From one- to three-dimensional architectures: Supramolecular isomerism of copper(I) 3,5-di(4-pyridyl)-1,2,4-triazolate involving in situ ligand synthesis

Solvothermal treatment of copper(II) salts, ammonia, and 4-cyanopyridine was chosen for the study of supramolecular isomerism of the target binary copper(I) 3,5-di(4-pyridyl)-1,2,4-triazolate (4-pytz). A 2D coordination network of alpha-[Cu(4-pytz)] (1, P2(1)/n, a = 7.9633(5) angstrom, b = 10.3757(6) angstrom, c = 13.1054(8) angstrom, beta = 105.673(1)degrees) was obtained at 120-160 degrees C using Cu(OH)(2) or Cu-2(OH)(2)CO3 as the copper(II) source, while a 3D network of beta-[Cu(4-pytz)] (2, Cc, a = 9.4278(5) angstrom, b = 24.7779(14) angstrom, c = 10.6761(6) angstrom, beta = 113.025(1)degrees) was obtained at 100 degrees C using Cu(OH)(2) as copper(II) source. A solvated copper(I) 3.5-di(4-pyridyl)1,2,4-triazolate [Cu(4-pytz)(NH3)]center dot 4H(2)O (3, P2(1)/c, a = 9.2065(8) angstrom, b = 25.574(2) angstrom, c = 6.8104(6) angstrom, beta = 90.256(2)degrees) with 1D coordination structure has also been synthesized at 100 degrees C using the Cu(NO3)(2)center dot 3H(2)O as copper(II) source. Novel hydrogen-bonded water-ammonia ribbons comprised of fused (H20)5 and (H20)4(NH3) pentagons were stabilized in the ID channels of 3. Networks 1 and 2 show structure-related photoluminescence properties, while 3 is nonemissive under UV irritation.