Synthesis, structure and supramolecular assembly in the crystalline state of a bifunctionalized arylimido derivative of hexamolybdate

A novel bifunctionalized arylimido derivative of hexamolybdate, (Bu4N)2[Mo6O17(&z.tbnd6;NAr)2]2− (Ar=o-CH3C6H4) 1, in which the two o-tolylimido groups are bounded to hexamolybdate at the cis positions, was synthesized by self-assembled metathesis of α-type octamolybdate ion and o-toluidine with DCC as a dehydration agent. The most interesting characteristic of 1 is that the cluster anions form dimers via the <f>π–π</f> stacking between one of its two phenyl rings, and four such dimers are linked in turn via C–H<f>⋯</f>O hydrogen bonding involving terminal hexamolybdate oxygen atoms into ring-like tetramers in the solid state. [Copyright &y& Elsevier]