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Reactions of Mn(NCS) 2  with 3-bromopyridine in acetonitrile lead to the formation of Mn(NCS) 2 (3-bromopyridine) 4  ( 1 ) and Mn(NCS) 2 (3-bromopyridine) 2 (MeCN) 2  ( 2 ) that were characterized by single crystal X-ray diffraction. Compounds  1  and  2  consist of discrete complexes, in which the Mn(II) cations are octahedrally coordinated by two  trans -N-bonding thiocyanate anions and four pyridine ( 1 ) or two pyridine and two acetonitrile ligands ( 2 ). Thermoanalytical measurements on  1  and  2  have shown that upon heating half of the 3-bromopyridine co-ligands from  1  or both acetonitrile ligands from  2  are removed leading to a crystalline phase with the composition [Mn(NCS) 2 (3-bromopyridine) 2 ]   n    ( 3-II ). From dry n-butanol a phase with the same composition was obtained ( 3-I ) that corresponds to a polymorphic or isomeric form of  3-II . Crystal structure analysis of  3-I  shows that in this form the Mn cations are linked by pairs of anionic ligands into linear chains. The results of magnetic measurements on  3-I  show antiferromagnetic interactions along the chains and the analysis of the magnetic susceptibility using the Fisher model for chains gave a  J  value of −5.76(5) K.

Synthesis, crystal structure and magnetic properties of coordination compounds of Mn(NCS) 2 with the 3-bromopyridine ligand