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

Abstract

The preparation of ethylenedithiotetrathiafulvalenes (EDT-TTF) directly functionalized on the TTF core with a primary, secondary or tertiary amide or an hydrazide functional group is described. The X-ray crystal structures of EDT-TTF-CO ₂ H, EDT-TTF-CONH ₂ , EDT-TTF-CONHMe and EDT-TTF-CONMe ₂ are reported. The solid state architectures adopted by those functionalized molecules appear to be a compromise between the hydrogen bond requirements of the OH, NH ₂ , CH and CO groups, which act as hydrogen bond donor and acceptor, respectively, and the S···S van der Waals interactions of the EDT-TTF moiety. 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 amide, EDT-TTF-CONHMe.