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The crystal structure of a new light-induced alteration product obtained from a natural non-stoichiometric arsenic sulfide (original chemical formula As 4 S 4.35 ) was solved in the space group Pccn, and refined to a final R index of 9.89%. Unit-cell parameters are: a = 19.352(7), b = 10.166(3), c = 8.697(4) Å, V = 1711(1) Å 3 ; Z = 8. The structural refinement results yielded a chemical formula close to As 4 S 5 . The structure consists of discrete, covalently bonded As 4 S 5  molecules, which are held together by van der Waals forces. The molecular packing is similar to that of the original crystal, which, in turn, is the same as to that of β-As 4 S 4 . The phase originated from a continuous, room-temperature, lightinduced alteration process that does not require a complete rearrangement of the molecular packing and therefore does not imply the loss of coherency between crystalline domains.

Light-induced alteration of arsenic sulfides: A new product with an orthorhombic crystal structure