The crystal structure of cumengéite, Pb21Cu20Cl42(OH)40, tetragonal, a= 15.065(2), c= 24.436(5) Å, V = 5546(2) Å3, space group I4/mmm, Z = 2, has been solved by direct methods and refined by least-squares to an R index of 7.1 % for 1158 observed (I > 2.5σ I) reflections. The cumengéite structure shows a very diverse range of cation coordinations. There are five distinct Pb sites with the following coordination polyhedra: octahedron, square antiprism, augmented trigonal prism, a very distorted biaugmented trigonal prism and a fairly regular biaugmented trigonal prism, the latter being only half-occupied; there are two distinct Cu sites with octahedral and square pyramidal coordination respectively. The coordination polyhedra share elements to form prominent columns or rods of polyhedra parallel to the c-axis and centred on the 4-fold axes of the unit cell. These rods form a body-centred array, and link by sharing elements of their coordination polyhedra.

The application of Raman spectroscopy to the study of the mixed cationic Pb-Cu and Pb-Cu-Ag minerals: boleite, cumengeite and diaboleite has enabled their molecular structures to be compared. Each of these three minerals shows different hydroxyl-stretching vibrational patterns, but some similarity exists in the Raman spectra of the hydroxyl-deformation modes. The low-wavenumber region is characterized by the bands assigned to the cation-chloride stretching and bending modes. Phosgenite is also a mixed chloride-carbonate mineral and a comparison is made with the molecular structure of the aforementioned minerals. Raman spectroscopy lends itself to the study of these types of minerals in complex mineral systems of secondary mineral formation.

The first Italian occurrence of cumengéite, a rare Pb and Cu hydroxychloride, is described from Vesuvius (Italy). Italian cumengéite has a volcanic origin (it occurs in the fumarole), which is unique for that mineral. The mineralogy of Vesuvius' fumarole is outlined briefly. A powder X-ray diffraction (XRD) pattern of cumengéite is presented. The crystal structure of cumengéite has been refined (R = 0.036) using single-crystal XRD data. Cumengéite is tetragonal, space group I4/mmm, a 15.1007(2), c 24.4940(4) Å. In the structure of cumengéite there are five independent Pb atoms, which are linked to 6—9 anions in five different ways. The structural study revealed the presence of two independent and previously unobserved water molecules, and led to the revision of the accepted chemical formula for the mineral: the new formula is Cu20Pb21Cl42(OH)40·6H2O. Analytical data taken from the literature for cumengéite from Boléo, Mexico (the type locality), as well as a new structural study carried out on the type material confirmed the new formula.