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|Title:||Structure and magnetism of Nickel(II) and Manganese(II) complexes of a nytronyl nitroxide carboxylic acid||Authors:||Schiodt, N. C.
Fabrizi De Biani, Fabrizia
|Issue Date:||1996||Project:||None||Journal:||INORGANICA CHIMICA ACTA||Abstract:||
The organic anionic radical 2-(4-carboxy-phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-oxide (NITpBA−) has two different types of potentially metal-coordinating sites. One is the carboxylate group, the other consists of the two oxygen atoms belonging to the nitronyl nitroxide part. The nitronyl nitroxides have generally revealed a rather weak coordinating ability and they have been found only to coordinate metal ions with a low electron density as in the case of hexafluoro-acetylecetonates. Howeverm, in the simple, carboxylate salt Mn(NITpBA)2(H2O)2, each MnII ion is coordinated simultaneously by water, carboxylate oxygens and radical oxygens with the NITpBA− ligands bridging the MnII ions such as to obtain a ladder-like structure. The NiII derivative has also been prepared and it was found to be isostructural with the Mn salt. Mn(NITpBA)2(H2O)2 crystallizes in the monoclinic system, P21/c (No. 14) space group, a = 12.644(2), b = 9.203(2), c = 13.598(2), β = 115.21 (1)°, V = 1431.6(4) Å3, Z = 2, refinement with 2150 reflections, 196 parameters, yielded R = 0.046 and Rw = 0.051. The magnetic susceptibility as a function of temperature of these compounds is readily accounted for on the basis of their structure. A chain model was adopted to reproduce the observed magnetic susceptibility of the NITpBAH free radical.
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