A Novel Hybrid Supramolecular Network Assembled from Perfect π−π Stacking of an Anionic Inorganic Layer and a Cationic Hydronium‐Ion‐Mediated Organic Layer

The synthesis and characterization of a three‐dimensional inorganic‐organic hybrid network [{Cu 2 (CA) 3 }{(H 3 O) 2 (phz) 3 }·G] n ( 1 ; H 2 CA = chloranilic acid, phz = phenazine; G = 2CH 3 COCH 3 ·2H 2 O) is described. The crystal structure of 1 shows that the 3D network assembly is based on a combination of two types of grid‐building sub‐units of (6,3) topology: an anionic metal‐organic coordination honeycomb grid, and a cationic hydronium‐ion‐mediated organic honeycomb grid. The inorganic and organic honeycomb nets are perfectly π−π‐stacked, creating an infinite number of open‐end channels (channel size about 8 Å in diameter). The solid framework of 1 retains its rigidity upon removal of the guest molecules under high vacuum to form compound [{Cu 2 (CA) 3 }{(H 3 O) 2 (phz) 3 }] n ( 2 ) as revealed by a single‐crystal X‐ray diffraction analysis. Compounds [{M 2 (CA) 3 }{(H 3 O) 2 (phz) 3 }·G] n (M = Cd, 3 ; M = Zn, 4 ; M = Co, 5 ; G = 2CH 3 COCH 3 ·2H 2 O) were also prepared and characterized as isostructures of 1 [crystal data for 1 : Cu 2 (CA) 3 (H 3 O) 2 (phz) 3 ·G, trigonal, space group P $\bar 3$ 1 m , formula mass = 1478.86, a = 13.7593(2) Å, c = 9.1869(2) Å, V = 1506.22(5) Å 3 , Z = 1; crystal data for 2 : Cu 2 (CA) 3 (H 3 O) 2 (phz) 3 , trigonal, space group P $\bar 3$ 1 m , formula mass = 1326.62, a = 13.7565(4) Å, c = 9.1544(5) Å, V = 1500.3(1) Å 3 , Z = 1]. The magnetic‐exchange coupling between the copper centers for compound 1 was analyzed on the basis of the Curie−Weiss expression and a dinuclear magnetic model. The negative values of the Weiss constant and the magnetic‐exchange coupling constant indicate an antiferromagnetic interaction between the copper centers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)