Structural isomerism in crystals of redox-active secondary ortho-diamides: the role of competing intra- and intermolecular hydrogen bonds in directing crystalline topologies

Chemistry : a European Journal
Stéphane A BaudronPatrick Batail

Abstract

The solid-state chemistry of a series of seven ortho-bis(alkylamido)ethylenedithiotetrathiafulvalene derivatives EDT-TTF-(CONHR)2 (R=Me, 1; Et, 2; Pr, 3; Bu, 4; Pent, 5; Hex, 6; and Bz, 7), in their neutral and one-electron-oxidized, radical cation states, was investigated with an eye on the topology of intra- and intermolecular hydrogen-bond motifs. In the case of neutral, monomolecular solids, an intramolecular N--H.O hydrogen bond seals a constrained seven-membered ring for 1, 2, 3, and 7, which is disrupted in butyl derivative 4 in favor of an antiparallel ladder at the expense of any intramolecular hydrogen bond. In the solid-state, the competition between intra- and intermolecular hydrogen bonding observed in solution depends on the packing of the molecules. Electrocrystallization of methyl derivative 1 with ReO4- or ClO4-, two anions of different volumes but otherwise identical charge and symmetry, revealed a fine sensitivity of the constrained seven-membered ring to the internal chemical pressure exerted by the anion. [1]2 *+ReO4 (sigmaRT=8.5 S cm(-1), activation energy Delta=600 K at high temperature) and beta"-[1]2 *+ClO4 (sigmaRT=0.03 S cm(-1), Delta=1600 K; under pressure at room temperature, the conductivity increa...Continue Reading

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Citations

Jul 1, 2015·Inorganic Chemistry·Sandrina OliveiraManuel Almeida
Oct 18, 2006·Angewandte Chemie·Josep Puigmartí-LuisDavid B Amabilino
Jul 20, 2007·Chemical Communications : Chem Comm·Hubertus Bart F M Nelissen, David K Smith
Feb 4, 2010·Acta Crystallographica. Section C, Crystal Structure Communications·Goverdhan Mehta, Saikat Sen
Oct 30, 2010·Chemistry : a European Journal·Abdelkrim El-GhayouryPatrick Batail
Jul 1, 2015·Beilstein Journal of Organic Chemistry·Olivier JeanninMarc Fourmigué
Jun 16, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Zheng ShiJie Dai
Apr 17, 2012·Journal of the American Chemical Society·Cyprien LemouchiPatrick Batail
Sep 30, 2016·Inorganic Chemistry·Sandra RabaçaManuel Almeida
Feb 26, 2013·Inorganic Chemistry·Sandra CarlssonPatrick Batail

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