Hydrous phyllosilicate minerals exhibit many variations in unit-cell shape and symmetry, distortion due to cation ordering, polytypic repeats along Z, and lateral modulations that can affect the ease of indexing of X-ray powder diffraction patterns. In indexing the patterns of monoclinic and triclinic hydrous phyllosilicates it is important that the indices of all overlapping but nonequivalent lines be listed and used in the indexing program, with weights assigned according to their multiplicities. Deviations from orthogonal unit-cell geometry show up by a broadening or a splitting of nearly superimposed lines, as occurs also if the observed ß angle differs from that produced by a layer shift of ideal magnitude (e.g., a/3). Observed powder intensities should be correlated with those expected from the structure, and an index should not be assigned solely on the basis of the calculated d-value that is closest to that observed. Assigned indices should not violate space group extinctions. Multilayer structures show up in reflections of type k ≠ 3n for C-centered unit cells, not in 00/reflections.

Penfieldite is a lead hydroxychloride mineral with composition Pb2Cl3(OH). It belongs to the hexagonal system, space group P, a = 11.393(3), c = 4.024(1) Å. The 4 Å c parameter corresponds to the basic sub-cell, whereas modulated structures are known with a true c axis 12 times longer. The average crystal structure of penfieldite has been solved with direct methods and refined to Rw = 0.041 for 871 refections collected with Mo-Kα radiation. The chemical and structural relationships between penfeldite and laurelite, Pb2F3(F,Cl,OH), are briefly discussed. An electron diffraction study of penfieldite revealed the occurrence, besides the common modulated structure with C = 12c, of domains with a 15c periodicity. Moreover, a 9c periodicity has been observed in crystals heated at 180°C Penfieldite is quickly destroyed above 200°C.