-4(CN)(6)] (6), composed of {Cu-6(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) Angstrom, b = 8.886(2) Angstrom, c = 15.397(3) Angstrom, Z = 4; C34H24Cu10N22 (2), triclinic, P (1) over bar, a = 9.1183(5) Angstrom, b = 9.9838(6) Angstrom, c = 12.7545(8) Angstrom, alpha = 94.206(1)degrees, beta = 90.492(1)degrees, gamma = 112.534(1)degrees, Z = 1; C28H20Cu6N14 (3), monoclinic, P2(1)/c, a = 9.7582(1) Angstrom, b = 17.1622(2) Angstrom, c = 9.901(1) Angstrom, beta = 106.869(1)degrees, Z = 2; C17H11Cu4N8 (4), monoclinic, P2(1)/c, a = 11.590(3) Angstrom, b = 20.555(4) Angstrom, c = 16.158(3) Angstrom, beta = 103.865(5)degrees, Z = 8; C16H10Cu3N7 (5), triclinic, P (1) over bar, a = 8.542(2) Angstrom, b = 9.802(2) Angstrom, c = 20.439(4) Angstrom, alpha = 82.468(5)degrees, beta = 83.126(5)degrees, gamma = 79.832(5)degrees, Z = 4; C6Cu5N6O4 (6), monoclinic, P2(1)/n, a = 7.466(1) Angstrom, b = 8.952(2) Angstrom, c = 11.116(2) Angstrom, beta = 92.816(5)degrees, Z = 4.