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Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-101012 (1), CCDC-101576 (2), and CCDC-101575 (3). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@chemcrys.cam.ac.uk).
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25
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B values are -0.8 and -1.2 K, respectively.
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50
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0346923483
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note
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Given the weakness of the magnetic couplings observed and the relatively long connection paths we invoke in these systems, we cannot rule out the possibility that simple through-space interactions could play a role in magnetic coupling. However, having carefully inspected the structures and packing diagrams for obvious π stacking or other close approaches, we have not found contacts more promising than these hydrogen-bonding pathways as explanations for the difference in magnetic behaviors seen between 2 and 3. Indeed, the shortest through-space coupling distance between nitroxyl spins in paramagnetic material 3 is 6.71 Å whereas the corresponding shortest distance in the coupled antiferromagnetic system 2 is 7.28 Å. These results strongly point toward a through-bond pathway. We thus prefer the interpretation of the hydrogen bond networks because of their self-consistency with the structural chemistry.
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