[Mn 2 (bipym)(H 2 O) 8 ] 4+ and [Fe(bipy)(CN) 4 ] − as building blocks in designing novel bipym- and cyanide-bridged heterobimetallic complexes (bipym = 2,2′-bipyrimidine and bipy = 2,2′-bipyridine)

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Two new cyano complexes, K[Fe(bipy)(CN)4]·H2O (1) and (μ-bipym)[Mn(H2O)3{Fe(bipy)(CN)4}]2[Fe(bipy)(CN)4]2·12H2O (2), have been synthesised and their structures determined by single-crystal X-ray diffraction. Complex 1 is made up of mononuclear [Fe(bipy)(CN)4]− anions, potassium cations and water molecules of crystallization. The iron(III) is six-coordinated, being surrounded by two nitrogen atoms of a chelating bipy and four carbon atoms of four cyanide groups [Fe–N and Fe–C 1.991(3)–1.990(3) and 1.958(5)–1.914(5) Å, respectively]. Complex 2 consists of centrosymmetric tetranuclear (μ-bipym)[Fe(H2O)3{Fe(bipy)(CN)4}]22+ cations, [Fe(bipy)(CN)4]− anions and water molecules of crystallization. The cyano-containing iron(III) complex of 1 is present in 2 but in the latter it acts not only as a counterion but also as a monodentate ligand towards the manganese atom through one of its four cyanide groups. Bond lengths and angles around the iron atoms in 2 are practically identical to those observed in 1. The manganese atom in 2 is six-coordinated with two bipym- and one cyanide-nitrogen atoms and three mer-water molecules comprising a distorted octahedral environment [Mn–N(bipym) 2.35(1) and 2.29(1) Å, Mn–N(cyanide) 2.19(2) and Mn–O 2.21(1)–2.12(2) Å]. The manganese–manganese and manganese–iron separations across the bis-chelating bipym and single-cyano bridge are 6.131(6) and 5.092(4) Å, respectively. Studies of the magnetic behaviour of 1 and 2 in the temperature range 1.9–300 K reveal that compound 1 is a magnetically isolated low-spin iron(III) complex with an important orbital contribution whereas significant antiferromagnetic interactions occur in 2 between the manganese(II) ions across bis-chelating bipym (J = −1.2 cm−1) and between the manganese(II) and iron(III) ions through the single-cyano bridge (j = −3.0 cm−1). The use of [FeIII(AA)(CN)4]− (AA = bidentate ligand) as a ligand towards metal ions appears very promising in designing new cyano-bridged polynuclear compounds.