Microtextures and crystal chemistry in P2(1)/c pigeonites

A single-crystal X-ray investigation was performed on crystals of P21/c natural pigeonite with varying Ca and Fe* ( = Fe2+ + Mn2+) contents, in order to verify the effect of microtextural disorder on structure refinements and to constrain the crystal chemistry of pigeonite. Antiphase domains and exsolution lamellae affect differently the refinement results. In a crystal free of exsolution the structure obtained after refinement with all reflections is an average of that of the antiphase domains and of their boundaries, whereas in an exsolved crystal it represents only the structure of the prevailing pigeonite lamellae. The refinement using only h + k odd reflections seems to give the structure of the Ca-free pigeonite characteristic of the antiphase domains rather than that of Ca-rich domain walls. The ratio of the scale factors in refinements with all reflections and with only h + k odd reflections allows the ratios of the exsolved augite and pigeonite phases to be estimated. The crystal chemistry of the investigated samples follows the trends outlined by data on Ca-free and Fe-free synthetic samples. In particular, it is shown that Ca and Fe* substitution for Mg induce similar changes in the average structure, i.e. both induce an expansion in the M1 polyhedron and decrease the difference between the M2–O3 distances.