New planar polynitrile dianion and its first coordination polymer with unexpected short M⋯M contacts (tcno2− = [(NC)2CC(O)C(CN)2]2−)

doi:10.1016/j.inoche.2008.04.038

Inorganic Chemistry Communications

Volume 11, Issue 8, August 2008, Pages 921-924

https://doi.org/10.1016/j.inoche.2008.04.038 Get rights and content

Abstract

A new planar polynitrile dianion ([tcno]²⁻ = [(NC)₂CC(O)C(CN)₂]²⁻) has been synthesized as its potassium salt, K₂[tcno] (1). The crystallization of 1 by the slow evaporation of an aqueous solution at room temperature gave two types of colourless crystals having two different shapes [1-A: fine plates and 1-B: needles] for which the crystal structure determinations showed similar geometries for the polynitrile anion in both the structures. The combination of this novel dianion with Cu(II) led to the coordination complex [Cu(tcno)₂(H₂O)₂] (2), which constitutes the first coordination complex of this dianion. The structure of 2 can be described as a coordination polymer in which the organic dianion acts as a μ₃-bridging ligand. Despite the fact that the Cu⋯Cu bridges have a large number of atoms, the Cu⋯Cu distance observed through this ligand is relatively short (Cu⋯Cu 3.644 Å) compared to those reported for several polynitrile metal complexes (>6 Å).

Graphical abstract

A new planar polynitrile dianion ([tcno]²⁻ = [(NC)₂CC(O)C(CN)₂]²⁻) has been synthesized and characterized. Its combination with Cu(II) metal ion led to the coordination complex [Cu(tcno)₂(H₂O)₂], which was characterized as the first example in which this anion acts as a ligand. The monodimensional structure in which the organic dianion acts as a μ₃-bridging ligand showed very short Cu⋯Cu contacts (3.644 Å) compared to those reported for several polynitrile metal complexes (>6 Å).

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Acknowledgements

The authors acknowledge the CNRS (Centre National de la Recherche Scientifique), the European Union for financial support (MAGMANet network of excellence and COST Action D35-WG-0011-05) and the Spanish Ministerio de Educación y Ciencia (Projects MAT2004-03849 and CSD 2007-00010 Consolider-Ingenio in Molecular Nanoscience). C.A. thanks the Ministère de l’Education Nationale, de la Recherche et de la Technologie for a PhD grant.

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New planar polynitrile dianion and its first coordination polymer with unexpected short M⋯M contacts (tcno2− = [(NC)2CC(O)C(CN)2]2−)

Abstract

Graphical abstract

Section snippets

Acknowledgements

Inorg. Chem.

Chem. Eur. J.

J. Chem. Soc., Dalton Trans.

J. Chem. Soc., Dalton Trans.

Eur. J. Inorg. Chem.

Inorg. Chim. Acta

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Chem. Soc., Dalton Trans.

Angew. Chem., Int. Ed. Engl.

Coord. Chem. Rev.

Inorg. Chim. Acta

J. Phys.: Condens. Matter

Inorg. Chem.

Chem. Eur. J.

Eur. J. Inorg. Chem.

Inorg. Chem.

Angew. Chem., Int. Ed. Engl.

New planar polynitrile dianion and its first coordination polymer with unexpected short M⋯M contacts (tcno²⁻ = [(NC)₂CC(O)C(CN)₂]²⁻)