Chemical and structural aspects of silver–triphenylarsine complexes and silver–tin complex salts

Abstract

Three compounds previously described as tin derivatives have been reinvestigated by X-ray diffraction and found to have the following formulae: Ag(AsPh₃)(NO₃)(1)[monoclinic, space group P2₁/c, a= 10.405(5), b= 18.895(12), c= 9.138(6)Å, β= 98.35(8)°, Z= 4; R= 0.0450 for 2 036 reflections]; Ag(AsPh₃)₂(NO₃)(2)[triclinic, space group P, a= 11.97(1), b= 12.02(1), c= 13.68(1)Å, α= 102.0(1), β= 113.3(1), γ= 104.0(1)°, Z= 2; R= 0.0468 for 4409 reflections]; Ag(AsPh₃)₃(NO₃)(3)[monoclinic, space group P2₁/n, a= 19.193(8), b= 14.003(7), c= 17.893(7)Å, β= 96.4(1)°, Z= 4; R= 0.0478 for 3 543 reflections]. In all these compounds the silver atom is co-ordinated, in an irregular fashion, by arsenic and oxygen atoms. In addition, two new silver–tin complex salts have been prepared and structurally characterized by X-ray diffraction: [Ag(AsPh₃)₄][SnPh₂(NO₃)₃](4)[triclinic, space group P, a= 22.57(2), b= 14.22(1), c= 14.07(1)Å, α= 90.9(1), β= 69.9(1), γ= 65.6(1)°, Z= 2; R= 0.0635 for 4 494 reflections] and [Ag(AsPh₃)₄][SnPh₂(NO₃)₂Cl](5)[triclinic, space group P, a= 22.68(2), b= 14.24(1), c= 14.24(1)Å, α= 90.66(6), β= 69.17(5), γ= 64.36(4)°, Z= 2; R= 0.0648 for 7 108 reflections]. These two compounds are isostructural and contain a tetrahedral [Ag(AsPh₃)₄]⁺ cation and a bipyramidal anion in which the tin atom is co-ordinated apically by two phenyl groups; the equatorial sites are occupied by six oxygen atoms from three NO₃^– ions in (4), and by four oxygen atoms from two NO₃^– ions and a chlorine in (5).