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", [Cu(6)(CN)(5)(trz)] (1) (trz = triazolate, C(2)N(3)H(2)(-)), 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 &mgr;(3)-bridging of Cu sites. An anionic layered compound, [Cu(OH(2))(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: C(7)H(2)Cu(6)N(8) (1), orthorhombic, Pcca, a = 11.108(2) Å, b = 8.886(2) Å, c = 15.397(3) Å, Z = 4; C(34)H(24)Cu(10)N(22) (2), triclinic, P&onemacr;, a = 9.1183(5) Å, b = 9.9838(6) Å, c = 12.7545(8) Å, alpha = 94.206(1) degrees, beta = 90.492(1) degrees, gamma = 112.534(1) degrees, Z = 1; C(28)H(20)Cu(6)N(14) (3), monoclinic, P2(1)/c, a = 9.7582(1) Å, b = 17.1622(2) Å, c = 9.901(1) Å, beta = 106.869(1) degrees, Z = 2; C(17)H(10)Cu(4)N(8) (4), monoclinic, P2(1)/c, a = 11.590(3) Å, b = 20.555(4) Å, c = 16.158(3) Å, beta = 103.865(5) degrees, Z = 8; C(16)H(10)Cu(3)N(7) (5), triclinic, P&onemacr;, a = 8.542(2) Å, b = 9.802(2) Å, c = 20.439(4) Å, alpha = 82.468(5) degrees, beta = 83.126(5) degrees, gamma = 79.832(5) degrees, Z = 4; C(6)Cu(5)N(6)O(4) (6), monoclinic, P2(1)/n, a = 7.466(1) Å, b = 8.952(2) Å, c = 11.116(2) Å, beta = 92.816(5) degrees, Z = 4.
Chesnut
Douglas J.
DJ
Department of Chemistry, Room 1-014, Center for Science and Technology, and W. M. Keck Center for Molecular Electronics, Syracuse University, Syracuse, New York 13244-4100.
Kusnetzow
Anakarin
A
Birge
Robert
R
Zubieta
Jon
J