Crystal and molecular structure of [{Cu(pmdien)F(H₂O)}₂][BF₄]₂ (pmdien = N,N,N′,N″,N″-pentamethyldiethylenetriamine): a novel dimeric cation with extremely short O–H  · · ·  F interactions

Abstract

The crystal and molecular structure of [{Cu(pmdien)F(H₂O)}₂][BF₄]₂1 (pmdien = N,N,N′,N″,N″-pentamethyldiethylenetriamine) has been determined. The cation exists in the solid state as a unique dimer, held together by O–H  · · ·  F hydrogen-bonding interactions [O  · · ·  F 2.567(2), O–H 0.83(3), F  · · ·  H 1.74(3) Å, F  · · ·  H–O 178.5(23) °]. The O  · · ·  F separation is the shortest ligand fluoride–ligand water hydrogen-bonding interaction in any copper(II) complex. The copper atom is five-co-ordinate and has a square-based pyramidal geometry comprising equatorially located pmdien (mean Cu–N 2.052 Å), and fluoride [Cu–F 1.888(1) Å] and axially located water [Cu–O 2.211(1) Å].

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