Acta Crystallographica Section B

Structural Science, Crystal Engineering and Materials

Volume 70, Part 1 (February 2014)

crystal engineering

Acta Cryst. (2014). B70, 181-190    [ doi:10.1107/S2052520613027170 ]

Spin-coupling in dimers of 2,3-dicyano-5,6-dichlorosemiquinone radical anions in the crystalline state

K. Molcanov, D. Babic, B. Kojic-Prodic, J. Stare, N. Maltar-Strmecki and L. Andros

Abstract: A crystal engineering approach is used to stabilize a radical anion in the crystalline state and to modulate the separation distance within [pi]-stacks of anion radicals. Alkali metal salts of 2,3-dicyano-5,6-dichlorosemiquinone (C8Cl2N2O2, DDQ^{\bullet -}) radical anions were prepared and their crystal structures determined: LiDDQ·2H2O·(CH3)2CO, RbDDQ·2H2O and CsDDQ·2H2O. In these structures, stacked dimers of radical anions are formed within [pi]-stacked columns. Within the stacked dimers, interplanar separation distances are significantly shorter than the sum of the van der Waals radii for two C atoms; the shortest is 2.812 Å for the Li salt and the longest is 2.925 Å for the Cs salt. Diamagnetic character, observed by electron paramagnetic resonance spectroscopy, indicates spin-coupling of the unpaired electrons within the radical anion dimer. The electron-rich cyano substituents on DDQ^{\bullet -} influence the electron redistribution within the ring skeleton. The crystalline compounds are also characterized by IR spectroscopy, complemented by quantum-chemical calculations based on both isolated and periodic models.

CCDC references: 964468, 964469, 964470, 964471 and 964472

Keywords: semiquinone radical; spin coupling; [pi]-interaction; diamagnetism; thermal analysis; IR spectroscopy; density functional theory calculations.

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[ doi:10.1107/S2052520613027170/bi5007sup7.txt ]
DFT optimized structures in CIF format

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[ doi:10.1107/S2052520613027170/bi5007sup8.pdf ]
ORTEP plots, IR spectra, geometries of fragments used for calculation of vibrations, refinement details for inversion twins


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