Preparation, Structures, and Physical Properties of Two Products from the Iodination of (Phthalocyaninato)iron(II)

(Phthalocyaninato)iron(II), Fe(pc), was oxidized in a solution of iodine in hot 1-chloronaphthalene. Two products were isolated: [FeCl(pc)]₂I₂, which is a new compound formed by reaction with the solvent, and the molecular conductor Fe(pc)I. [FeCl(pc)]₂I₂ crystallizes in space group C1i-P1 of the triclinic system with 1 formula unit in a cell of dimensions a = 12.270 (7) Å, b = 13.202 (7) Å, c = 8.335 (6) Å, a = 92.80 (3)°, β = 97.17 (3)°, and γ = 101.97 (2)° at 113 K. Full-matrix least-squares refinement of 388 variables gives a final value for R (on F₀²) of 0.066 for 6847 observations. The structure consists of two square-pyramidal FeCl(pc) units linked by I₂ via the axial chloro ligands. The four halogens form an essentially linear unit. The ⁵⁷Fe Mössbauer spectrum is consistent with this structure. Fe(pc)I crystallizes in space group D_4h²-P4/mcc of the tetragonal system with 2 formula units in a cell of dimensions a = 13.84 (2) Å and c = 6.77 (1) Å at 97 K. Full-matrix least-squares refinement of 35 variables gives a final value of 0.177 for the R index (on F₀²) for 620 observations. The structure consists of chains of Fe(pc) molecules, stacked metal over metal. Adjacent Fe(pc) molecules in the unit cell are staggered by 40°. Disordered chains of I3- lie in channels between the Fe(pc) stacks. The iodine is identified as I3- by resonance Raman spectroscopy. The single-crystal conductivity of Fe(pc)I is 20 Ω^-1 cm^-1 at 20 °C; the conductivity increases with decreasing temperature.