Crystal Engineering with Oxo‐ and Cyanocarbon Anions: Synthesis and Structural Characterization of Triorganotin(IV) Pentacyanopropenides and Hexacyanoazapentadienides

The first triorganotin(IV) pentacyanopropenides, [R3Sn(H2O)(2)][C-3(CN)(5)] (R = Me (2), nBu (3), Ph (4) were prepared by treatment of Ag[C-3(CN)(5)] (1) with equimolar amounts of R3SnCl in reagent grade THF. In a similar manner, dark red [R3Sn(H2O)(2)][N{C(CN)C(CN)(2)}(2)] (6) containing the hexacyanoazapentadienyl anion was prepared in 55 % yield. The molecular structure of [Ph3Sn(H2O)(2)][C-3(CN)(5)] (4) was determined by X-ray diffraction. The crystal structure consists of separated trigonal-bipyramidal [Ph3Sn(H2O)(2)](+) cations and nearly planar [C-3(CN)(5)](-) anions which are linked through O-H center dot center dot center dot N hydrogen bonds to give a three-dimensional network.