Issue 5, 2010

Hydrothermal preparation, crystal structures and properties of novel Mn(ii) metal–organic frameworks with 5-nitro-1,2,3-benzenetricarboxylate and various dipyridyl ligands

Abstract

Five Mn(II) coordination polymers, [Mn3.5(O2N-btb)2(O2N–Hbtb)0.5(2,2′-bipy)2(H2O)4]·1.5H2O (1), [Mn3(O2N-btb)2(4,4′-bipy)3(H2O)2]·2H2O (2), [Mn3(O2N-btb)2(bpe)(H2O)8]·bpe(3), [Mn3(O2N-btb)2(bpa)(H2O)5]·0.5bpa H2O (4) and [Mn3(O2N-btb)2(bpp)2(H2O)4] (5), were prepared by hydrothermal reactions of Mn(II) acetate with O2N–H3btb (O2N–H3btb = 5-nitro-1,2,3-benzenetricarboxylic acid) in the presence of different dipyridyl co-ligands (2,2′-bipy = 2,2′-bipyridyl, 4,4′-bipy = 4,4′-bipyridyl, bpe = 1,2-bi(4-pyridyl)ethene, bpa = 1,2-bi(4-pyridyl)ethane and bpp = 1,3-di(4-pyridyl)propane). Their crystal structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra and TG analyses. Complex 1 shows a 3D (3,5)-connected coordination framework with (42·5)(4·122)(4·5·7)2(42·5·6·7·9·123·13) topology. Notably, the μ7-bridging mode of O2N-btb in 1 has never been found in coordination complexes with 1,2,3-benzenetricarboxylate and its derivatives. Complex 2 exhibits a 3D (4,5)-connected framework with (42·67·8)(64·82)(42·64) topology. Complex 3 shows a 2D 3-connected network with 63 topology. Complex 4 is a 2D (3,4,5)-connected framework with (43)(3·4·5)(3·42·83)(3·4·5·6·72·82·9·10)(43·52·62·72·8) topology, whereas the structure of 5 has a 2D (3,4)-connected (42·6)(42·63·8) framework. The 2D layers in 3 are extended to form a 2-fold interpenetrated 3D supramolecular network, and those in 4 and 5 afford the 3D supramolecular structures via H-bonding interactions. A structural comparison of these complexes demonstrates that the characteristics of auxiliary ligands play a key role in governing the coordination motifs and the final supramolecular lattices. Moreover, the magnetic properties of these Mn(II) complexes were investigated and discussed in detail.

Graphical abstract: Hydrothermal preparation, crystal structures and properties of novel Mn(ii) metal–organic frameworks with 5-nitro-1,2,3-benzenetricarboxylate and various dipyridyl ligands

Supplementary files

Article information

Article type
Paper
Submitted
09 Nov 2009
Accepted
19 Nov 2009
First published
22 Dec 2009

CrystEngComm, 2010,12, 1439-1449

Hydrothermal preparation, crystal structures and properties of novel Mn(II) metal–organic frameworks with 5-nitro-1,2,3-benzenetricarboxylate and various dipyridyl ligands

L. Ma, B. Liu, L. Wang, J. Hu and M. Du, CrystEngComm, 2010, 12, 1439 DOI: 10.1039/B923522C

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