Pentafluorobenzoato‐dimolybdenum(II) Solvate and Co‐crystal Complexes with Benzene and Naphthalin

The quadruply bonded Mo 2 4+ complex Mo 2 (DAniF) 3 (OOCC 6 F 5 ) ( 1 ) [DAniF = N , N ′‐bis(4‐methoxyphenyl)formamidinate] was synthesized. The solvate Mo 2 (DAniF) 3 (OOCC 6 F 5 ) · (C 6 H 6 ) ( 2 ) and co‐crystal Mo 2 (DAniF) 3 (OOCC 6 F 5 ) · (C 10 H 8 ) ( 3 ) complexes were obtained by self‐assembly of crystals of 1 with benzene and naphthalin, respectively. Compounds 1 , 2 , and 3 were structurally characterized by single‐crystal X‐ray diffraction. In monomer 1 , the Mo–Mo bond length of 2.0874(6) Å is typical for dimolybdenum quadruple bonds. The solvate complex 2 was stabilized by weak π–π stacking interactions between the benzene molecule and the pentafluorophenyl ring (as indicated by a center‐to‐center distance of 3.838(10) Å and a center‐to‐plane distance of 3.712(4) Å between phenyl and pentafluorophenyl ring) and intermolecular C–H ··· F–C interactions (the shortest F ··· H distance is 2.560(2) Å). In complex 3 , a one‐dimensional chain was formed by C–H ··· F–C interactions between the hydrogen atoms in naphthalin and the fluorine atoms in the monomer (H ··· F distances of 2.582(2) Å). Information on the structures in solution of the three crystals was obtained by 1 H NMR spectroscopy.