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The nature of the symmetry changes associated with phase transitions in stibnite, Sb2S3, has been investigated by powder and single crystal X-ray diffraction. Above 420 K stibnite (I) is centrosymmetric Pbnm. Stibnite (II) is stable between 290 and 420 K and is acentric P2 1 nm. Below 290 K stibnite (III) is stable and systematic absences indicates that this phase is monoclinic with space group P2 1  or Pm, or triclinic P1, but the cell dimensions remain geometrically orthorhombic. These findings are in agreement with variations in physical and electrical properties reported in the literature.

X-ray diffraction evidence for a monoclinic form of stibnite, Sb 2 S 3 , below 290 K