The ligand molecule N10-(2′-mercaptoethanoyl)-2,2,5,5-tetramethyl-3,4-dithia-7,10-diazabicyclo[5.3.0]decane has been prepared and characterized by 1H and 13C NMR spectroscopy and by mass spectrometry. The protected analogue, N10-[(2′-triphenylmethylthio)ethanoyl]2,2,5,5-tetramethyl-3,4-dithia-7,10-diazabicyclo[5.3.0]decane dimethanol hemihydrate, was examined by the same techniques and also by X-ray crystallography. Crystals were triclinic, P-1, a = 11.125(2), b = 11.986(2), c = 13.562(3) Å, α = 103.54(3)°, β = 90.29(3)°, γ = 107.11(3)°, and Z = 2. The crystal was unstable in air at room temperature, so measurements were made on a crystal sealed in a tube that contained methanol vapour Intensities were measured with a Rigaku AFC6R diffractometer and monochromated CuKα radiation (λ = 1.54178 Å). The structure was solved by direct methods and refined to R = 0.1497, wR = 0.0655 based on 5000 independent reflections. The high residuals were caused by solvent disorder. Bond lengths and angles were normal. The reaction of the ligand with oxotrichlorobis(triphenylphosphine)rhenium(V) yielded an unexpected asymmetric complex, oxo(1,1-dimethyl-1,8-dimercapto-3,6-diazaoctan-7-onato-N3,N6,S1,S8) rhenium(V). Crystals were monoclinic, P21/n, a = 10.633(2), b = 11.221(2), c = 11.678(1) Å, β = 116.10(1)°, Z = 4. Intensities were measured with a Siemens P4 diffractometer and monochromated MoKα radiation (λ = 0.71073 Å). The structure was solved by the heavy atom method and refined to R = 0.0471, wR = 0.0340 based on 2866 unique reflections. Most bond lengths and angles were normal. The Re≡O distance of 1.681(5) Å was longer than normal. It is postulated that this was caused by competitive π bonding between the deprotonated amidic nitrogen atom and the rhenium atom, as shown by the short Re—N distance (1.997(6) Å) compared to the equivalent distance for the amine nitrogen atom (Re—N, 2.151(4) Å). Key words: N2S2 ligands, rhenium, crystal structure.
N-Tris[(2-aminoethyl)-2-(diphenylphosphoryl) acetamide)] — novel CMPO tripodand: synthesis, extraction studies and luminescent properties of lanthanide complexes
