A dodecanuclear cyclic molybdenum cluster. Preparation and X-ray structure of [{(Mo3(μ3-O)(μ-O)3(H2O)5)(μ-OH)2}4](CH3C6H4SO3)8.41H2O

Shibahara, Takashi; Sasaki, Mari; Sakane, Genta

crystal structure molybdenum aqua hydroxo oxo; structure molybdenum hydroxo oxo cluster; molybdenum aqua hydroxo oxo dodecanuclear cluster
The x-ray crystal structure anal. of the prepd. incomplete cubane-type [Mo3(μ3-O)(μ-O)3(H2O)9]4+ revealed a cyclic structure consisting of four incomplete cubane-type Mo(IV) aqua clusters, [{(Mo3(μ3-O)(μ-O)3(H2O)5)(μ-OH)2}4](pts)8.41H2O (pts = p-CH3C6H4SO3).  The compd. crystd. in the triclinic space group P-1, Z = 1, R = 0.044.  The cluster cation has a center of symmetry, and eight OH ligands bridge the four incomplete cubane-type Mo3O4 cores.  Four types of Mo-O distances exist: (i) Mo-O (μ-O within Mo3O4 cores, 1.914[5] angstrom), (ii) Mo-O (μ3-O within Mo3O4 cores, 2.024[4] angstrom), (iii) Mo-O (OH bridge between two Mo3O4 cores, 2.094[11] angstrom), (iv) Mo-O (ligating H2O mols., 2.154[7] angstrom).  The six independent Mo-Mo distances are classified into two groups: four shorter ones range between 2.483 and 2.499 angstrom (mean 2.489[4] angstrom) and two longer ones range between 2.514 and 2.517 angstrom (mean 2.516[2] angstrom).  Elongation of the Mo-Mo distances is due to the larger trans influence of the bridging OH as compared with that of the H2O ligand.

Inorganica Chimica Acta

Elsevier B.V.

237

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