This out-of-center "primary" distortion is inherent to the oxide fluoride anions of the early d0transition metals and arises from dπ-pπ metal-oxide orbital interactions.1,2 In the [NbOF4]1-anion,the Nb5+ moves from the center of the square pyramid toward the oxide ligand to form a short Nb=O bond and long trans Nb-F bond.The result of single-crystal X-ray diffraction indicates that the primary distortion of the [NbOF4]1-anion is affected by the coordination environment that is created by the three-dimensional extended structure.The formation of bonds between the oxide and/or trans-fluoride ligands of the [NbOF4]1-anions weakens the n component of the Nb=O bond.At the same time,hydrogen bond interactions between the equatorial fluorides and the 1,10-phenanthroline groups both lengthen the equatorial Nb-F bonds and can further reduce the symmetry of the [NbOF4]1-anion.These combined three-dimensional bond network interactions that serve to lengthen the Nb=O bond and thereby decrease the primary distortion of the [NbOF4]1-anion are illustrated in the structures of a new niobium oxide fluoride phases,[Ci2N2H8][NbOF4]·H3O,that was synthesized and characterized using X-ray diffraction.Crystal data for [C12N2H8][NbOF4]·H3O:monoclinic,space group P2(l)/n,with a=16.603(3) (A),b =3.9437(7) (A),c=20.240(4) (A),and Z=4.