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Title: Assembling metal phosphonates in the presence of monodentate-terminal and bidentate-bridging pyridine ligands. Use of non-covalent and covalent-coordinate interactions to build polymeric metal-phosphonate architectures
Keywords: Butyl Phosphate Complexes
Ray Crystal-Structures
Pyrazole Ligands
Copper Phosphonates
Cage Structures
Model Compounds
Issue Date: 2008
Citation: DALTON TRANSACTIONS, (39), 5358-5367
Abstract: The cubic transition metal phosphonates [(BuPO3M)-Bu-t(2-apy)](4) (M= Zn (1), Co (2), whose core resembles the D4R SBU of zeolites, have been synthesized from a reaction between the corresponding metal acetate, tert-butylphosphonic acid and 2-aminopyridine (2-apy) at room temperature. X-Ray structure determination reveals that the molecules of 1 and 2, which crystallize in the tetragonal I4(1)/a space group with crystallographically imposed (4) over bar symmetry, form a 3-D supramolecular assembly aided by N-H center dot center dot center dot O hydrogen bonding. When the same reaction was carried out by using a bridging bidentate Lewis base such as 4,4'-bipyridine, insoluble precipitate is obtained for both zinc and cobalt. In the case of other metal salts such as copper, manganese and nickel, however, one-dimensional polymeric compounds such as [M((BuPO3H)-Bu-t) 2(4,4 '-bipy)(H2O)(2)](n) (M= Cu (3), Mn (4)), [{Ni(4,4 '-bipy)(H2O)(4)}-{ (BuPO3H)-Bu-t}(2){H2O}](n) (5) have been isolated. The solid-state structures of 3-5 have been determined by single crystal X-ray diffraction studies. Compounds 3 and 4 are isostructural and crystallize in the triclinic P (1) over bar space group with two phosphonate ligands coordinated to the metal centers in a [1.100] fashion, whereas in the case of compound 5, the polymeric backbone is formed by Ni-4,4 '-bipy units and the phosphonate anions show no bonding interaction to the metal. The 1-D polymeric chains of 3-5 organize in the solid-state as 3-D supramolecular assemblies with the aid of extensive hydrogen bonding interaction between coordinated water molecules and P-OH or P=O groups of the phosphonate ligands.
ISSN: 1477-9226
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