Diversity of chain, interwoven and network structures formed by metal complexes with 2,3,5,6-tetrafluoro-1,4-bis(4-pyridyl-sulfenyl)benzene

The preparations are reported of a range of complexes formed by 2,3,5,6-tet rafluoro-1,4-bis(4-pyridylsulfenyl)benzene (L) with Mn-II, Co-II, Ni-II, Zn -II and Cd-II, and single crystal X-ray diffraction studies have been made on four of the compounds. In the complex CoLI2. 0.5CH(2)Cl(2), the organic ligand bridges tetrahedrally coordinated Co-II centres so as to form chains . The compound Cd2L3(NO3)(4) has a more complex structure in which seven-co ordinate Cd centres are linked by two different types of L bridges so as to form arrays of 90-membered macrocycles comprising sheets of linked alterna ting enantiomeric helices. In the complexes MnL2(EtOH)(2)X-2 (X = Br or NCS ), the bis(pyridyl) ligand utilises only one of its pyridyl units to coordi nate directly to the metal atom. In both cases the Mn coordination environm ent comprises an all-trans octahedral arrangement of two anions, two ethano l ligands and two pyridyl units derived from two different L ligands. Howev er in both compounds the non-coordinated pyridyl units bridge adjacent Mn c entres by forming hydrogen bonds to the ethanol ligands. The resulting, com plex networks are, however, dramatically different. The isothiocyanate comp lex forms sheets of partially interpenetrating helices whereas the bromide forms a system of triply interpenetrating (4,4) nets of 'over 2-under 2' ty pe. X- and Q-Band EPR spectra of the manganese complexes are reported as ar e relevant spectroscopic results for the other complexes.