Centres [Formula: see text] formed in α-quartz by 77 K x irradiation and warming above ca. 165 K, both exhibit a reversible change in symmetry of the centres from C1 at 75 K to C2 at 295 K, as observed by X-band electronic paramagnetic resonance spectroscopy. Each centre contains a Ge3+ ion (S = 1/2) substituted for a Si4+ ion, with a nearby Na+ interstitial ion. Spin-Hamiltonian electronic Zeeman, 73Ge and 23Na nuclear hyperfine and quadrupole parameter matrices for these centres were measured at temperatures 75, 190, and 295 K. They show that the change is associated with the defect reorienting between sites related by a two-fold crystallographic axis a, with energy barrier 0.223(6) eV for A and 0.178(14) eV for C. In both centres, ca. 50% of the spin density is located in a Ge sp orbital; in A, the sp orbital is oriented close to a, while in C it is nearly parallel to an O–Si–O bond-angle bisector that is nearly normal to a. Theoretical hyperfine matrices indicate that the Na ions are located near a, in a c-axis channel near the Ge site. Above ca. 270 K, A and C are observably in equilibrium, and are thus deemed to be isomeric species.