Rational Synthesis and Characterization of Two Three‐Dimensional Metal‐Organic Frameworks Incorporating Silver Chains and 1,2,3,4,5,6‐Cyclohexanehexacarboxylate

Two new silver polycarboxylate coordination polymers, [Ag 3 (H 3 L)(H 2 O) 2 ] n · 2 n H 2 O ( 1 ) and [Ag 6 L(NH 3 )(H 2 O) 3 ] n · n H 2 O ( 2 ), have been obtained from the reaction of [Ag(NH 3 ) 2 ](OH) (freshly synthesized from Ag 2 O and aqueous ammonia) with cis , cis , cis , cis , cis ‐1,2,3,4,5,6‐cyclohexanehexacarboxylic acid (H 6 L) by control of the molar ratio of starting materials. The X‐ray crystal structure analysis reveals that both of them crystallize in the triclinic space group P $\bar {1}$ with a = 6.375(4), b = 9.505(6), c = 15.097(8) Å, α = 93.249(14), β = 100.364(15), γ = 96.453(15)°, V = 891.4(9) Å 3 , Z = 2 for 1 , and a = 8.0380(7), b = 10.1220(9), c = 13.8458(12) Å, α = 76.3450(10), β = 80.9370(10), γ = 68.7230(10)°, V = 1016.83(15) Å 3 , Z = 2 for 2 . Complex 1 features a three‐dimensional (3D) metal‐organic framework (MOF) with one‐dimensional (1D) rectangular channels surrounded by carboxylato‐supported Ag–Ag dimers, Ag–Ag chains, and half deprotonated [H 3 L] 3– ligands. Each [H 3 L] 3– ligand connects eight Ag I atoms. The weakly coordinated water ligands and lattice water molecules are located at the channels and form interesting 1D hydrogen‐bonded T4(2)8(2) water tapes with cyclic R 8 6 (16) (H 2 O) 8 and R 4 4 (8) (H 2 O) 4 units. Complex 2 is also a 3D MOF structure constructed by two types of Ag–Ag chains with Ag8 cluster units and linear Ag4 units, respectively, and fully deprotonated L 6– ligands. The silver( I ) atoms in 2 exhibit linear, T‐shaped, Y‐shaped, and tetrahedral coordination geometries. Each L 6– ligand connects thirteen Ag I atoms. The intrachain robust argentophilic interactions play a vital role in the formation of the structure. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)