Issue 10, 2002
From the journal:

New Journal of Chemistry

The hydrogen oxalate anion allows one-dimensional columnar aggregation of organometallic sandwich cations

Dario Braga,*a   Matthieu Eckert,a   Matteo Fraccastoro,a   Lucia Maini,a   Fabrizia Grepioni,*b   Andrea Caneschic  and  Roberta Sessoli*c  

* Corresponding authors

a Dipartimento di Chimica G. Ciamician, Via F. Selmi 2, Università di Bologna, Bologna, Italy
E-mail: dbraga@ciam.unibo.it
Web: http://www.ciam.unibo.it/crystal_eng

b Dipartimento di Chimica, Via Vienna 2, Università di Sassari, Sassari, Italy
E-mail: grepioni@ssmain.uniss.it

c Dipartimento di Chimica, Polo Scientifico, Via della Lastruccia 3, Sesto Fiorentino (Fi), Italy
E-mail: roberta.sessoli@unifi.it

Abstract

Oxalic acid reacts with sandwich compounds such as decamethyl ferrocene, decamethyl cobaltocene, bis-benzene chromium and cobaltocene, in the presence of oxygen, via a multi-step process involving oxidation, deprotonation and precipitation, to form crystalline superstructures containing columns of organometallic sandwich cations and hydrogen oxalate anions. Five novel crystalline compounds are reported, namely [Fe(η5-C5Me5)2][HC2O4]·[H2C2O4]0.5, 1a, [Co(η5-C5Me5)2][HC2O4]·[H2C2O4]0.5, 1b, [Fe(η5-C5Me5)2][HC2O4]·[H2C2O4], 2, [Cr(η6-C6H6)2][HC2O4]·[H2O], 3, and [Co(η5-C5H5)2][HC2O4]·[H2C2O4]0.5[H2O] 4. The anionic network in [M(η5-C5Me5)2][HC2O4]·[H2C2O4]0.5 (M = Fe, Co) is based on an unusual deca-atomic ring formed by hydrogen oxalate anions linked side-to-side via(−)O–H⋯O(−) hydrogen bonding interactions. The magnetic behaviour of compounds 1a, 2, and 3 has been investigated by SQUID magnetometry. Both compounds 1a and 2 present weak antiferromagnetic interactions, which are significantly stronger in 1a. The structure of the chloride salt [(η5-C5H5)2Co][Cl]·[H2C2O4][H2O], 5, is also described.

Graphical abstract: The hydrogen oxalate anion allows one-dimensional columnar aggregation of organometallic sandwich cations

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Article information

DOI
https://doi.org/10.1039/B205782D
Article type
Paper
Submitted
14 Jun 2002
Accepted
18 Jul 2002
First published
27 Aug 2002

New J. Chem., 2002,26, 1280-1286

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The hydrogen oxalate anion allows one-dimensional columnar aggregation of organometallic sandwich cations

D. Braga, M. Eckert, M. Fraccastoro, L. Maini, F. Grepioni, A. Caneschi and R. Sessoli, New J. Chem., 2002, 26, 1280 DOI: 10.1039/B205782D

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