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The crystal structures of the monoclinic compounds Ag(NH 3 ) 2 Ag 2 Fe(CN) 6  (a = 948.2, b = 1235.5, c = 1246.8 pm, β = 94.98°. Z = 4. space group Cc) and Ag(NH 3 ) 2 Ag 2 Co(CN) 6  (a = 772.1, b = 1347.9, c = 1405.2 pm, β = 101.25°, Z = 4, C 2 /c) have been determined by x-ray methods from single crystals. Using 1947 and 2739 reflections, resp.. R factors of about 5% were reached. Both compounds are similar in containing approximately linear Ag(NH 3 ) 2  +  dumb-bells (Ag-N = 216 pm) and dimeric Ag 2 N 6  units. The latter consist of distorted edge-sharing tetrahedra (average Ag-N = 229 and 231 pm, resp.), the cavities of which are provided by the nitrogen ends of six surrounding M(CN) 6  3-  octahedra (Fe -C =195 pm, Co -C = 189 pm, C - N = 115 and 114 pm, resp.). In the iron complex, which is elpasolite-related, the central Ag 2 N 2  ring is planar (Ag-Ag = 327.0 pm). By contrast the unit is folded (Ag-Ag = 307.8 pm, dihedral angle 126° between AgN 2  triangles) in the cobalt complex, which has a different structure as discussed in detail

zeitschrift für naturforschung b

Silberdiammin-disilber-hexacyanometallate(III): Kantenverknüpfte Doppeltetraeder-Einheiten Ag 2 N 6  in den unterschiedlichen Strukturen von Eisen- und Cobaltkomplex / Silverdiammine Disilver Hexacyanometallates(III): Edge-Sharing Tetrahedra Ag 2 N 6  in the Different Structures of Iron and Cobalt Complex