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Issue 12, 2018
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From a square core to square opening: structural diversity and magnetic properties of the oxo-bridged [CrIIINbV] complexes

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Abstract

Three heterometallic oxo-bridged compounds, [Cr2(phen)4(μ-O)4Nb2(C2O4)4]·2H2O (1; phen = 1,10-phenanthroline), [Cr2(terpy)2(H2O)2(μ-O)4Nb2(C2O4)4]·4H2O (2; terpy = 2,2′;6′,2′′-terpyridine) and [Cr(terpy)(C2O4)(H2O)][Cr2(terpy)2(C2O4)2(μ-O)2Nb(C2O4)2]·3H2O (3), have been synthesized using a building block approach and characterized by IR spectroscopy, single-crystal and powder X-ray diffraction, magnetization measurements, and DFT calculations. The molecular structures of 1 and 2, crystallizing in P42212 and P21/n space groups, respectively, contain a square-shaped {CrIII2(μ-O)4NbV2} unit, while that of complex salt 3 (P[1 with combining macron] space group) consists of a mononuclear cation containing CrIII and trinuclear anions in which two CrIII ions are bridged by a –O–NbV–O– fragment. Besides hydrogen-bonding patterns resulting in a 1D- or 3D-supramolecular arrangement in 1–3, an unusual intermolecular contact has been noticed between parallel oxalate moieties occurring due to the electrostatic attraction of electron-rich carbonyl oxygen and severely electron-depleted carbon atoms in the crystal packing of 2. The antiferromagnetic coupling observed in all three compounds, determined from magnetization measurements (J = −13.51(2), −8.41(1) and −7.44(4) cm−1 for 1, 2 and 3, respectively) and confirmed by DFT calculations, originates from two CrIII ions with spin 3/2 interacting through diamagnetic –O–NbV–O– bridge(s).

Graphical abstract: From a square core to square opening: structural diversity and magnetic properties of the oxo-bridged [CrIIINbV] complexes

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Supplementary files

Article information


Submitted
14 Dec 2017
Accepted
05 Feb 2018
First published
06 Feb 2018

Dalton Trans., 2018,47, 4183-4190
Article type
Paper

From a square core to square opening: structural diversity and magnetic properties of the oxo-bridged [CrIIINbV] complexes

M. Jurić, L. Androš Dubraja, J. Popović, K. Molčanov, F. Torić, D. Pajić and I. Lončarić, Dalton Trans., 2018, 47, 4183
DOI: 10.1039/C7DT04724J

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