Pyrimidine-2-thione (HSpym) reacts with lead(II) thiocyanate and lead(II) bromide in N,N-dimethylformamide (DMF) to form poly[(μ-isothiocyanato-κ2
N:S)(μ4-pyrimidine-2-thiolato-κ6
N
1,S:S:S:S,N
3)lead(II)], [Pb(C4H3N2S)(NCS)]
n
or [Pb(Spym)(NCS)]
n
, (I), and the polymeric one-dimensional (1D) compound catena-poly[[μ4-bromido-di-μ-bromido-(μ-pyrimidine-2-thiolato-κ3
N
1,S:S)(μ-pyrimidine-2-thione-κ3
N
1,S:S)dilead(II)] N,N-dimethylformamide monosolvate], {[Pb2Br3(C4H3N2S)(C4H4N2S)]·C3H7NO}
n
or {[Pb2Br3(Spym)(HSpym)]·DMF}
n
, (IIa), respectively. Poly[μ4-bromido-di-μ3-bromido-(μ-pyrimidine-2-thiolato-κ3
N
1,S:S)(μ-pyrimidine-2-thione-κ3
N
1,S:S)dilead(II)], [Pb2Br3(C4H3N2S)(C4H4N2S)]
n
or [Pb2Br3(Spym)(HSpym)]
n
, (IIb), could be obtained as a mixture with (IIa) when using a lesser amount of solvent. In the crystal structures of the pseudohalide/halide PbII stable compounds, coordination of anionic and neutral HSpym has been observed. Both Spym− (in the thiolate tautomeric form) and NCS− ligands were responsible for the two-dimensional (2D) arrangement in (I). The Br− ligands establish the 1D polymeric arrangement in (IIa). Eight-coordinated metal centres have been observed in both compounds, when considering the Pb...S and Pb...Br interactions. Both compounds were characterized by FT–IR and diffuse reflectance spectroscopies, as well as by powder X-ray diffraction. Compound (IIa) and its desolvated version (IIb) represent the first structurally characterized PbII compounds containing neutral HSpym and anionic Spym− ligands. After a prolonged time in solution, (IIa) is converted to another compound due to complete deprotonation of HSpym. The structural characterization of (I) and (II) suggests HSpym as a good candidate for the removal of PbII ions from solutions containing thiocyanate or bromide ions.
Reversible solid-state structural conversion between a three-dimensional network and a one-dimensional chain of Cu(ii) triazole coordination polymers in acidic/basic-suspensions or vapors