Synthesis, spectral (IR, UV-Vis and variable temperature NMR) characterization and crystal structure of (N-benzyl-N-furfuryldithicarbamato-S,S')(thiocyanato-N)(triphenylphosphine)nickel(II).

Planar (N-benzyl-N-furfuryldithiocarbamato-S,S')(thiocyanato-N)(triphenylphospine)nickel(II), [Ni(bfdtc)(NCS)(PPh3)], (1) was prepared from bis(N-benzyl-N-furfuryldithiocarbamato-S,S')nickel(II), [Ni(bfdtc)2], (2) and characterized by elemental analysis, cyclic voltammetry, electronic, IR and variable temperature (1)H and (13)C NMR spectra. For complex 1, the thioureide vCN value is shifted to higher wavenumber compared to 2 and N(13)CS2 carbon signal observed for 1 is additionally shielded compared to the parent complex 2, suggesting increased strength of the thioureide bond due to the presence of the π-accepting phosphine. In the room temperature (13)C NMR spectrum of 1, two pseudo doublets are observed in the aliphatic region. Variable temperature (13)C NMR spectral studies suggest that the fast thiocyanate exchange appears to be responsible for the appearance of pseudo doublets. Single crystal X-ray structural analysis of 1 and 2 confirm the presence of four coordinated nickel in a distorted square planar arrangement with the NiS2PN and NiS4 chromophores, respectively. The NiS bonds are symmetric in 2 (2.1914(14) and 2.2073(13)Å). But significant asymmetry in NiS bond distances was observed in 1 (2.2202(8)Å and 2.1841Å). This observation clearly supports the less effective trans effect of SCN(-) over PPh3. Cyclic voltammetric studies revealed easier reduction of nickel(II) to nickel(I) in complex 1 compared to 2.

4-(2-Chloro-ethyl)morpholinium picrate.

The title compound, C(6)H(13)ClNO(+)·C(6)H(2)N(3)O(7) (-), was synthesized from picric acid and 4-(2-chloro-ethyl)morpholine. The crystal structure is stabilized by C-H⋯O and N-H⋯O hydrogen-bond inter-actions.

3-Anilinothio-carbonyl-4-hydroxy-chromen-2-one.

The geometrical parameters of the title compound, C(16)H(11)NO(3)S, are in the usual ranges. The two aromatic residues are not coplanar and are twisted by a dihedral angle of 66.63 (6)°. The crystal structure is stabilized by N-H⋯O and O-H⋯S inter-actions.

3-(6-Methyl-2-pyrid-yl)-2-phen-oxy-3,4-dihydro-1,3,2-benzoxaza-phosphirine 2-oxide.

In the title compound, C(19)H(17)N(2)O(3)P, the six-membered 1,3,2-oxaza-phospho-rine ring adopts a twist-boat conformation with the phosphoryl O atom in an equatorial position. The P=O(oxide) bond length is 1.457 (1) Šand the average value of the P-O distances is 1.588 Å. The crystal structure is stabilized by C-H⋯O and C-H⋯π inter-actions.