Low-dimensional compounds containing cyanido groups. XXIII. Synthesis and crystal structures of three ionic iron(II) complexes

Abstract Three new ionic [Fe(phen)3](N(CN)2)2 · 4.5 H2O (1), [Fe(dmeophen)3](N(CN)2)2 · 1.5 H2O (2) and [Fe(dmeophen)3](C(CN)3)2 (3) complexes have been synthesized (phen is 1,10-phenanthroline, dmeophen is 4,7-dimethoxy-1,10-phenanthroline). X-ray structural analysis ((1): C2/c, a = 18.1041(3), b = 16.8244(3), c = 24.6691(5) Å, β = 92.138(2)°; (2): C2/c, a = 22.0291(10), b = 18.8654(5), c = 11.6914(5) Å, β = 114.872(5)°; (3): Pbca, a = 12.0841(5), b = 22.0624(13), c = 34.2729 (16) Å) revealed that the structures of all discussed complexes consist of one [Fe(phen)3]2+ or [Fe(dmeophen)3]2+ complex cation and two uncoordinated tcm or dca counteranions (tcm is tricyanomethanide, dca is dicyanamide); water molecules were found in (1) and (2), too. In the cations, the Fe(II) atom is coordinated by six nitrogen atoms of chelate coordinated neutral ligands forming a distorted octahedron coordination geometry. One of the anions in each structure is disordered. Weak π–π interactions between planar dca anions and pyridine rings of phen in (1) and O—H … O and O—H … N hydrogen bonds in (1) and (2) stabilize their structures.

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