A family of pyridyl-functionalized arylacetylene C–H hydrogen bonding (HB) receptors were synthesized and binding interactions to perrhenate (ReO4–) studied in the solid state. The protonation and alkylation state of the pyridine nitrogen dictate the location and denticity of the interactions. X-ray structures of neutral 1 and singly charged 2a+·ReO4– reveal the formation of favorable self-complementary dimers, owing to the presence of nitrogen HB acceptor sites. Dismissal of these dimers upon elimination of nitrogen HB acceptors on the receptor result in an array of multidentate C–H HB receptor–guest contacts.