The crystal chemistry of amide-functionalized ethylenedithiotetrathiafulvalenes: EDT-TTF-CONRR ' (R, R ' = H, Me)

TThe preparation of ethylenedithiotetrathiafulvalenes (EDT-TTF) directly fu nctionalized on the TTF core with a primary, secondary or tertiary amide or an hydrazide functional group is described. The X-ray crystal structures o f EDT-TTF-CO2H, EDT-TTF-CONH2, EDT-TTF-CONHMe and EDT-TTF-CONMe2 are report ed. The solid state architectures adopted by those functionalized molecules appear to be a compromise between the hydrogen bond requirements of the OH , NH2, CH and C=O groups, which act as hydrogen bond donor and acceptor, re spectively, and the S ... S van der Waals interactions of the EDT-TTF moiet y. The activation of the hydrogen atom of the TTF core, ortho to the amidic group, enhances its involvement in short C-H ... O bonds, giving rise to a characteristic chelating R-2(1) (7) motif as observed in the secondary ami de, EDT-TTF-CONHMe.