A 2-D metal-organic open framework having 1-D channels, [Cu(C10H26N6)](3)[C6H3(COO)(3)](2).18H(2)O (1), was constructed by the self-assembly of the Cu(II) complex of hexaazamacrocycle A (A = C10H26N6) with-sodium 1,3,5benzenetricarboxylate (BTC3-) in DMSO-H2O solution. 1 crystallizes in the trigonal space group P3 with a = b = 17.705(1) (A) over circle, c = 6.940(1) (A) over circle, alpha = beta = 90degrees, gamma = 120degrees, V = 1884.0(3) (A) over circle (3), Z = 1, and rho(calcd) = 1.428 g cm(-3). The X-ray crystal structure of 1 indicates that each Cu(II) macrocyclic unit binds two BTC3- ions in a trans position and each BTC3- ion coordinates three Cu(II) macrocyclic complexes to form 2-D coordination polymer layers with honeycomb cavities (effective size 8,1 A), 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.6H(2)O (2) was assembled. 2 crystallizes in the trigonal R3 space group with a = b = 20.461(1) (A) over circle, c = 24.159(1) (A) over circle, alpha = beta = 90degrees, gamma = 120degrees, V = 8759.2(7) (A) over circle (3), Z = 3, and rho(calcd) = 1.280 g cm(-3). In 2, highly ordered 2-D noncovalent phenol layers are formed by the edge-to-face pi-pi interactions between the phenol molecules and are alternately packed with the coordination polymer layers in the crystal lattice.