6533b824fe1ef96bd12808fc

RESEARCH PRODUCT

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

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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(OH2)〛2〚Fe(CN)6〛}Cl (1)·2 MeOH·12 H2O crystallizes in the triclinic space group P 1 , with a = 12.010(2) A, b = 16.316(3) A, c = 16.325(3) A, α = 97.47(3)°, β = 92.14(3)°, γ = 92.43(3)°, V = 3166(1) A3 and Z = 4. The tetranuclear compound {〚Zn(phen)2〛2〚Fe(CN)6〛2}2– (2) cocrystallizes with 〚Zn(bpy)3〛2+ and 32 H2O molecules in the monoclinic space group C2/c with a = 42.047(8) A, b = 13.541(2) A, c = 28.781(5) A, β = 120.23(3)°, V = 14158(4) A3 and Z = 2. The pentanuclear compound {〚Zn(bpy)2(H2O)〛〚Zn(bpy)2〛2〚Fe(CN)6〛2}(3)·23 H2O crystallizes in the triclinic space group P 1 with a = 15.308(3) A, b = 17.496(4) A, c = 20.050(4) A, a = 64.25(3)°, β = 72.96(3)°, γ = 88.50(3)°, V = 14158(4) A3 and Z = 5. The decanuclear compound {〚Zn(phen)2〛〚Fe(CN)6〛}2{〚Zn(phen)2〛〚Zn(phen)2(OH2)〛〚Fe(CN)6〛}2(4)·4 MeOH·26 H2O crystallizes in the monoclinic space group C2/c, with a = 48.14(1) A, b = 13.585(3) A, c = 34.131(7) A, β = 112.05(3)°, V = 20689(7) A3 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.