Three N-ethoxycarbonyl-N'-arylthioureas were synthesized and their structures were determined by X-ray diffraction. In the crystal of these compounds, there are inter- and intramolecular hy-drogen bonds, and the intermolecular hydrogen bonds assembled the compounds 1 and 2 into 1D catenulate supramolecular structure. The π-π interaction among the catenulate supermolecules connected the adjacent catenulate supermolecules together. While in the crystal of 3, the intermolecular hydrogen bonds assembled 3 into dimers. The adjacent dimers are assembled to 1D catenulate supramolecular structure by the intermolecular π-π interaction among aryl-ring.

Key words: thiourea, hydrogen bond, π-π interaction, supramolecular