No abstract

A series of mononuclear iron(III) complexes of the type [Fe(L)Cl(3)], where L is a systematically modified N(2)O or N(3)O ligand with a methoxyethyl/tetrahydrofuryl ether oxygen donor atom, have been isolated and studied as models for catechol dioxygenases. The X-ray crystal structures of [Fe(L2)Cl(3)] 2, [Fe(L6)Cl(3)] 6, [Fe(L5)(TCC)Cl] 5a, where H(2)TCC = tetrachlorocatechol, [Fe(L6)(TCC)Br] 6a, and the μ-oxo dimer [{Fe(L6)Cl}(2)O](ClO(4))(2) 6b have been successfully determined. In [Fe(L2)Cl(3)] 2 the N(2)O ligand is facially coordinated to iron(III) through the pyridine and secondary amine nitrogen atoms and the tetrahydrofuryl oxygen atom. In [Fe(L6)Cl(3)] 6, [Fe(L5)(TCC)Cl] 5a and [Fe(L6)(TCC)Br] 6a the N(3)O donor ligands L5 and L6 act as a tridentate N3 donor ligand coordinated through two pyridine and one secondary amine nitrogen atoms, whereas the ether oxygen is not coordinated. The spectral and electrochemical properties of the adducts [Fe(L)(DBC)Cl] of 1-8, where H(2)DBC = 3,5-di-tert-butylcatechol, in DMF and their solvated adduct species [Fe(L)(DBC)(Sol)](+), where Sol = DMF/H(2)O, generated in situ in dichloromethane, respectively, have been investigated. The product analysis demonstrates that the adducts [Fe(L)(DBC)Cl] effect cleavage of catechol in the presence of O(2) in DMF to give mainly the intradiol (I) product with a small amount of the extradiol (E) product (E/I, 0.2:1-0.7:1). Interestingly, the solvated species [Fe(L)(DBC)(Sol)](+) derived from 1-4 cleave H(2)DBC to provide mainly the extradiol cleavage products with lower amounts of intradiol products (E/I, 2.3:1-4.3:1) in dichloromethane. In contrast, the solvated species [Fe(L)(DBC)(Sol)](+) derived from 5-8 cleave H(2)DBC to provide both extradiol and intradiol products (E/I, 0.6:1-2.3:1) due to the involvement of the ether oxygen donor of the methoxyethyl/tetrahydrofuryl arm in the coordination to iron(III) upon removal of a chloride ion.

No abstract

In 3‐methyl­anilinium picrate (3‐MAP), C7H10N+·C6H2N3O7−, one of the nitro groups in the picrate ion is rotationally disordered with site occupancy factors of 0.80 and 0.20. The expected proton transfer took place between picric acid and 3‐methyl­aniline, and the amine group is hydrogen bonded to two of the phenolate O atoms. The ortho‐nitro groups deviate greatly from the benzene plane of the picrate ion, facilitating hydrogen‐bond formation. While the cations are stacked as columns along the [001] direction, the anions are stacked in an offset fashion.

In the title mol­ecular complex, 2C6H6N2O2·C6H3N3O7, an undissociated picric acid mol­ecule is sandwiched between two crystallographically independent nitro­aniline mol­ecules. The mol­ecules stack in columns down the a axis, with the packing stabilized by N—H⋯O and C—H⋯O hydrogen bonds and π–π stacking inter­actions.