ja400740v_si_001.cif (244.67 kB)

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

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posted on 24.04.2013, 00:00 by Julien Lieffrig, Olivier Jeannin, Marc Fourmigué
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 Ia3̅ space group (a = 22.573(5) Å, V = 11502(4) Å3), with the Br ion located on 3̅ 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 Pa3̅ 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) Å3) is found with (1)2·(Et3S+I).