SYNTHESIS AND STRUCTURE OF ORGANYLTRIPHENYLPHOSPHONIUM DICYANOARGENTATES: [Ph3P(CH2)3PPh3]2+ [Ag(CN)2]– [Br]– AND [Ph3PR]+ [Ag(CN)2]–, R = CH2CH2OH, CH2C6H4F-4

Abstract

The reaction of potassium dicyanoargentate with organyltriphenylphosphonium bromides in an aqueous solution has led to synthesis of complexes [Ph3P(CH2)3PPh3]2+[Ag(CN)2]–[Br]– (1), [Ph3PR]+[Ag(CN)2]–, R = CH2CH2OH (2), CH2C6H4F-4 (3), whose structures have been characterized by X-ray diffraction analysis (XRD). It is known that the absorption range of cyano groups in IR spectra of organic and inorganic compounds is in the form of a narrow interval of 2200-2000 cm-1, which points at the absence of strong surroundings influence on vibrations of these bonds. The absorption bands in the range 1450-1435 cm-1 peculiar to the P-Ph bands that are present in the spectra of compounds 1, 2, 3 are apparent in the range 1437-1439 cm-1. The XRD data have been obtained at 293 K on a Bruker D8 QUEST automatic four-circle diffractometer: crystals 1 (C41H36AgBrN2P2, М 806.44, triclinic syngony, crystal size 0.72 × 0.37 × 0.3 mm), 2 (C22H20AgN2OP, M 467.24, triclinic syngony, crystal size 0.8 × 0.52 × 0.35 mm), 3 (C27H21AgFN2P, M 531.30, monoclinic syngony, crystal size 0.28 × 0.23 × 0.22 mm). According to the XRD data, crystals 1, 2, 3 contain organyltriphenylphosphonium cations and linear dicyanoargentate anions. Besides, bromide anions are observed in crystal 1. A characteristic feature of complexes with the [Ag(CN)2]− anions is their perspective utility for development of new nano- and liquid crystal systems. The organyltriphenylphosphonium cations have a distorted tetrahedral configuration: the CPC angles vary within the range 106.70(8)° - 113.37(9)°. In the [Ag(CN)2]−anions the CAgC angles equal 171.75(10)° – 178.37(8)°.