Conformational polymorphism of an oligothiophene the title compound (T4S), is reported for the first time. Efficient synthesis of T4S produced, in addition to the triclinic, deep orange crystals reported previously, a second (yellow, monoclinic) form of T4S, whose structure as revealed by single-crystal X-ray diffraction is presented here. The synthetic pathway is outlined and the molecular structure and crystal packing are discussed. The significantly different π-delocalization in the two conformations indicates the need for very careful molecular characterization.
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