Sodium tetrasulphide, Na2S4, is tetragonal and crystallizes in space group I742d with cell dimensions a = 9.5965(3) and c = 11.7885(5) A, and with Z= 8. Three-dimensional intensity data were collected with a linear diffractometer (PAILRED) using Mo Ira radiation. Positional and anisotropic temperaturefactor parameters for all atoms were refined by a full-matrix least-squares method to R (F)= 0.030 based on 1749 independent reflexions with lo>A1. The crystal structure is built up of unbranched $42-ions surrounded by Na + ions. The distance between different S]-ions is about 3.60 A. The $24 -ions lie on a twofold axis and the sulphur-sulphur bond distances are 2.074(1) A (end) and 2.061(1) A (middle). The sulphur-sulphur bond angle is 109.76(2) ~ and the dihedral angle is 97.81 °. The sodium-sulphur coordination polyhedra consists of two types: a distorted tetrahedron with two pairs of distances of 2.826(I) and 2-842(1) ~ and a distorted octahedron with three pairs of distances of 2.887(1), 3.043(1) and 3"081(1) A.
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