On the structure of aragonite - Lawrence Bragg revisited

The structure of aragonite was first determined by Lawrence Bragg in 1924 in what is the now standard space-group setting Pnma (No. 62). Subsequent studies have all taken his structure as their starting points, despite Bragg's own stated doubts and some earlier etching studies which indicated that the underlying symmetry may really be polar. We have reinvestigated the structure and found that there are many reflections with significant intensity among those that should be systematically extinct in Pnma. Some of these reflections have been subjected to further experimental analysis and have been shown not to be due to Renninger effects. A possible model that satisfies these observations is one where the true structure is in space group P (1) over bar and the structure is twinned about the three axial twofold rotation axes of Pnma. The space group P1 cannot be ruled out. Evidence for these conclusions is presented. The crystal chemistry of aragonite is revisited and described in terms of the stuffed alloy CaC. The carbonate group is confirmed to be non-planar in the crystal.