A new monoclinic variation of Mg 2 C 3 was synthesized from the elements under high-pressure (HP), high-temperature (HT) conditions. Formation of the new compound, which can be recovered to ambient conditions, was observed in situ using X-ray diffraction with synchrotron radiation. The structural solution was achieved by utilizing accurate theoretical results obtained from ab initio evolutionary structure prediction algorithm USPEX. Like the previously known orthorhombic Pnnm structure (α-Mg 2 C 3 ), the new monoclinic C2/m structure (β-Mg 2 C 3 ) contains linear C 3 4− chains that are isoelectronic with CO 2 . Unlike α-Mg 2 C 3 , which contains alternating layers of C 3 4− chains oriented in opposite directions, all C 3 4− chains within β-Mg 2 C 3 are nearly aligned along the crystallographic c-axis. Hydrolysis of β-Mg 2 C 3 yields C 3 H 4 , as detected by mass spectrometry, while Raman and NMR measurements show clear CC stretching near 1200 cm −1 and 13 C resonances confirming the presence of the rare allylenide anion.