Crystal synthesis of 1,4-phenylenediamine salts and coordination networks

para-Phenylenediamine (ppda) may be ground together with metal chloride salts MCl2 to produce the coordination network compounds [{(ppda)MCl2}(n)] {M Zn (2), Cd (4), Cu (6)}. Its dihydrochloride salt [H(2)ppda]Cl-2 can be ground with MCl2 to produce the layered salt structures [H(2)ppda][MCl4] {M Zn (1), Cd (3), Cu (5)}, which (when M Zn or Cd) may then be converted into 2 or 4 respectively by grinding with solid KOH. Alternatively, [H(2)ppda][MCl4] will react directly with appropriate basic metal compounds (hydroxides and/or carbonates) to give 2 or 4, which can then be converted back to the salts by reaction with gaseous HCl. The interconversion of 5 and 6 is more complicated, with different combinations of starting material giving different products. The crystal structure of 2 has been solved ab initio from the powder-diffraction data, and is shown to consist of zigzag polymeric chains containing alternating ppda and MCl2 units.