Synthesis of Amphiphilic Metal Organics Using p-Monothiohydroquinolate,an Ambidentate Ligand That Bears a Hard and a Soft Donor. One- and Two-Dimensional Solid-State Structures of Fe2(CO)6(μ-SC6H4-4-OH)2.nSolv (Solv = C6H6, n = 1; Solv = HSC6H4-4-OH, n = 2)

Article abstract of DOI:10.1021/ic00126a010

Triiron dodecacarbonyl reacts with the potential ambidentate ligand 4-hydroxythiophenol (p-monothiohydroquinone) to give Fe2(CO)6(μ-SC6H4-4-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 softmetal and π-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 Fe2(CO)6(μ-SC6H4-4-OH)2.C6H6, 1.C6H6. Derivative 1.C6H6, crystallizes in the triclinicspace group P1- with Z = 2, a = 10.305(5) ?. b = 11.898(6) ?, c= 12.037(6) ?, α = 102.85(4)°, β = 95.47(4)°, γ = 112.06(4)°, R = 0.039, and Rw = 0.050 at 20°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 Fe2(CO)6(S)2 moieties. In the presence of excess ligand, 1 forms the ligand solvate Fe2(CO)6(μ-SC6H4-4-OH)2.2HSC6H4-4-OH, 1.2HSC6H4-4-OH. Derivative 1.2HSC6H4-4-OH crystallizes in the orthorhombic space aroup P212121, with Z = 4, a = 8.967(4) ?, b = 12.218(5) ?, c = 31.708(8) ?, R = 0.065, and Rw = 0.074 at 20°C. The crystal structure of 1.2HSC6H4-4-OH consists of chiral two-dimensional nets of annelated40-membered rings. The nets of 1.2HSC6H4-4-OH may be formulated as chains of 1 that are bridged by hydrophilic 4-hydroxythiophenol. The two Fe2S2 moieties within a given ring are connected bytwo chains of unequal length, one consisting of 13 covalent bonds and three hydrogen bonds, and the other consisting of 15 covalent bonds and five hydrogen bonds. Furthermore, the two-dimensional nets of 1.2HSC6H4-4-OH are not planar; instead, they are folded and stacked to give corrugated layers. Folding the two-dimensional net of 1.2HSC6H4-4-OH creates a lamellar superstructure that orients the amphoteric hydroxy groups of 1 within the bilayers (cf. 1.C6H6). Thus, the hydrophilic/hydrophobic properties of the molecule ofcocrystallization Solv of the 1.nSolv compounds apparently influence the dimensionality of their respective solid-state structures.