On Dimensionality of Halogen-Bonded Thiophene Solid-State Assemblies

We report on the structures of three dibromothiophene compounds ( 4 , 5 , and 12 ) and the analysis of the patterns of self-assembly in the solid state by C Br⋅⋅⋅Br C halogen bonds of a selected set of 16 di- or poly-bromine (poly)thiophene monomers sorted according to the dimensionality of their halogen-bonded, extended frameworks thereby identifying syn- or anti-strings and layers. We conclude that in 1 , 2 , 9 , and 10 , the antiparallel orientation of successive C Br⋅⋅⋅Br C halogen-bonded dibromothiophene units along extended anti-strings is linked to the occurrence of solid-state polymerization.