Four polymorphs of a cobaloxime complex with different solid‐state photoisomerization rates

The complex (2-cyanoethyl)bis(dimethylglyoximato)(triphenylphosphine)cobalt(III), [Co(C4H7N2O2)2(C3H4N){P(C6H5)3}], when it was crystallized rapidly from an aqueous methanol solution, has four crystal forms, three of which were obtained separately from different solvents in large amounts. The crystal structures of the four forms were determined by X-rays. The molecular structures in the four forms have different conformations around the Co—C and Co—P bonds. The packing energy calculation indicated that the four forms have approximately the same energy. The 2-cyanoethyl group of this complex was isomerized to the 1-cyanoethyl group when the powdered sample of the complex was irradiated with a xenon lamp. For three crystal forms prepared separately, the solid-state photoisomerization rates were measured from the change in the IR spectra, assuming first-order kinetics. A quantitative relationship between the rate constant and the size of the reaction cavity for the 2-cyanoethyl group has been obtained for the three crystal forms.