Triiron dodecacarbonyl reacts with the potential ambidentate ligand 4-hydroxythiophneol (p-monothiohydroquinone) to give Fe-2(CO)(6)(mu-SC6H4-OH)(2) (1). A preference for binding the soft sulfur donor atom of 4-hydroxythiophenol rather than the hard oxygen donor atom is found when a soft metal and pi-acid ancillary ligands are employed; the amphoteric hydroxy groups of 1 are free to form intermolecular hydrogen bonds. When recrystallized from benzene, 1 yields the benzene solvate Fe-2(CO)(6)(mu-SC6H4-OH)(2) . C6H6, 1 . C6H6. Derivative 1 . C6H6 crystallizes in the triclinic space group P ($) over bar 1 with Z = 2, a = 10.305(5) Angstrom, b = 11.898(6) Angstrom, c = 12.037(6) Angstrom, alpha = 102.85(4)degrees, beta = 95.47(4)degrees, gamma = 112.06(4)degrees, R = 0.039, and R(w) = 0.050 at 20 degrees C. The structure of 1 . C6H6 in the solid-state consists of one-dimensional chains of hydrogen-bonded 1. The hydrophilic groups of adjacent chains face one another; thus the pairs of chains are insulated in one direction by the hydrophobic benzene solvate and in the other by the hydrophobic Fe-2(CO)(6)(S)(2) moieties. In the presence of excess ligand, 1 forms the ligand solvate Fe-2(CO)(6)(mu-SC6H4-4-OH)(2) . 2HSC(6)H(4)-OH, 1 . 2HSC(6)H(4)-4-OH. Derivative 1 . 2HSC(6)H(4)-4-OH crystallizes in the orthorhombic space group P2(1)2(1)2(1), with Z = 4, a = 8.967(4) Angstrom, b = 12.218(5) Angstrom, c = 31.708(8) Angstrom, R = 0.065, and R(w) = 0.074 at 20 degrees C. The crystal structure of 1 . 2HSC(6)H(4)-4-OH consists of chiral two-dimensional nets of annelated 40-membered rings.