Structural diversity of cyanide-bridged bimetallic clusters based on hexacyanometallate building blocks

Abstract

Four new cyanide-bridged bimetallic complexes, with different geometries and nuclearities, have been synthesized and characterized by single crystal X-ray crystallography. The trinuclear compound {〚Zn(bpy) 2(OH 2)〛 2〚Fe(CN) 6〛}Cl ( 1)·2 MeOH·12 H 2O crystallizes in the triclinic space group P 1 , with a = 12.010(2) Å, b = 16.316(3) Å, c = 16.325(3) Å, α = 97.47(3)°, β = 92.14(3)°, γ = 92.43(3)°, V = 3166(1) Å 3 and Z = 4. The tetranuclear compound {〚Zn(phen) 2〛 2〚Fe(CN) 6〛 2} 2– ( 2) cocrystallizes with 〚Zn(bpy) 3〛 2+ and 32 H 2O molecules in the monoclinic space group C2/ c with a = 42.047(8) Å, b = 13.541(2) Å, c = 28.781(5) Å, β = 120.23(3)°, V = 14158(4) Å 3 and Z = 2. The pentanuclear compound {〚Zn(bpy) 2(H 2O)〛〚Zn(bpy) 2〛 2〚Fe(CN) 6〛 2}( 3)·23 H 2O crystallizes in the triclinic space group P 1 with a = 15.308(3) Å, b = 17.496(4) Å, c = 20.050(4) Å, a = 64.25(3)°, β = 72.96(3)°, γ = 88.50(3)°, V = 14158(4) Å 3 and Z = 5. The decanuclear compound {〚Zn(phen) 2〛〚Fe(CN) 6〛} 2{〚Zn(phen) 2〛〚Zn(phen) 2(OH 2)〛〚Fe(CN) 6〛} 2( 4)·4 MeOH·26 H 2O crystallizes in the monoclinic space group C2/ c, with a = 48.14(1) Å, b = 13.585(3) Å, c = 34.131(7) Å, β = 112.05(3)°, V = 20689(7) Å 3 and Z = 4. The unusual geometries discovered in this mixed Fe(III)/Zn(II) chemistry provide excellent models for the design of high-spin cyanide-bridged transition-metal clusters.