The Crystal and Molecular Structure of Quadrivalent Osmium Porphyrin; μ-Oxo-bis[methoxo(octaethylporphinato)osmium(IV)]

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Abstract
The crystal structure of the title complex has been determined by the X-ray method. The complex crystallizes in the monoclinic space group P2/c with a=24.171(9), b=14.037(3), c=24.401(9) Å, β=119.68(9)°, and Z=4. The structure was solved by the heavy-atom method and refined to R=0.094 for 3838 reflections. Two independent dimers exist with a crystallographically imposed two-fold axis in the unit cell. The two dimers are in an approximately orthogonal arrangement, and they take very similar conformations. The noticeable structural parameters are the average distances of 2.033(28) Å for OsIV–N, 1.808(3) Å for OsIV–O2−, and 1.997(29) Å for OsIV–OCH3. The two porphinato cores bridged by a μ-oxo oxygen atom rotate around the approximately linear Os–O–Os bond (the average valence angle=178°) by 23(1)° from the eclipsed form. The porphine ring is planar within 0.10 Å, and deviation of the Os atom from the porphinato plane of the four nitrogen atoms is 0.06 Å. These results were compared, in the relation of the specific physicochemical properties in solution, with those of the corresponding RuIV complexes reported previously.

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