The ionic complexes simultaneously containing negatively charged coordination structures of metal phthalocyanines and fullerene anions, viz., {(MnPc)-Pc-II(CH3CH2S-) (x) center dot(I-)(1-x) }center dot(C-60 (center dot-))center dot center dot(PMDAE(+))(2)center dot C6H4Cl2 (PMDAE is N,N,N',N',N'-pentamethyldiaminoethane, x = 0.87, 1) and {(ZnPc)-Pc-II(CH3CH2S-)(y)center dot(I-)(1-y) }(2)center dot(C-60 (-))(2)center dot(PMDAE(+))(4)center dot(C6H4Cl2) (y = 0.5, 2) were synthesized. The both compounds were obtained as single crystals, which made it possible to study their crystal structures. In complex 1, the fullerene radical anions form honeycomb-like layers in which each fullerene has three neighbors with center-to-center interfullerene distances of 10.13-10.29 . Rather long distances between the C-60 (center dot-) radical anions results in the retention of monomeric C-60 (center dot-) in this complex down to the temperature of 110(2) K. In complex 2, fullerenes form dimers (C-60 (-))(2) bonded by one C-C bond. The dimers are packed in corrugated honeycomb-like layers with interfullerene center-to-center distances of 9.90-10.11 . Manganese(II) and zinc(II) phthalocyanines coordinate iodide and ethanethiolate anions to the central metal atom to form unusual negatively charged coordination structures (MPc)-Pc-II(An(-)) (An(-) is anion) packed in dimers {(MPc)-Pc-II(An(-))}(2) with a short distance between the phthalocyanine planes (3.14 in 1 and 3.27 in 2). The pthalocyanine dimers also form layers with the PMDAE(+) cations, and these layers alternate with the fullerene layers. The packing of spherical fullerenes with planar phthalocyanine molecules is attained by the insertion of fullerenes between the phenylene groups of phthalocyanines. The pi-pi-interactions of the porphyrin macrocycle with five- or six-membered fullerene rings are characteristic of the earlier studied ionic porphyrin and fullerene complexes. Such interactions are not observed for ionic complexes 1 and 2.
