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The crystal structure of Na 2 S 4 O 6  · 2H 2 O has been redetermined from three-dimensional X-ray intensity data and refined to  R  = 0.025 ( R w   = 0.018) for 1620 observed reflections. The structure is monoclinic, space group  C 2, with  a  = 14.4726(5),  b  = 6.3716(3),  c  = 5.4402(3) Å,  β  = 105.53(1) °,  Z  = 2. Except for the chirality of the structure and the hydrogen positions, for which no information is given in the earlier work of Foss and Hordvik (1964), their structural model was confirmed by the present study. The tetrathionate anion possesses a two-fold symmetry axis. From the two independent S – S bonds of the anion the central bond is significantly shorter than the terminal one [2.019(1) Å versus 2.115(1) Å]. The S–S–S bond angle formed about the central S – S bond by the sulfur atoms is 89.55(2)°. The terminal SO 3  groups of the anion have almost perfect trigonal symmetry [S–O: 1.447(1)–1.450(1) Å, O–S–O: 113.39(6)– 113.82(5)°]. The sodium cation is surrounded by six oxygen atoms in a distorted octahedral arrangement. [Na–O: 2.358(1)–2.465(1) Å]. By sharing opposite faces, columns of NaO 6  octahedra are formed, which run parallel to  b  axis and are linked together through the sulfonate groups of the tetrathionate anions and through hydrogen bonds, in which the water molecules are involved. The chirality of the structure was determined with the Hamilton and the Bijvoet methods. Both indicated that the earlier structure proposal of Foss and Hordvik (1964) should be inversed for our crystal.

Crystal structure and chirality of sodium tetrathionate dihydrate, Na 2 S 4 O 6 · 2H 2 O