A dihydroxidotetracopper(II) framework supported by 4,4′‐(adamantane‐1,3‐diyl)bis(1,2,4‐triazole) and benzene‐1,3,5‐tricarboxylate bridges |
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Authors: | Ganna A Senchyk Andrey B Lysenko Harald Krautscheid Joachim Sieler Konstantin V Domasevitch |
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Abstract: | The new bifunctional ligand 4,4′‐(adamantane‐1,3‐diyl)bis(1,2,4‐triazole) (tr2ad) and benzene‐1,3,5‐tricarboxylate sustain complementary coordination bridging for the three‐dimensional framework of polybisμ3‐4,4′‐(adamantane‐1,3‐diyl)bis(1,2,4‐triazole)‐κ3N1:N2:N1′]bis(μ4‐benzene‐1,3,5‐tricarboxylato‐κ4O1:O1′:O3:O5)di‐μ3‐hydroxido‐κ6O:O:O‐tetracopper(II)] dihydrate], {Cu4(C9H3O6)2(OH)2(C14H18N6)2]·2H2O}n. The net node is a centrosymmetric (μ3‐OH)2Cu4 cluster Cu—O = 1.9525 (14)–2.0770 (15) Å and Cu...Cu = 3.0536 (5) Å] involving two independent copper ions in tetragonal pyramidal CuO4N and trigonal bipyramidal CuO3N2 environments. One carboxylate group of the anion is bridging and the other two are monodentate, leading to the connection of three hydroxide clusters and the generation of neutral coordination layers separated by 9.3583 (5) Å. The interlayer linkage is effected by μ3‐tr2ad ligands, with one triazole group N1:N2‐bridging and the second monodentate Cu—N = 1.9893 (19), 2.010 (2) and 2.411 (2) Å]. In total, the hydroxide clusters are linked to six close neighbors within the carboxylate layer and to four neighbors via tr2ad bridges. Hydrogen bonding of solvent water molecules to noncoordinated triazole N atoms and carboxylate groups provides two additional links for the net, which adopts a 12‐connected topology corresponding to hexagonal closest packing. The study also introduces a new type of bis(triazole) ligand, which may find wider applications for supramolecular synthesis. |
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