1D cadmium(II) thiocyanate systems: Synthesis and characterization of three new polymeric 1D cadmium(II) thiocyanato complexes

Three new cadmium(II) thiocyanato complexes, [{Cd(NCS)2(val)}·H2O]n1, [Cd(NCS)2(3-ampy)2]n2, and [Cd(NCS)2(pyrazolinone)]n3, (val = d,l-valine, 3-ampy = 3-aminopyridine and pyrazolinone = 3-methyl-1-phenyl-2-pyrazolin-5-one) have been synthesized and structurally characterized. The X-ray structure analysis revealed di-μ-N,S thiocyanato bridges connecting cadmium centers in a 1D chain with the co-ligand blocking the remaining coordination sites. The structure of complex 1 features six coordinate Cd(II) centers, each cadmium is surrounded by two N atoms and two S atoms from two bridging N,S-thiocyanato groups giving rise to a zigzag 1D chain and two oxygen atoms of the alternating chelating μ-O,O′-valine that coordinates as zwitterionic terminal amino acid. The structure of complex 2 consists of octahedral Cd(II) centers, connected by di-μ-N,S-bridging NCS groups, thus forming a 1D chain system along the [1 0 1] direction. The amino-groups are forming one intra-chain NH⋯N hydrogen bond and one interchain NH⋯N hydrogen bond to N-atoms of adjacent chains. The structure of 3 reveals di-μ-N,S-NCS doubly bridged unusual penta-coordinated cadmium centers with the alternating monodentate pyrazolinone ligand blocking the fifth coordination site. IR spectra and thermal properties of complexes are reported.