Expanded halogen-bonded anion organic networks with star-shaped iodoethynyl-substituted molecules: from corrugated 2D hexagonal lattices to pyrite-type 2-fold interpenetrated cubic lattices.

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(-), Et3MeN(+)I(-), Et4N(+)Br(-), Et3BuN(+)Br(-), Me-DABCO(+)I(-), Bu3S(+)I(-), Bu4N(+)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 Ia3 space group (a = 22.573(5) Å, V = 11502(4) Å(3)), with the Br(-) ion located on 3 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 Pa3 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 Pa3̅, a = 22.4310(15) Å, V = 11286.2(13) Å(3)) is found with (1)2·(Et3S(+)I(-)).