A hybrid consisting of coordination polymer and noncovalent organic networks: A highly ordered 2-D phenol network assembled by edge-to-face π-π interactions

A 2-D metal-organic open framework having 1-D channels, [Cu(C₁₀H₂₆N₆)]₃ [C₆H₃(COO)₃ ]₂·18H₂O (1), was constructed by the self-assembly of the Cu(II) complex of hexaazamacrocycle A (A = C₁₀H₂₆N₆) with sodium 1,3,5-benzenetricarboxylate (BTC^3- in DMSO-H₂O solution. 1 crystallizes in the trigonal space group P3 with a = b = 17.705(1) Å, c = 6.940(1) Å, α = β = 90°, γ = 120°, V = 1884,0(3) ų, Z = 1, and ρ_calcd = 1.428 g cm^-3. The X-ray crystal structure of 1 indicates that each Cu(II) macrocyclic unit binds two BTC^3- ions in a trans position and each BTC^3- ion coordinates three Cu(II) macrocyclic complexes to form 2-D coordination polymer layers with honeycomb cavities (effective size 8,1 Å), and the layers are packed to generate 1-D channels perpendicularly to the 2-D layers. Solid 1 binds guest molecules such as MeOH, EtOH, and PhOH with different binding constant and capacity. By the treatment of 1 with aqueous solution of phenol, a hybrid solid [Cu(C₁₀H₂₆N₆)]₃ [C₆H₃(COO)₃]₂· 9PhOH·6H₂O (2) was assembled. 2 crystallizes in the trigonal R3 space group with a = b = 20.461 (1) Å, c = 24.159(1) Å, α = β = 90°, y = 120°, V = 8759.2(7) ų, Z = 3, and ρ_calcd = 1.280 g cm^-3. In 2, highly ordered 2-D noncovalent phenol layers are formed by the edge-to-face π-π interactions between the phenol molecules and are alternately packed with the coordination polymer layers in the crystal lattice.