Slyvka Y. Anionic copper(I) halide pi-сomplexes with 2-butyne-1,4-diol: synthesis and crystal structure.

By direct interaction of MX (M - Na+, K+, NH4+, Rb+, Cs+, imH+ (im - imidazolium), bimH+ (bim - benzimidazolium), 2­ampH+ (2-ainopyridinium), 4­ampH+ (4­aminopyridinium), pip(H+)2 (pip - piperazinium), X = Cl), CuX and 2-butyne-1,4-diol HOCH2CCCH2OH, and also partially by means of the alternating-current electrochemical technique 15 new compounds, 13 of them are the anionic copper(I) chloride pi-complexes with 2-butyne-1,4-diol, 1 molecular pi-complex and 1 double salt (3-amp)6 [Cu11Cl17] have been obtained and X-ray structurally investigated. The structures of anionic copper(I) chloride pi-complexes with 2-butyne-1,4-diol are built up of discrete [CuCl2(HOCH2CCCH2OH)]- complex anions and the corresponding cations. The cooper(I) atom in complex anion, which coordinates only a triple CC bond of 2-butyne-1,4-diol, completes its environment to three by coordination of the two Cl atoms. In Na[CuCl2(HOCH2CCCH2OH)] 2H2O and Ca[CuCl2(HOCH2CCCH2OH)]2 4H2O compounds structure, sodium and calcium atoms, besides central copper(I) atom, form octahedral and trigonal-antiprismatic environments respectively: sodium cation involves chlorine atoms, oxygen ones from 2-butyne-1,4-diol and water, calcium cation oxygen atoms from the ligand and water molecules. In contrast to 2- and 4-aminopyridinium cations,, in the case of 3-aminopyridininium cation only cubic phase of (3-ampH)6[Cu11Cl17] is formed. Hydrogen bonds which are determined by the outersphere cations cause a definite stacking type of the complex anion and, as a result, lead to a formation of peculiar frameworks of the pi-complexes structure.