Spectral studies and crystal structures of molybdenum(VI) complexes containing pyridine or picoline as auxiliary ligands: interaction energy calculations and free radical scavenging studies

Three cis-MoO2 complexes [MoO2(CAB)(py)] (1), [MoO2(CAB)(3-pic)] (2) and [MoO2(CAB)(4-pic)] (3) which vary in the nature of the heterocyclic bases in the auxiliary coordination site derived from an ONO donor aroylhydrazone (H(2)CAB) have been synthesized and characterized by various physicochemical methods. The single-crystal X-ray diffraction studies reveal that the complexes adopt a distorted octahedral N2O4 coordination sphere around the Mo(VI) center in which the ONO donor atoms of hydrazone moiety and one oxido oxygen constitute the NO3 basal plane and the axial position by the other oxido oxygen and nitrogen atom of coordinated pyridine molecule in [MoO2(CAB)(py)] (1) or picoline molecule in [MoO2(CAB)(3-pic)] (2) and [MoO2(CAB)(4-pic)] (3). The hydrogen bonding interaction generates a two-dimensional supramolecular sheet-like architecture in [MoO2(CAB)(py)] (1) and [MoO2(CAB)(3-pic)] (2), whereas a three-dimensional network was observed in [MoO2(CAB)(4-pic)] (3). The interaction energy calculations reveal that the dispersion energy component dominates over other components and [MoO2(CAB)(3-pic)] (2) is found to be energetically more stable. Furthermore, the aroylhydrazone shows free radical scavenging activity, whereas the complexes are inactive.

Automated summary

Three cis-MoO2 complexes with different auxiliary coordination sites were synthesized and characterized. Hydrogen bonding interaction led to the formation of two-dimensional or three-dimensional supramolecular structures. Energy calculations revealed one of the complexes to be more stable, while the aroylhydrazone showed free radical scavenging activity.