The Richter cyclization was used for the synthesis of 6-halo-3-(hydroxymethyl)cinnolin-4(1H)-ones. X-ray analysis revealed that these compounds exist as dimers in their crystal state, wherein two molecules are linked by intermolecular double and bifurcated hydrogen bonds that can explain their low solubility. Theoretical study of bifurcated hydrogen bonds responsible for the dimerization was carried out by DFT calculations as well as by topological analysis of the electron density distribution within the framework of Bader's theory.