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The crystal structures of trans-[OsCl 2 (acac) 2 ] (triclinic, space group P1̄, a = 7.4114(5), b = 7.6419(9), c = 7.9944(6) Å, α = 62.692(7), β = 87.687(6), γ = 60.667(6)°, Z = 1), trans-[OsBr 2 (acac) 2 ] (triclinic, space group P1̄, a = 7.467(3), b = 7.621(3), c = 8.260(3) Å, α = 115.03(3), β = 92.78(3), γ = 117.91(3)°, Z = 1), cis-[OsCl 2 (acac) 2 ] (monoclinic, space group C 2 /c, a = 13.8532(13), b = 7.7990(8), c = 13.6202(12) Å, β = 108.375(10)°, Z = 4) and cis-[OsBr 2 (acac) 2 ] (monoclinic, space group C 2 /c, a = 13.944(2), b = 8.0347(13), c = 13.743(2) Å, β = 106.757(12)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. To enhance the spectroscopic resolution, the IR and Raman spectra of the six complexes have been measured at low temperature (10 K). Using the molecular parameters of the X-ray determinations normal coordinate analyses based on a modified valence force field have been performed for trans-[OsCl 2 (acac) 2 ], trans-[OsBr 2 (acac) 2 ] and cis-[OsCl 2 (acac) 2 ], and the normal modes of vibration assigned. With sets of 31 or 32 force constants, taking into account the innerligand vibrations, a good agreement between observed and calculated frequencies has been achieved. The valence force constants for the X-Os-X axes are f d (OsCl) = 1.81, f d (OsBr) =1.61 mdyn/Å, and for the Cl′-Os-O* axis are f d (OsCl’) = 1.94, f d (OsO*) = 2.81 mdyn/Å and f d (OsO) ranges from 3.27 to 3.31 mdyn/Å.

zeitschrift für naturforschung b

Kristallstrukturen, Schwingungsspektren und Normalkoordinaten- analysen von cis- und trans-[OsX 2 (acac) 2 ], X = Cl, Br, I / Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of cis- and trans-[OsX 2 (acac) 2 ], X = Cl, Br, I