Issue 88, 2014

Unusual solvent-mediated hydrolysis of dicarboxylate monoester ligands in copper(ii) complexes toward simultaneous crystallization of new dicarboxylate derivatives

Abstract

A series of copper(II) complexes, [Cu(cmb)2(im)2] (1), [Cu(cmn)2(im)4] (3) and [Cu(cmp)2(im)2] (5), bearing various dicarboxylate monoester derivatives, [cmb = 2-carbomethoxy-benzoate; cmn = 8-carbomethoxy-naphthalene-1-carboxylate; cmp = 2-carbomethoxy-phenyl-2-benzoate], were generated from copper(II) acetate, imidazole (im) and an aromatic anhydride [phthalic, 1,8-naphthalic or biphenic anhydride for 1, 3 or 5, respectively]. Unusual solvent-mediated transformations of the crystals of two copper dicarboxylate monoester complexes to new crystals of the corresponding dicarboxylate derivatives by the hydrolysis of ester groups were observed and investigated. Crystals of 1 underwent a transformation to crystals of copper(II) phthalate 2D coordination polymer {[Cu2(pht)2(im)4·H2O]·H2O}n (2) (pht = phthalate) upon moistening with aqueous methanol. Similarly, crystals of 3, after wetting with aqueous dimethylformamide (DMF), were transformed to crystals of a metallacycle [Cu(nap)(im)(DMF)(H2O)]2 (4) (nap = 1,8-naphthalenedicarboxylate). In contrast to 1 and 3, the crystals of 5 were found to be stable under ambient conditions. Compounds 1–5 were characterized by IR and UV-vis spectroscopy and single crystal and powder X-ray diffraction. Topological analysis showed that in the 12 transformation the overall 2D network topology was modified from the 4-connected H-bonded sql net [Shubnikov tetragonal plane net] to the 3-connected metal–organic hcb net [Shubnikov hexagonal plane net/(6, 3)], whereas no topology change was detected during an analogous 34 transformation, with both structures exhibiting topologically equal H-bonded sql nets.

Graphical abstract: Unusual solvent-mediated hydrolysis of dicarboxylate monoester ligands in copper(ii) complexes toward simultaneous crystallization of new dicarboxylate derivatives

Supplementary files

Article information

Article type
Paper
Submitted
19 Jun 2014
Accepted
11 Sep 2014
First published
11 Sep 2014

RSC Adv., 2014,4, 47876-47886

Author version available

Unusual solvent-mediated hydrolysis of dicarboxylate monoester ligands in copper(II) complexes toward simultaneous crystallization of new dicarboxylate derivatives

J. K. Nath, A. M. Kirillov and J. B. Baruah, RSC Adv., 2014, 4, 47876 DOI: 10.1039/C4RA05776G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements