Synthesis and characterization of the pentadentate macrobicyclic ligand, 14-thia-1,4,8,11-tetraazabicyclo[9.5.3]nonadecane (L1) and its nickel(II) complexes. X-ray crystal structure of [Ni(L1)(ClO4)](ClO4)·2[Ni(L1)(OH2)](ClO4)2·6H2O
The pentadentate macrobicycle,14-thia-1,4,8,11-tetraazabicyclo[9.5.3]nonadecane (L1), has been synthesized by high dilution cyclization of 1-thia-4,8-diazacyclododecane ([10]aneN2S) (2) with N,N'-bis(α-chloro acetamido) propane (3) and subsequent reduction of the di-oxo intermediate. The structure of the [Ni(L1)(ClO4)](ClO4)·2[Ni(L1)(OH2)](ClO4)2·6H2O complex (monoclinic, P21/c, a = 13.9261(4) Å, b = 30.279(2) Å, c = 17.1248(3) Å, β = 94.5065(3)°) at R = 0.039 (Rw = 0.034) for 911 parameters using 18 266 reflections with I > 3σI has been determined. The ligand adopts a trans-III configuration. The Ni(II) ion is pseudooctahedral with Ni-S = 2.3896(10) Å in [Ni(L1)(ClO4)]+ and 2.4193(10) Å, 2.4225(10) Å, in the two [Ni(L1)(H2O)]2+ cations. Both nickel(II) and nickel(III) complexes are six-coordinate in solution. Oxidation of the [Ni(L1)(OH2)]2+ complex with K2S2O8 in aqueous solution yielded an ESR active Ni(III) species and the frozen solution spectrum displayed axial symmetry with g[Formula: see text] = 2.159 and g|| = 2.024. In CH3CN, the [Ni(L1)(solv)]2+ complex showed two reversible redox waves corresponding to the Ni2+/+ couple at E1/2 = -1.807 V vs. Fc+/0 and Ni3+/2+ couple at E1/2 = 0.715 V vs. Fc+/0.Key words: synthesis, structure, polydentate macrobicycle, nickel(II).