Article ID Journal Published Year Pages File Type
1303964 Inorganic Chemistry Communications 2012 5 Pages PDF
Abstract

The crystal and molecular structures of two copper(II) dinuclear complexes bridged by the inorganic pyrophosphate tetraanion, namely, [Cu(bipy)(cis-H2P2O7)]2·3H2O 1 and [Cu2(terpy)2(HP2O7)]·2H2O(OH) 2, are reported (bipy = 2,2′-pyridine; terpy = 2,2′:6′,2″-terpyridine). Both compounds are characterized by two very strong OHO interactions which play a fundamental role in their crystal structure building. Compound 1 is identical to the recently reported compound 1a (Marino et al. Inorg. Chem. 50 (2011) 378–389), except for the supramolecular interaction which is revised in the present communication. Analysis of our data for 1 reveals the existence of a strong double well OH⋯O′ ↔ O⋯(HO)′ interaction around an inversion center (OO: 2.433(2) Å), which binds dinuclear units together into [100] polymeric chains. Dinuclear compound 2 is monoclinic, halved by a twofold axis bisecting it through the central O atom of the bridge. The extreme disorder found in the solvates in 2 prevented an accurate description of the solvato content, and a detailed analysis of the H-bonding scheme. However, the extremely short O⋯O = 2.473(2) Å intermolecular distance points to a (quasi) symmetrical OHO interaction.

Graphical abstractThe crystal and molecular structures of two copper(II) dinuclear complexes bridged by the inorganic pyrophosphate tetraanion, [Cu(bipy)(cis-H2P2O7)]2·3H2O 1 and [Cu2(terpy)2(HP2O7)]·2H2O(OH) 2, are reported (bipy = 2,2′-pyridine; terpy=2,2′:6′,2″-terpyridine). Both compounds are characterized by two very strong OHO interactions which play a fundamental role in their crystal structure building. The EPR spectra of powder samples do not show fine structure indicating that a zero-field splitting parameter is D = 0.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Dinuclear pyrophosphate-bridged Cu(II) complexes ► H-bonding and π⋯π interactions in supramolecular building ► Unusually strong HOH interactions in Cu(II) pyrophosphates ► EPR powder spectra

Related Topics
Physical Sciences and Engineering Chemistry Inorganic Chemistry
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