Ambient temperature X-ray diffraction data were collected at different pressures from two crystals of β-As4S4, which were made by heating realgar under vacuum at 295ºC for 24 h. These data were used to calculate the unit-cell parameters at pressures up to 6.86 GPa. Above 2.86 GPa, it was only possible to make an approximate measurement of the unit-cell parameters. As expected for a crystal structure that contains molecular units held together by weak van der Waals interactions, β-As4S4 has an exceptionally high compressibility. The compressibility data were fitted to a third-order Birch–Murnaghan equation of state with a resulting volume V0 = 808.2(2) Å3, bulk modulus K0 = 10.9(2) GPa and K' = 8.9(3). These values are extremely close to those reported for the low-temperature polymorph of As4S4, realgar, which contains the same As4S4 cage-molecule. Structural analysis showed that the unit-cell contraction is due mainly to the reduction in intermolecular distances, which causes a substantial reduction in the unit-cell volume (∼21% at 6.86 GPa). The cage-like As4S4 molecules are only slightly affected. No phase transitions occur in the pressure range investigated.

Micro-Raman spectra, collected across the entire pressure range, show that the peaks associated with As–As stretching have the greatest pressure dependence; the S–As–S bending frequency and the As–S stretching have a much weaker dependence or no variation at all as the pressure increases; this is in excellent agreement with the structural data.

Wakabayashilite is a rare mineral with ideal formula [(As,Sb)6S9][As4S5]. Its structure consists of an [M6S9] bundle-like unit (M = As, Sb) running along the [001] axis and [As4S5] cage-like molecules. In this study, samples of wakabayashilite from different occurrences (Khaidarkan, Kyrgyzstan; Jas Roux, France; White Caps mine, USA; Nishinomaki mine, Japan) were selected to verify the possible presence of different molecular groups replacing the As4S5 molecule. Given the chemical (electron probe microanalysis-wavelength dispersive spectroscopy), spectroscopic (micro-Raman) and structural (single-crystal X-ray diffraction) results obtained, it appears evident that only the As4S5 molecular group is present in the wakabayashilite structure and that the apparent non-stoichiometry reported in literature is actually due to unreliable chemical analyses. The structural role of the minor elements (Cu, Zn and Tl) in wakabayashilite is also discussed.

Bonazziite is a new mineral from Khaidarkan deposit, Kyrgyzstan and represents the natural analogue of the β-form of the well known As4S4 compound. It occurs as rare crystals up to 100 μm across associated with realgar, sulfur, wakabayashilite, alacránite, non-stoichiometric As4S4+x sulfides and stibnite in a calcite matrix. In thick section, bonazziite is opaque with a resinous lustre and a dark-orange streak. It is brittle; the Vickers hardness (VHN15) is 70 kg/mm2 (range: 60–76) (Mohs hardness of ∼2½). In plane-polarized incident light, bonazziite is strongly bireflectant and pleochroic from orange to light red. The mineral shows orange to red internal reflections. Between crossed polars, the mineral is strongly anisotropic with greyish to light-blue rotation tints. Reflectance percentages in air for Rmin and Rmax are 19.9, 22.2 (471.1 nm), 19.1, 21.3 (548.3 nm), 18.8, 19.7 (586.6 nm) and 17.8, 18.9 (652.3 nm), respectively. Bonazziite is monoclinic, space group C2/c, with a = 9.956(1), b = 9.308(1), c = 8.869(1) Å, β = 102.55(2)° and V = 802.3(2) Å3, Z = 4. The crystal structure [R1 = 0.0263 for 735 reflections with Fo > 4σ(Fo)] is based on the As4S4 cage-like molecule, in which each As atom links one As and two S atoms. The As4S4 molecule is identical to that found in the structure of realgar. The six strongest powder diffraction lines [d in Å (I/I0) (hkl)] are: 5.74 (100) (1̄11); 4.10 (60) (021); 3.92 (50) (1̄12); 3.12 (60) (022, 310); 2.95 (50) (221, 202); 2.86 (80) (2̄22, 1̄31). a mean of six electron microprobe analyses gave the formula As3.95S4.05, on the basis of eight atoms. The new mineral has been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA No. 2013-141) and named for Paola Bonazzi, in recognition of her seminal contributions to the study of arsenic sulfides and their alteration induced by exposure to light.