3-(Diallylamino)propanenitrile ((C3H5)2NC2H4CN9 L) π-Complexes with Copper(I) Ionic Salts. Syntheses and Crystal Structures of Compounds [Cu(H~+L)ClO4]ClO4 · H2O, [Cu(H~+L)BF4]BF4 · H2O, and [Cu(H~+L)(H2O)]SiF6 · H2O

摘要

Qualitative single crystals of π-complexes Cu(H~+L)(ClO4)]ClO4 · H2O (I), Cu(H~+L)(BF4)[BF4· H2O (II), and [Cu(H~+L)(H2O)]SiF6 · H2O (III) are synthesized from solutions of 3-(diallylamino)pro-panenitrile (L) in propanol, ethanol, and methanol-water acidified with the corresponding acid to pH 3.5-5 and from the copper(II) salts (Cu(ClO4)2 · 6H2O, Cu(BF4)2 · 6H2O, and CuSiF6 · 4H2O) using the alternating-current electrochemical method on copper wire electrodes. The crystal structures of the complexes are determined. All compounds crystallize in the monoclinic crystal system: complexes I and II are isostruc-tural, space group P21, Z= 4. For compound III, space group P21/c, Z= 8. Unit cell parameters: for I a = 7.8153(3), b = 16.7824(7), c = 12.4426(5) A, β = 93.410(2)°, V= 1629.1(1) A~3; for II, a = 7.6755(4), b = 16.7119(7), c = 12.3784(6) A, β = 94.354(2)°, V= 1583.2(1) A~3; and for III a = 9.826(2), b = 24.009(3), c = 12.061(2) A, β = 91.820(6)°, V= 2843.9(7) A~3. The trigonal pyramidal coordination of the copper atom in complexes I-III is formed by two C=C bonds of the allyl groups of H+L, the nitrile N atom of the adjacent cation of the ligand, and the O or F atom of the ClO4 or BF4 anions. In structure III, the apical position of the pyramid is occupied by the O atom of the water molecule, since the SiF6~(2-) anion is considerably remote from the copper(I) atom. However, this anion is bound to the organic cation by hydrogen bonds F-H (2.05-2.51 A).