Synthesis and Cofacial π-Stacked Packing Arrangement of 6,13-Bis(alkylthio)pentacene

6,13-Bis(alkylthio)pentacenes directed toward organic field-effect transistors (OFETs) were synthesized by the ZnI2-mediated reaction of trans-6,13-dihydroxy-6,13-dihydropentacene with alkylthiols, followed by the dehydrogenative aromatization of the resulting trans-6,13-bis(alkylthio)-6,13-dihydropentacenes with p-chloranil. The X-ray crystallographic analysis of 6,13-bis(methylthio)pentacene reveals that this compound is arranged as a result of cofacial π-stacking with S−S and S−π interactions.