Acetylene and ammonia are known to form a stable orthorhombic co-crystal under the surface conditions of Saturn's moon Titan (1.5 bar = 150 kPa, 94 K). Such a material represents a potential new class of organic minerals that could play an important role in Titan's geology. In this work, the thermal expansion of this co-crystalline system has been derived from in situ powder X-ray diffraction data obtained between 85 and 120 K. The results indicate significant anisotropy, with the majority of the expansion occurring along the c axis (∼2% over the temperature range of interest). Rietveld refinements reveal little change to the structure compared with that previously reported by Boese, Bläser & Jansen [J. Am. Chem. Soc. (2009), 131, 2104–2106]. The expansion is consistent with the alignment of C—H...N interactions along the chains in the a and b axes, and weak intermolecular bonding in the structural layers along the c axis.