Preparation and Crystallography of 1,2-Bis(chloromercurio)tetrafluorobenzene Adducts with Nitrobenzene and Nitrotoluenes

Co-crystallization of 1,2-bis(chloromercurio)tetrafluorobenzene (II) with nitrobenzene (1) and three nitrotoluene isomers (2−4) results in four complexes with a ratio of organometallic to organic components of 1:1 and one complex with a corresponding ratio of 2:1. All crystals of complexes with a 1:1 ratio have a platelike shape, while crystals of the complex with a 2:1 ratio are needlelike. X-ray studies reveal supramolecular organization in the 1:1 “plate” complexes, showing that they are built of molecular layers where the central section of layers is stabilized with nonbonded interactions of Hg atoms, while the layer surface is formed with phenyl rings of both co-crystal components. Two types of layer superposition in these complexes were found: parallel, producing an acentric structure, and antiparallel, that leads to a centrosymmetric space group. This indicates that supramolecular organization involving Hg nonbonded interactions in some cases will be helpful to produce acentric structures of polar molecules by incorporating them in co-crystals with II. In the 2:1 complex, molecules are organized in 1D associates (chains), that are stabilized with the same types of interactions. In both types of complexes, external crystal shape corresponds to internal supramolecular organization in co-crystals: platelike layered and needlelike chain crystals.