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• The BF 2 -complexes containing pairs of diketonate ligands bound via a sulfur atom were obtained. • The structure of BF 2 -complexes is similar to the structure of aromatic sulfides. • The structure of BF 2 -complexes is also largely determined by intermolecular interactions. Four binuclear diketonate complexes of boron difluoride have been prepared. Obtained complexes contain the following pairs of ligands connected through a sulfur atom with their central carbon atoms: acetylacetone-acetylacetone, acetylacetone-acetoacetic ester, acetylacetone-dibenzoylmethane, acetylacetone-benzoylacetone. Molecular and crystal structure have been identified for three complexes. Their structure is similar to the one of aromatic sulfides. Effect of γ-substituents on chelate cycle structure and on the substituents next to β-carbon atoms has been discussed. [ABSTRACT FROM AUTHOR]