Dithiourea 1a self-assembles to form an orthogonal dimer structure both in solution and in the solid state, wherein the four thiourea groups establish a closed network of hydrogen bonds through a head-to-tail binding mode. This novel dimer structure was elucidated on the basis of 1H NMR spectra, vapor pressure osmometry, and X-ray crystal structure analysis. Furthermore, a series of m-xylylene type dithioureas were synthesized and their ...