The Encapsulation of Ferrocyanide by Copper(II) Complexes of Tripodal Tetradentate Ligands. Novel H-Bonding Networks Incorporating Heptanuclear and Pentanuclear Heterometallic Assemblies Richard J. Parker, ² Leone Spiccia,* ,² Stuart R. Batten, ² John D. Cashion, ‡ and Gary D. Fallon ² School of Chemistry, PO Box 23, Monash University, Victoria 3800, Australia, and Department of Physics, PO Box 27, Monash University, Victoria 3800, Australia ReceiVed December 27, 2000 Substitution of the weakly binding aqua ligand in [Cu(tren)OH 2 ] 2+ and [Cu(tpa)OH 2 ] 2+ (tren ) tris(2-aminoethyl)- amine; tpa ) tris(2-pyridylmethyl)amine) by a cyano ligand on ferricyanide results in the assembly of heteropolynuclear cations around the cyanometalate core. In water, the reduction of the Fe III core to Fe II generates complexes that feature heteropolycations in which ferrocyanide is encapsulated by the Cu II moieties: [{Cu(tpa)- CN} 6 Fe][ClO 4 ] 8 ‚3H 2 O 1,[{Cu(tren)CN} 6 Fe][ClO 4 ] 8 ‚10H 2 O 2,[{Cu(tren)CN} 6 Fe][Fe(CN) 6 ] 2 [ClO 4 ] 2 ‚15.8H 2 O 3, and [{Cu(tren)CN} 6 Fe][{Cu(tren)CN} 4 Fe(CN) 2 ][Fe(CN) 6 ] 4 ‚6DMSO‚21H 2 O 4. The formation of discrete molecules, in preference to extended networks or polymeric structures, has been encouraged through the use of branched tetradentate ligands in conjunction with copper(II), a metal center with the propensity to form five-coordinate complexes. Complex 3 crystallizes in the monoclinic space group P2 1 /c (#14) with a ) 14.8674(10), b ) 25.9587(10), c ) 27.5617(10) Å,  ) 100.8300(10) °, and Z ) 4, and it is comprised of almost spherical heptanuclear cations, [{Cu(tren)CN} 6 Fe] 8+ , whose charge is balanced by two ferricyanide and two perchlorate counteranions. Complex 4 crystallizes in the triclinic space group P1 (# 1) with a ) 14.8094(8), b ) 17.3901(7), c ) 21.1565(11) Å, R) 110.750(3),  ) 90.206(2), γ ) 112.754(3) °, and Z ) 1, and it is comprised of the heptanuclear [{Cu(tren)CN} 6 Fe] 8+ cation and pentanuclear [{Cu(tren)CN} 4 Fe(CN) 2 ] 4+ cation, whose terminal cyano ligands are oriented trans to each other. The charge is balanced exclusively by ferricyanide counteranions. In both complexes, H-bonding interactions between hydrogens on primary amines of the tren ligand, terminal cyano groups of the ferricyanide counterions, and the solvent of crystallization generate intricate 3D H-bonding networks. 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