Hydrohalides of Lewis bases may act as halogen bond (XB) acceptors and combine two directional interactions, namely, hydrogen bonds (HB) and XBs in the same solid. 3-(1,3,5-Trimethyl-1H-pyrazol-4-yl)acetylacetone (C11H16N2O2, HacacMePz) was protonated with HX (X = Cl or Br) to afford the hydrohalides, C11H17N2O2+·X- or H2acacMePz+·X- (1, X = Cl; 2, X = Br). Hydrohalides 1 and 2 are isomorphous and adopt a classical dipole packing. Consistent with the observation for most β-diketones, the enol form with an intramolecular HB is observed. Additional noteworthy interactions are HBs of the protonated pyrazolium towards the X- anion at donor-acceptor distances of 2.9671 (17) Å for 1 and 3.159 (4) Å for 2. Cocrystallization of hydrobromide 2 with the XB donor tetrafluorodiiodobenzene (TFDIB) leads to the adduct C11H17N2O2+·Br-·0.5C6F4I2·H2O or (H2acacMePz+·Br-)2·(H2O)2·TFDIB (3), in which the XB donor TFDIB is situated on a crystallographic centre of inversion. Classical HBs link organic cations, water molecules and Br- anions into chains along [010]. Almost orthogonal to this interaction, XBs with Br...I = 3.2956 (4) Å connect neighbouring chains along [102] into two-dimensional sheets in the (10-2) plane. Assisted by their negative charge, halide anions represent particularly good nucleophiles towards XB donors.
Keywords: QTAIM; crystal engineering; electron density; halogen bonds; hydrogen bonds.
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