Halogen bonding interactions between halide anions and neutral polyiodinated linkers are used for the elaboration of anion organic frameworks, by analogy with well-known MOF derivatives. The extended, 3-fold symmetry, 1,3,5-tris(iodoethynyl)-2,4,6-trifluorobenzene (1) cocrystallizes with a variety of halide salts, namely, Et3S+I-, Et 3MeN+I-, Et4N+Br -, Et3BuN+Br-, Me-DABCO +I-, Bu3S+I-, Bu 4N+Br-, Ph3S+Br -, Ph4P+Br-, and PPN +Br-. Salts with 1:1 stoichiometry formulated as (1)·(C+,X-) show recurrent formation of corrugated (6,3) networks, with the large cavities thus generated, filled either by the cations and solvent (CHCl3) molecules and/or by interpenetration (up to 4-fold interpenetration). The 2:1 salt formulated as (1)2· (Et3BuN+Br-) crystallizes in the cubic Ia3Ì... space group (a = 22.573(5) Å, V = 11502(4) Å3), with the Br- ion located on 3Ì... site and molecule 1 on a 3-fold axis. The 6-fold, unprecedented octahedral coordination of the bromide anion generates an hexagonal three-dimensional network of Pa3Ì... symmetry, as observed in the pyrite model structure, at variance with the usual, but lower-symmetry, rutile-type topology. In this complex system, the I centering gives rise to a 2-fold interpenetration of class Ia, while the cations and solvent molecules are found disordered within interconnected cavities. Another related cubic structure of comparable unit cell volume (space group Pa3Ì..., a = 22.4310(15) Å, V = 11286.2(13) Å3) is found with (1)2·(Et3S +I-). © 2013 American Chemical Society;
