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Crystals of 1,10-phenanthrolinium penta-fluorido-oxidotungstate(VI), (1,10-phen-H)[WOF 5 ] (1,10-phen = 1,10-phenanthroline, C 12 H 8 N 2 ), were obtained upon hydrolysis of WF 6 (1,10-phen) in CH 3 CN at 193 K. The (1,10-phen-H)[WOF 5 ] salt contains a rare example of a [WOF 5 ] - anion in which the oxygen and fluorine atoms are ordered. This ordering was verified by bond-valence determinations and structural comparisons with [Xe 2 F 11 ][WOF 5 ] and Lewis acid-base adducts of WOF 4 with main-group donor ligands. The crystal packing is controlled by N-H⋯F hydrogen bonding that is directed exclusively to the axial F atom as a result of its increased basicity caused by the trans influence of the oxido ligand.

Crystal structure of an ordered [WOF5]− salt: (1,10-phen-H)[WOF5] (1,10-phen = 1,10-phenanthroline)

Crystal structure of an ordered [WOF₅]⁻ salt: (1,10-phen-H)[WOF₅] (1,10-phen = 1,10-phenanthroline)