Anorpiment, As_(2)S_(3), the triclinic dimorph of orpiment

Abstract

The new mineral anorpiment, As_(2)S_(3), the triclinic dimorph of orpiment, has space group P1 and cell parameters a = 5.7577(2), b = 8.7169(3), c = 10.2682(7) Å, α = 78.152(7), β = 75.817(7), γ = 89.861(6)º, V = 488.38(4) Å^3 and Z = 4. It occurs at the Palomo mine, Castrovirreyna Province, Huancavelica Department, Peru. It is a low-temperature hydrothermal mineral associated with dufrénoysite, muscovite, orpiment, pyrite and realgar. It occurs in drusy crusts of wedge-shaped, transparent, greenish yellow crystals. The streak is yellow. The lustre is resinous on crystal faces, but pearly on cleavage surfaces. The Mohs hardness is about 1½. The mineral is sectile with an irregular fracture and one perfect and easy cleavage on {001}. The measured and calculated densities are 3.33 and 3.321 g cm^(-3), respectively. All indices of refraction are greater than 2. The mineral is optically biaxial (—) with 2V = 35-40º and no observed dispersion. The acute bisectrix (X) is approximately perpendicular to the {001} cleavage. Electron microprobe analyses yielded the averages and ranges in wt.%: As 58.21 (57.74-59.03), S 38.72 (38.33-39.00), total 96.94 (96.07-97.75), providing the empirical formula (based on 5 atoms) As_(1.96)S_(3.04). The strongest powder X-ray diffraction lines are [d (hkl) I] 4.867(002) 97, 4.519 (110,111) 77, 3.702 (111) 46, 3.609 (022,112) 82, 2.880 (201,022,121,023) 75, 2.552 (113,131,132) 100, 2.469 (114,130,131) 96. The structure of anorpiment [R_1 = 0.021 for 1484 reflections with F_o > 4σ(F)] consists of layers of covalently bonded As and S atoms. Each S atom bonds to two As atoms at As-S-As angles between 100.45 and 104.15º. Each As atom is strongly bonded to three S atoms at S-As-S angles between 91.28 and 103.59º, forming an AsS_3 pyramid with As at its apex. The As-S linkages within the layers form rings of six AsS_3 pyramids. Interlayer bonding forces are interpreted as van der Waals. The structure of anorpiment is similar to that of orpiment in that it is composed of layers of As2S_3 macromolecules, but arranged in a different stacking sequence.

Files

Additional details