Ionic complexes containing C-60(center dot-) radical anions and metalloporphyrins coordinatively bound to N,N',N'-trimethylpiperazinium cations {(TMP+)(2)center dot(MTPP)-T-II}center dot(C-60(-))(2)center dot(C6H4CI2)(2)center dot(C6H5CN)(2) [M = Zn (1) and Mn (2)] have been obtained. The crystal structures of 1 and 2 solved at 250 and 270 K, respectively, show layered packing in which fullerene layers alternate with the (TMP)(2)center dot(MTPP)-T-II ones. Fullerenes form pairs in the layer with short center-to-center distances of 10.044 and 10.077 A, respectively. The structures of 1 and 2 solved at 100 K indicate the formation of singly bonded (060)2 dimers. That results in the transition of 1 from the paramagnetic to diamagnetic state accompanied by the disappearance of the electron paramagnetic resonance (EPR) signal of C-60(center dot-) at 220-150 K. Dimerization in 2 results in a decrease in the magnetic moment from 6.36 to 6.00 mu 8 at 200-150 K and a change in the shape of EPA signal. The room- temperature EPA signal shows a major broad component at g = 2.0678 (Delta H = 111.6 mT) attributed to both paramagnetic C-60. and high-spin (TMP+)(2) (MNTPP)-T-II species having strong exchange interaction. After dimerization, the signal is characteristic of isolated high-spin (MTPP)-T-II = 6 with |A| = 7.3 mT and g(II) 2). Two IMP+ cations can coordinate to M-II in (TMP+)2. MIITPP. However, a weak coordination bond is formed only with one cation with the M-II center dot center dot center dot N(TMP+) distances of 2.489(2)-2.688(3) A. As a result, metal atoms displace by +/- 0.232(3) angstrom (1, 250 K), +/- 0.231(1) angstrom (1, 100 K) and +/- 0.4684(7) angstrom (2,270K) out of the porphyrin plane lobe located above and below the porphyrin plane with equal occupancies for both positions. The symmetry of the crystal structure of 2 decreases from monoclinic to triclinic under cooling. That results in unequal 0.85/0.15 occupation of the Mn-II positions at 100 K with displacement of the metal by 0.391(2) and 0.554(4) angstrom, respectively.