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

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.12H(2)O crystallizes in the triclinic space group P (1) over bar, with a = 12.010(2) Angstrom, b = 16.316(3) Angstrom, c=16.325(3) Angstrom, alpha = 97.47(3)degrees, beta = 92.14(3)degrees, gamma = 92.43(3)degrees, V = 3166(1) Angstrom(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 H2O molecules in the monoclinic space group C2/c with a = 42.047(8) Angstrom, b = 13.541(2) Angstrom, c = 28.781(5) Angstrom, beta = 120.23(3)degrees, V = 14158(4) Angstrom(3) and Z = 2. The pentanuclear compound {[Zn(bpy)(2)(H2O)] [Zn(bpy)(2)](2)[Fe(CN)(6)](2)} (3).23H(2)O crystallizes in the triclinic space group P (1) over bar with a = 15.308(3) Angstrom, b = 17.496(4) Angstrom, c = 20.050(4) Angstrom, a = 64.25(3)degrees, beta = 72.96(3)degrees, gamma = 88.50(3)degrees, V = 14158(4) Angstrom(3) 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).4MeOH.26 H2O crystallizes in the monoclinic space group C2/c, with a = 48.14(1) Angstrom, b = 13.585(3) Angstrom, c = 34.131(7) Angstrom, beta = 112.05(3)degrees, V = 20689(7) Angstrom(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.