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Three new ionic [Fe( phen ) 3 ](N(CN) 2 ) 2  · 4.5 H 2 O ( 1 ), [Fe( dmeophen ) 3 ](N(CN) 2 ) 2  · 1.5 H 2 O ( 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 ):  C 2/ c ,  a  = 18.1041(3),  b  = 16.8244(3),  c  = 24.6691(5) Å,  β  = 92.138(2)°; ( 2 ):  C 2/ 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.

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