Issue 14, 2012

Hydro-ionothermal syntheses, crystal structures, and properties of five new divalent metal iminophosphonates

Abstract

The use of a moderately hydrophobic ionic liquid, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF4]), as a cosolvent with water, has been investigated in the synthesis of metal phosphonates. This hydro-ionothermal synthesis has been carried out through a systematic combinatorial investigation of several divalent metal chlorides and two related ligands, iminobis(methylphosphonic acid) and N-methyliminiobis(methylphosphonic acid). These reactions resulted in five new divalent metal phosphonates. We present here the synthetic techniques utilized as well as the X-ray structures and characteristic properties of each of these compounds. Co(HO3PCH2NH2CH2PO3H)2, (1), consists of sheets that are hydrogen bonded together by pairs of P–O⋯H groups. Co(H2O)2(HO3PCH2NH2CH2PO3H)2, (2), consists of chains that are connected through an extensive network of hydrogen bonds. Co(HO3PCH2NH(CH3)CH2PO3H)2, (3), is made up of sheets that are hydrogen bonded together by pairing P–O⋯H interactions. Zn3(O3PCH2NH2CH2PO3)2, (4), is isostructural to a previously reported cobalt compound which is a non-porous 3-dimensional network. CuClPO3CH2NH2CH3, (5), formed as a result of an in situ N–C bond cleavage. Ladders built of Cu–O–P–O 8-membered rings are crosslinked by bridging chloride atoms to form sheets. 1, 3, 4 and 5 have been synthesized using the hydrophobic ionic liquid 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF4]) with water as a cosolvent, while 2 has been synthesized from identical conditions in the absence of the [BdMIM][BF4]. We also report the microwave assisted hydro-ionothermal synthesis of the known polymorph of 2, Co(H2O)2(HO3PCH2NH2CH2PO3H)2, (6), synthesized in two hours providing high quality crystals in good yield. The compounds have been characterized by thermogravimetric analysis and IR spectroscopy, and their magnetic properties have been investigated.

Graphical abstract: Hydro-ionothermal syntheses, crystal structures, and properties of five new divalent metal iminophosphonates

Supplementary files

Article information

Article type
Paper
Submitted
10 Oct 2011
Accepted
12 Jan 2012
First published
23 Feb 2012

Dalton Trans., 2012,41, 3995-4006

Hydro-ionothermal syntheses, crystal structures, and properties of five new divalent metal iminophosphonates

K. J. Gagnon, A. V. Prosvirin, K. R. Dunbar, S. J. Teat and A. Clearfield, Dalton Trans., 2012, 41, 3995 DOI: 10.1039/C2DT11907B

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