STRUCTURAL STUDIES OF 7 COMPOUNDS OF COBALT(III) WITH TRANS-6,13-DIAMINO-6,13-DIMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECANE

The structures of seven compounds of trans-6,13-diamino-6,13-dimethyl- 1,4,8,11-tetraazacyclotetradecane (diam) with cobalt(III) have been determined by X-ray diffractometry: (1), trans-alpha-[{Co(diam-N5)}2(O2)](ClO4)4.2H2O (monoclinic, P2(1)/n, a 10.673(2), b 22-924(8), c 19.332(5) angstrom, beta 114.19(2)-degrees, R 0.044 for 4547 reflections); (2), trans-alpha-[Co(diam-N5)Cl](ClO4)2 (orthorhombic, P2(1)2(1)2(1), a 9.043(4), b 11.214(4), c 21.431(8) angstrom, R 0.055 for 1541 reflections); (3), trans-alpha-Co(diamH-N5)Cl] [ZnCl4]Cl.H2O (orthorhombic, Pna2(1), a 25.26(5), b 9.866(2), c 9.457(2) angstrom, R 0.108 for 1686 reflections); (4), trans-alpha-[Co(diamH-N5)(H2O)]Cl3.ClO4 (monoclinic, P2(1)/n, a 12.928(8), b 8.554(5), c 20.624(12) angstrom, beta 106.00(4)-degrees, R 0.060 for 2094 reflections); (5), trans-gamma-[Co(diamH-N5)Cl] Cl3.3H2O (orthorhombic, P2(1)2(1)2(1), a 12.895(7), b 12.898(9), c 13.417(4) angstrom, R 0.062 for 860 reflections); (6), trans-beta-[Co(diamH-N5)Cl] [ZnCl4] Cl.1/2H2O1/2C3H7OH (triclinic, P1BAR, a 10.469(4), b 9.167(5), c 15.464(6) angstrom, alpha 73.74(4), beta 71.15(3), gamma 73.70(1)-degrees, R 0.045 for 3685 reflections)-, (7), trans-beta-[Co(diamH-2-N4)Cl2] [ZnCl4] Cl.1/2H2O.1/2C2H5OH (triclinic, P1BAR, a 10.138(2), b 12.011(3), c 12.451(2) angstrom, alpha 79-87(2), beta 66.64(1), gamma 66.64(1)-degrees, 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 ammonio substituent in a skew conformation. Compounds (6) and (7) have the R,R,S,S configuration (3), (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.