Molecular and Inner Complex Compounds of Dioxomolybdenum(VI) with Disubstituted Salicydenealcoholimines: Crystal Structure of 1: 1 Dioxo(3,5-Dibromosalicylidenemonoethanoliminato)molybdenum(VI) Solvate with Methanol [MoO2(L1) • MeOH] (L1 = C9H7Br2NO2)

Complexes of dioxomolybdenum(VI) of the molecular (MoO2Cl2 center dot 2H(2)L) and inner complex ([MoO2L center dot Solv]) types are synthesized (H2L are azomethines, derivatives of disubstituted R-1,R-2-salicylaldehydes (R-1, R-2 = 3.5-Br-2; R-1 = 3-MeO, R-2 = 5-Br) and monoethanolamine; Solv is a methanol, dimethylformamide, pyridine, or a-picoline molecule). The cis-octahedral structure of the complexes is concluded on the basis of the IR spectroscopic data. In the molecular compounds, the ligands are coordinated via the O atom of the carbonyl group of the H2L tautomeric form. In the inner complex compounds, the ligands are coordinated in the deprotonated benzoid form. The structure of [MoO2(L-1) center dot MeOH] (I) (where L-1 is C9H7Br2NO2) is determined by X-ray diffraction analysis (CIF file CCDC no. 1898088). In the mononuclear molecule of compound I, the Mo atom has the octahedral coordination by two oxo ligands, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) two-charge ligand (L-1)(2-), and the O atom of the methanol molecule. The neutral N(1) and O(1) atoms of the L-1 and MeOH ligands, respectively, are arranged in the trans positions to the O(oxo) ligands. The Mo-N(1) (2.265 angstrom) and Mo-O(1) (2.372 angstrom) bonds are substantially elongated due to the structural manifestation of the trans effect of the multiply bonded oxo ligands. The intermolecular hydrogen bonds (MeOH)O-H center dot center dot center dot O(oxo) join the molecules into supramolecular 1D chains.