Abstract
Two new dinuclear halogenoargentate(I) anions, [Ag2Cl4]2– and [Ag2Br4]2–, containing distorted trigonal-planar co-ordinated silver(I), have been characterised by means of crystal structure determination. Bis(tetraphenylphosphonium) di-µ-chloro-dichlorodiargentate(I) and bis(tetraphenylphosphonium) di-µ-bromo-dibromodiargentate(I) both crystallize in the monoclinic space group P21/n with Z= 2 and a= 14.190(9), b= 8.062(3), c= 19.177(10)Å, β= 101.64(4)°, and a= 14.525(9), b= 7.914(3), c= 20.010(10)Å, β= 103.16(5)°, respectively. Both anions are centrosymmetric and planar or approximately planar, silver(I) being displaced 0.0014(8) and 0.0587(6)Å from the ligand plane in [Ag2Cl4]2– and [Ag2Br4]2–, respectively. In [Ag2Cl4]2– the bridging Ag–Cl distances differ considerably from one another, i.e. 2.447(1) and 2.792(2)Å, the terminal Ag–Cl bond being 2.358(2)Å. In [Ag2Br4]2– there is less discrepancy between bridging distances: 2.617(1) and 2.752(2)Å; Ag–Br(terminal) is 2.491(1)Å.

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