A new synthetic route to isothiocyanate containing materials is presented. Five isothiocyanate 4-methylpyridine (γ-picoline) compounds were prepared by refluxing metal powders (Fe, Co, Ni and Cu) with thiourea in γ-picoline. The isothiocyanate ligand is generated in situ by the isomerization of thiourea to NH4+SCN− at reflux temperatures. The complexes [Fe(NCS)2(pic)4]·pic (1), [Co(NCS)2(pic)4]·pic (2), [Ni(NCS)2(pic)4] (3), [Cu(NCS)2(pic)4]·2/3pic·1/3H2O (4), [Cu(NCS)(pic)2]x (5) (where pic=γ-picoline) were characterized by X-ray crystallography; the structural data for compounds 1–3 and 5 are presented.

Three new isothiocyanate-4-methylpyridine anionic compounds were prepared by refluxing metal powders (Mn, Fe, and Cu) with thiourea in 4-methylpyridine (γ-picoline). The isothiocyanate ligand is believed to be generated in situ by the isomerization of thiourea to NH4+SCN− at reflux temperatures. The complexes (Hpic)2[Mn(NCS)4(pic)2]·2pic (1), (Hpic)2[Fe(NCS)4(pic)2]·2pic (2), and (Hpic)[Cu(NCS)3(pic)2]·pic (3) (where pic=γ-picoline) were characterized by single crystal X-ray crystallography. Compounds 1 and 2 are isostructural with four equatorially bound isothiocyanate ligands and two axially bound γ-picoline molecules. Compound 3 is a five-coordinate Cu(II) molecule with a distorted square pyramidal geometry. Coordinated picoline and two isothiocyanates form the basal plane and the remaining isothiocyanate is bound at the apex. The structural data for compounds 1, 2, and 3 are presented.

The three compounds Ga2Cl4(4-mepy)2 (1), [GaCl2(4-mepy)4]GaCl4·12(4-mepy) (2) and GaCl2(4-mepy)2(S2CNEt2) (3) (4-mepy = 4-methylpyridine) have been prepared from reactions of gallium (II) chloride in 4-methylpyridine and characterized by single-crystal X-ray analysis. Small variations in the reaction conditions of gallium(II) chloride can produce crystals with substantially different structural properties. The three compounds described here encompass a neutral gallium(II) dimer in which each gallium is four-coordinate, an ionic compound containing both anionic and cationic gallium complex ions with different coordination numbers and a neutral six-coordinate heteroleptic dialkyldithiocarbamate species.