Structural Studies of Seven Compounds of Cobalt(III) With trans-6,13-Diamino-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane

Abstract

The structures of seven compounds of trans-6,13-diamino-6,13-dimethyl-1,4,8,11-tetraacyclotetradecane (diam) with cobalt(III) have been determined by X-ray diffractometry: (1), trans-α-[{Co(diam-N₅)}₂(O₂)](ClO₄)₄.2H₂O (monoclinic, P2₁/n, a 10.673(2), b 22.924(8), c 19.332(5) Ǻ,β 114 19(2)°, R 0.044 for 4547reflections); (2), trans-α-[Co(diam-N₅)Cl](ClO₄)₂ (orthorhombic, P 2₁2₁2₁, a 9.043(4), b 11.214(4), c 21.431(8) A, R 0.055 for 1541 reflections); (3), trans-α- Co(diamH-N₅)Cl] [ZnCl₄] Cl.H₂O (orthorhombic, Pna 2₁, a 25.26(5), b 9.866(2), c 9.457(2) 1, R 0.108 for 1686 reflections); (4), trans-α-[Co(diamH-N₅)(H₂O)Cl₃.ClO₄ (monoclinic, P 2₁/n, a 12.928(8), b 8.554(5), c 20.624(12) A, β 106.00(4)°, R 0.060 for 2094 reflections); (5), trans-γ-[Co(diamH-N₅)Cl]Cl₃.3H₂O (orthorhombic, P2₁2₁2₁, a 12.895(7), b 12.898(9), c 13 -417(4) Ǻ, R 0.062 for 860 reflections); (6), trans-β-[Co(diamHN₅) Cl] [ZnCl₄]CI.½H₂O.½C₃.H₇OH(triclinic, P1, a 10.469(4), b 9.167(5), c 15.464(6) Ǻ, α 73.74(4), β 71.15(3), γ 73.70(1)°, R 0.045 for 3685 reflections); (7), trans-β-[Co(diamH₂- N₄)Cl₂] [ZnCl₄]Cl.½H₂O.½C₂.H₅OH(triclinic, P1, a 10.138(2), b 12.011(3), c 12-451(2) Ǻ, α 79,87(2), β 66.64(1), γ 66.64(1)°, R 0.035 for 2637 reflections). The cations of compounds (1)-(6) all have pentadentate diam (diam-N₅ or diamH-N₅) with one primary amino substituent coordinated trans to the additional ligand. Compounds (1)-(4) have the pentadentate macrocycle in cyclam configuration (1). R,S,R,S, with all four secondary amine groups on the same side of the molecular plane, with one six-membered chelate ring in a boat conformation with the amino substituent coordinated, and the other in a chair conformation. Compound (5) has the pentadentate macrocycle in configuration (2), R,R,S,R, with one NH group alone on one side of the molecular plane with the six-membered chelate ring with the non-coordinated amrnonio substituent in a skew conformation. Compounds (6) and (7) have the R,R,S,S configuration (S'), (6) having diamH-N5 with one amine substituent coordinated, and (7) with planar tetradentate diamH2-N4 in the macrocycle conformation usual for planar coordinated cyclam compounds, the ammonio substituents being equatorially oriented.