Synthese, Schwingungsspektren und Kristallstrukturen der Nitratoargentate (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN und (Ph4P)[Ag2(NO3)3

Abstract

AbstractSynthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN and (Ph4P)[Ag2(NO3)3]Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN (1), whereas (Ph4P)[Ag2(NO3)3] (2) is obtained in a long‐time reaction from (Ph4P)Br and excess AgNO3 in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations.1: Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R1 = 0.0348. 1 contains isolated complex units [Ag(NO3)2(CH3CN)]−, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH3CN molecule with a short Ag—N distance of 220.7(4) pm.2: Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R1 = 0.072. In the polymeric anions [Ag2(NO3)3]− each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph4P)+ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms.