Crystals of iodine-doped zirconium(IV) diphthalocyanine, [ZrPC2](I3I2)-I-. (where Pc = C32H16N8), were grown directly in the reaction of pure zirconium powder with phthalonitrile under a stream of iodine at 260 degreesC. [ZrPc2](I3I2)-I-. crystallizes in the space group P2(1)/m, (No. 11) of the monoclinic system with lattice parameters of a = 6.735(1), b = 25.023(5), and c = 17.440(3) Angstrom, beta = 99.43(3)degrees, and Z = 2. The crystals of [ZrPc2](I3I2)-I-. are built up from two pseudo-monodimensional aggregates: one-electron-oxidized [ZrPc2](+) units; weak interacting triiodide I-3(-) ions with neutral diiodine molecules. The I-3(-) ions and neutral I-2 molecules in the crystal of [ZrPc2](I3I2)-I-. have been also detected by Raman spectroscopy. The [ZrPc2](+) units form stacks along the a axis, while the polymeric (I3-...I2I3-...I2...)-I-...-I-... zigzag chains are located in the crystal along the b axis, so both pseudo-monodimensional aggregates are perpendicular to each other. This arrangement is different from that found in the tetragonal crystals of [ZrPc2](I-3)(2/3) in which both monodimensional aggregates, i.e., the stacks of partially oxidized [ZrPc2](2/3+) units and chains of symmetric triiodide ions, are parallel. EPR experiment together with the X-ray single-crystal analysis clearly shown that oxidation of the diamagnetic ZrPc2 complex by iodine is ligand centered and homogeneously affecting both phthalocyaninato rings of ZrPc2; thus, the formal oxidation state of both Pc rings in [ZrPc2](I3I2)-I-. is nonintegral (-1.5). The UV-vis spectrum of [ZrPc2](I3I2)-I-. is very similar to the spectrum of unoxidized ZrPc2 complex in the B Soret and Q spectral region. However, in the spectrum of [ZrPc2](I3I2)-I-. one additional band at similar to502 nm is observed, which indicates the existence of the one-electron-oxidized phthalocyaninato(-) radical ligand and is assigned to the electronic transition from a deeper level to the half-occupied HOMO level. The single-crystal electrical conductivity data show anisotropy and nonmetallic character in conductivity (dsigma/dT > 0). The charge transport mainly proceeds along the pseudo-monodimensional stacks of [ZrPc2]+ units. The relatively high conductivity along the stacks of one-electron-oxidized [ZrPc2](+) units results from the staggering orientation of Pc rings (rotation angle 45.0(2)degrees) that leads to the short inter-ring C-alpha(pyrrole)-C-alpha(pyrrole) contacts (2.839(3)-3.024(3) Angstrom). These C-alpha-pyrrole atoms make appreciable contribution to the partially occupied pi-molecular orbital of Pc macrocycle and the greatest overlap of the HOMO orbitals that form the conduction band of partially oxidized molecular crystals.