The crystal structure of a clinopyroxene with composition (Na0.75Ca0.25)(Cr0.75Mg0.25)Si2O6 was refined at 100, 150, 200, 250 and 298 K. The work was performed in the context of an investigation on the low-temperature behaviour of A
3+Si2O6 (with A dominant in Na and M = transition elements) pyroxenes in order to provide new insights concerning the phase transition and anomalies recently found in the low-temperature behaviour of NaTiSi2O6 and NaGaSi2O6 compounds. The refinements were done in the C2/c space group (wR
2 between 0.048 and 0.068), and no change of symmetry was observed down to 100 K. Highly-anisotropic axial thermal expansion occurs with the scheme αb ≥ αb > αc.
The M2, M1 and T polyhedra expand with α
M2 > α
as generally observed in pyroxenes. A discontinuity in the M1 polyhedral volume is observed between 200 and 250 K, similar to the one observed in NaGaSi2O6 between 190 and 235 K.
The atomic displacement parameters are scaled according to the following pattern: U
M2 > U
O2 > U
O3 ≥ U
01 > U
T ≥ U
M1 Comparison with previous data along the CaMgSi2O-NaCrSi2O6 join suggests significant positional disorder for the O1 oxygen, due to repulsion of the 2p orbitals of O1 and the non-bondine 3d electrons of Cr.