Na[Ag(CN)2], Mr = 182-90, monoclinic, C2/c, a = 6-572 (1), b = 3-710 (1), c = 17.346 (2)/~, fl = 92.05 (1) °, V = 422.66/~3, Z=4, Dx = 2.874 Mg m -3, A(Mo Kte) = 0.71073/~, /x = 4.527 mm-1, F(000) = 336. The structure was refined to R=0.072, wR=0.052 for 293 absorptioncorrected observed reflections. The Ag atoms of linear NC--Ag---CN groups are arranged in layers parallel to (001). The Na ions occupy octahedral holes between pseudohexagonal nitrogen layers with the sequence ABAB.Experimental. This very stable compound is easily obtained by reaction of NaCN with AgCN in aqueous suspension. All attempts, however, to grow good-quality single crystals failed up to now, so that only powder diffraction data have been recorded in the literature. We have succeeded in growing single crystals by slow recrystallization from a 1:1 ethanolwater mixture. Unfortunately most of these crystals were also of poor quality, mainly because of intergrowth and a high degree of disorder. After inspection of a large number of crystals by microscopy and film methods a clear crystal fragment (30 x 30 × 60 Ixm) could be isolated, which proved suitable for a structure determination. Gandolfi and Guinier patterns showed the fragment to be the same phase as the other crystals and the bulk material.For data collection, an Enraf-Nonius CAD-4 diffractometer was used (MoKa, A=0.71073A, graphite monochromator). Lattice parameters were refined from 20 values of 25 reflections in the range 4.8-36 °. Intensities measured for 2 _< 0___ 20°; oy-20-scan technique (scan width 0.85 ° + 0.34 ° tan0). Three standard reflections indicated a 2.2% loss of intensity during data collection. Mergin~ of the 1308 collected intensities [(sin0)max/A = 0.481 A; -5 _< h <_ + 5, -5 ___ k ___ + 5, -24 _< l ___ + 24] gave 293 unique reflections (Rin t = 0"031) with F> 3a(F), which were considered as observed and used for all calculations (program system SHELX76; Sheldrick, 1976).