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 (BTC3-) in DMSO−H2O solution. 1 crystallizes in the trigonal space group P3̄ with a = b =
17.705(1) Å, c = 6.940(1) Å, α = β = 90°, γ = 120°, V = 1884.0(3) Å3, Z = 1, and ρcalcd = 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 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°, γ = 120°, V = 8759.2(7) Å3, Z = 3, and ρcalcd = 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.