COMPLEXES OF THE LIGAND 1,5,8,12-TETRAAZADODECANE (3,2,3-TET) WITH MANGANESE(III) AND WITH A VALENCE-TRAPPED MANGANESE(III) MANGANESE(IV) HEXANUCLEAR ARRAY - CRYSTAL AND MOLECULAR-STRUCTURES OF [TRANS-MN(3-IOBZ)2(3,2,3-TET)](CLO4) AND [MN6(3,2,3-TET)4O6(OAC)3]I5.2H2O.4C4H8O

Mononuclear Mn(III) complexes containing two coordinated carboxylates and the tetraamine 1,5,8,12-tetraazadodecane (3,2,3-tet) have been synthesized by using substituted benzoates. The complexes irai-bis(3-iodobenzoato)(1,5,8,12-tetraazadodecane)-manganese(HI) Perchlorate (6) and tra-bis(4-nitrobenzoato)(1,5,8,12-tetraazadodecane)manganese(III) iodide (7) were prepared, and 6 was structurally characterized. Complex 6 crystallizes in the monoclinic space group P21/c, Z = 4, with a = 22.973 (9) Å, b = 12.029 (3) Å, c = 10.833 (5) Å, and β = 102.38 (3)°, and the structure has been refined to an R of 0.035. The geometry around the Mn(III) ion is an irregular octahedron with monodentate benzoato ligands bound in trans positions. With acetate and benzoate as the carboxylate groups, a number of hexanuclear species have been isolated. A hexanuclear complex [Mn6-(3,2,3-tet)4(OAc)306]l5·2H2O·4C4H8O (3) has been structurally characterized. It crystallizes in the monoclinic space group C2/c, Z = 4, with a = 27.733 (13) Å, b = 13.663 (7) Å, c = 27.020 (14) Å, and β = 124.16 (3)°, and the structure has been refined to an R of 0.055. The asymmetric unit contains three types of manganese ions, a Mn(IV) ion octahedrally coordinated to a 3,2,3-tet ligand and two µ2-OxO groups, a Mn(III) ion coordinated to a 3,2,3-tet ligand, a µ3-OxO group, and a µ2-acetato ligand, and a Mn(III) ion with six oxygen donor atoms, two µ2-OxO groups, two µ3-OxO groups, and two µ-acetato groups. Preparation of related benzoate complexes is also described. ESR, infrared, and visible spectra of these complexes have been measured and are discussed. © 1990, American Chemical Society. All rights reserved.