The heterometallic clusters Os 2 Fe(CO) 10 ( μ -X) 2 (X = OH, I) were obtained from the binuclear osmium complexes Os 2 (CO) 6 X n (X = Cl, n = 4; X = I, n = 2). The structure of Os 2 Fe(CO) 10 ( μ -OH) 2 was determined by a single-crystal X-ray diffraction analysis. The crystal is triclinic and crystallizes in the space group P l¯ and a = 14.009( 6 ), b = 13.330( 4 ), c = 9.511(2)Å, α = 103.69(2), β = 81.83(3), γ = 102.22(3)°, V = 1699(1) Å 3 , Z = 4, D calc = 2.969g cm −3 , R = 0.093 for 2359 independent reflections ( F o > 6 σ ( F o )). The cluster consists of an open triangular OsFeOs metal core with no Os-Os bond. The bridging OH groups are coordinated semiaxially and span the Os-Os edge. On heating in the presence of an excess of Fe 2 (CO) 9 , the Os 2 Fe(CO) 10 ( μ -I) 2 cluster is converted to Os 2 Fe(CO) 12 . The co-crystallate Os 2 Fe(CO) 12 · 0.41Os 3 (CO) 12 was isolated from the solution of Os 2 Fe(CO) 10 ( μ -I) 2 , as the product of decomposition of the initial cluster. It crystallizes in the monoclinic system, space group P 2 1 / n , with a = 8.056(2), b = 14.743(2), c = 14.520(2)Å, β = 100.62(1)°, V = 1695.0(5)Å 3 , Z = 4, D calc = 3.179g cm −3 and R = 0.0250 for 1997 independent reflections ( F o > 4 σ ( F o )).