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The hydrazinium monofluoride NHF crystallizes with orthorhombic symmetry, space group P222, a=4.592 Å, b=8.217 Å, c=12.341 Å, and 8 formula units. The structure was determined by the permutation method in projection, and by the three-dimensional Patterson function, refined by Full-Matrix-Least-Squares ( R=0.056). The structure consists of NH- and F-ions, bonded with hydrogen bonds N−H ... N and N−H ... F. Each NH ion is surrounded by four F-ions and two nitrogen atoms of two different NH ions. Each F ion is connected with four different NH ions. [ABSTRACT FROM AUTHOR]