New Ag I Organometallic Coordination Polymers and M II (M = Cu II and Co II ) Inorganic Supramolecular Complexes Generated from New Fulvene‐Type Ligands

Two novel fulvene‐type organic ligands L1 and L2 have been synthesized by aroylation reaction of substituted cyclopentadienyl anions. L1 crystallized in the monoclinic space group P 2 1 , a = 6.7498(4), b = 20.5769(11), c = 8.9532(5) Å, β = 109.5060(10)°, and Z = 2. L2 crystallized in the triclinic space group P $\bar 1$ , a = 11.4126(10), b = 11.4763(10), c = 11.7719(10) Å, α = 67.050(2), β = 74.509(2), γ = 61.148(2)°, and Z = 2. The coordination chemistry of L1 and L2 has been investigated. One novel Ag I ‐containing organometallic coordination polymer 3 , based on both Ag I −C and Ag I −N interactions, has been synthesized by combination of L1 and AgClO 4 in a benzene/dichloromethane mixed‐solvent system. Two new M II ‐containing [M = Cu II ( 4 ) and Co II ( 5 )] supramolecular complexes with seven‐membered metalla‐ring unit have been prepared by combination of L2 and the corresponding M(OAc) 2 ·2H 2 O (M = Cu II and Co II ) salts in ethanol. The isostructural compounds 4 and 5 crystallized in the triclinic space group P $\bar 1$ [ 4 : a = 8.8808(5), b = 10.9928(7), c = 14.2196(9) Å, α = 99.9750(10), β = 95.8190(10), γ = 93.5610(10)°, and Z = 1; 5 : a = 8.7964(10), b = 10.8103(12), c = 14.3765(15) Å, α = 99.681(2), β = 95.930(2), γ = 93.429(2)°, and Z = 1]. In the solid state, molecular complexes 4 and 5 are bound by strong intermolecular N ··· O−H hydrogen bonds in a hand‐in‐hand fashion to give a novel one‐dimensional chain motif. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)