Contrasting Networks and Entanglements in Uranyl Ion Complexes with Adipic and trans , trans -Muconic Acids.

Adipic (hexane-1,6-dicarboxylic, adpH 2 ) and trans , trans -muconic ( trans , trans -hexa-2,4-diene-1,6-dicarboxylic, mucH 2 ) acids have been reacted with uranyl cations under solvo-hydrothermal conditions, yielding nine homo- or heterometallic complexes displaying in their crystal structure the effects of the different flexibility of the ligands. The complexes [PPh 4 ] 2 [(UO 2 ) 2 (adp) 3 ] ( 1 ) and [Ni(bipy) 3 ][(UO 2 ) 2 (muc) 3 ]·5H 2 O ( 2 ), where bipy is 2,2'-bipyridine, crystallize as diperiodic networks with the hcb topology, the layers being strongly puckered or quasiplanar, respectively. Whereas [(UO 2 ) 2 (adp) 3 Ni(cyclam)]·2H 2 O ( 3 ), where cyclam is 1,4,8,11-tetraazacyclotetradecane, crystallizes as a diperiodic network, [(UO 2 ) 2 (muc) 3 Ni(cyclam)]·2H 2 O ( 4 ) is a triperiodic framework in which the Ni II cations are introduced as pillars within a uranyl-muc 2- framework with the mog topology. [UO 2 (adp)(HCOO) 2 Cu( R , S -Me 6 cyclam)]·2H 2 O ( 5 ), where R , S -Me 6 cyclam is 7( R ),14( S )-5,5,7,12,12,14-hexamethylcyclam, is a diperiodic assembly with the sql topology, and it crystallizes together with [H 2 NMe 2 ] 2 [(UO 2 ) 2 (adp) 3 ] ( 6 ), a highly corrugated hcb network with a square-wave profile, which displays 3-fold parallel interpenetration. In contrast, [(UO 2 ) 3 (muc) 2 (O) 2 Cu( R , S -Me 6 cyclam)] ( 7 ) is a diperiodic assembly containing hexanuclear, μ 3 -oxido-bridged secondary building units which are the nodes of a network with the hxl topology. The two related complexes [PPh 3 Me] 2 [(UO 2 ) 2 (adp) 3 ]·4H 2 O ( 8 ) and [PPh 3 Me] 2 [(UO 2 ) 2 (muc) 3 ]·H 2 O ( 9 ) crystallize as hcb networks, but their different shapes, undulated or quasiplanar, respectively, result in different entanglements, 2-fold parallel interpenetration in 8 and 2-fold inclined 2D → 3D polycatenation in 9 .