1,3-Butadiene on Titan: Crystal Structure, Thermal Expansivity, and Raman Signatures

Titan is one of the most Earth-like objects in the Solar System, hosting a nitrogen-rich atmosphere and an impressive inventory of organics ranging from simple to complex. 1,3-Butadiene has been suggested to be one of the photochemical products that could be present on Titan’s surface. As the simplest conjugated hydrocarbon, it is expected to partake in many chemical processes that influence Titan’s geology and evolution. However, the crystal structure and thermal expansivity of 1,3-butadiene, two of its most fundamental properties, have remained largely unknown for over eight decades, especially at cryogenic conditions often encountered on planetary bodies. In this work, a series of powder X-ray diffraction and micro-Raman experiments have been conducted in order to elucidate the crystal structure and thermal behavior of solid 1,3-butadiene between 85 and 165 K. Specifically, a single crystalline phase (space group P21/c) is observed in the temperature range of study in which the butadiene molecules form layers of zigzag chains that are stabilized by an intricate network of intermolecular C–H···π interactions. This monoclinic structure is shown to exhibit significant anisotropic thermal expansion along the three directions with the majority occurring along the crystallographic b-axis. The calculated bulk density of 1,3-butadiene (0.877 g/cm3 at 150 K) is considerably lower than previously realized. These results help enhance our understanding of the putative molecular solids that make up Titan’s surface and could hold important implications for physical as well as mechanical processes occurring on this icy satellite.