Weaving a 2D net of hydrogen and halogen bonds: cocrystal of a pyrazolium bromide with tetrafluorodiiodobenzene.

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) plane. Assisted by their negative charge, halide anions represent particularly good nucleophiles towards XB donors. [ABSTRACT FROM AUTHOR]