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We describe the syntheses and crystal structures of two mol-ecular salts containing the 1,1-di-methyl-hydrazinium cation, namely 1,1-di-methyl-hydrazin-1-ium bromide, C2H9N2 (+)·Br(-), (I), and 2,2-di-methyl-hydrazin-1-ium di-hydrogen phosphite, C2H9N2 (+)·H2PO3 (-), (II). In (I), the cation is protonated at the methyl-ated N atom and N-H⋯Br hydrogen bonds generate [010] chains in the crystal. In (II), the cation is protonated at the terminal N atom and cation-to-anion N-H⋯O and anion-to-anion O-H⋯O hydrogen bonds generate (001) sheets.

acta crystallographica. section e, crystallographic communications

Different cation-protonation patterns in molecular salts of unsymmetrical dimethyhydrazine: C2H9N2·Br and C2H9N2·H2PO3