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The hexasodium salt of benzenehexasulphonic acid, C~,(SO,Na) 6, forms an octahydrate which is stable in air. The compound is monoclinic with a = 8.360 (1), b = 13.981 (l),e = 12.692 (1) A, y = 118 ° 36 (I)', Z = 2, space group P2./b. The intensities were measured on an automatic Syntex P1 diffractometer. The structure was solved by direct methods and refined by the least-squares technique to a final R of 0.053. The configuration of the anion is determined by steric forces between the large SO 3 groups. The observed average values ofthe bond lengths and angles are C