Synthese und Kristallstruktur von Bis[1,5-ditolyIpentaazadienido-silber(I)] und Bis[1,3-diphenyItriazenido-silber(I)] / Synthesis and Crystal Structure of Bis[1,5-ditolylpentaazadienido-silver(I)] and Bis[1,3-diphenyltriazenido-silver(I)]

Abstract

The reaction of 1,5-ditolylpentaazadiene with Ag(NH3)2 + in concentrated ammonia yields orange-red [Ag(TolNNNNNTol)]2. This compound crystallizes in the monoclinic space group P21/n with the lattice constants a= 525.7, b = 1236.1, c = 2189.6 pm, β = 90.88°. Z = 4. In the centrosymmetric and approximately planar dimers the Ag+ ions are coordinated by the outer N atoms N1 and N5 of the N5 chain forming a twelve-membered Ag2N10 ring. The coordination is almost linear with N1-Ag-N5′ = 160° and Ag-N1 = 218, Ag-N5′ = 216 pm. [Ag(PhNNNPh)]2 was obtained by the reaction of 1,3-diphenyltriazenidc with AgNO3 in THF. It crystallizes from pyridine in yellow, monoclinic needles with the space group C2/c. The lattice constants are a = 2602.3. b = 547.1, c = 1693.4 pm, β = 118.13°. Z = 4. The centrosymmetric complexes are planar and satisfy nearly the symmetry D2h. The N3 chains bridge the Ag ions in an eight-membered ring with N1 - Ag-N3′ = 167° and Ag-N1 = 215, Ag-N3′ = 214 pm. The Ag+ ions exhibit a very short distance of Ag-Ag′ = 266.9 pm that must be interpreted by bonding interactions.