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Uranyl Ion Coordination by Benzene‐1,2,3‐tricarboxylate: Building Chains and Networks from Binuclear Bricks
Author(s) -
Thuéry Pierre,
Harrowfield Jack
Publication year - 2022
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100917
Subject(s) - chemistry , uranyl , crystallography , dimer , ligand (biochemistry) , counterion , benzene , crystal structure , hydrogen bond , hydrothermal synthesis , inorganic chemistry , stereochemistry , ion , hydrothermal circulation , molecule , organic chemistry , biochemistry , receptor , seismology , geology
Benzene‐1,2,3‐tricarboxylic acid (123btcH 3 ) was used to synthesize 7 uranyl ion complexes under hydro‐solvothermal conditions, in the presence of different structure‐directing agents. [Zn(phen) 3 ][Zn 2 (123btc)(phen) 4 ][(UO 2 ) 2 (123btc) 2 (OH)(CH 3 CN)] ⋅ 3H 2 O ( 1 , phen=1,10‐phenanthroline), the only discrete species in the series, crystallizes as a binuclear, cup‐shaped dimer. Both [PPh 3 Me][UO 2 (123btc)] ( 2 ) and [C(NH 2 ) 3 ][UO 2 (123btc)] ⋅ 0.5H 2 O ( 3 ) contain anionic, monoperiodic coordination polymers based on quasi‐planar, binuclear (UO 2 ) 2 (123btc) 2 2− subunits in which two oxygen atoms of each ligand are uncoordinated. Similar chains are found in [UO 2 (123btc)K(18C6)] ⋅ H 2 O ( 4 , 18C6=18‐crown‐6), the potassium cations being decorating groups bound to carboxylato and uranyl oxo donors. An analogous decorating role to monoperiodic polymers is played by UO 2 (DMF) 2 (H 2 O) 2 2+ cations in [(UO 2 ) 3 (123btc) 2 (DMF) 2 (H 2 O) 2 ] ( 5 ), while bridging of chains by UO 2 (NMP) 3 2+ cations in [(UO 2 ) 3 (123btc) 2 (NMP) 3 ] ( 6 ) yields a diperiodic network with V 2 O 5 topology. [NH 4 ][UO 2 (123btc)] ( 7 ), which does not contain the dimeric subunit found in the other cases, crystallizes as a diperiodic network with sql topology, the layers being associated through hydrogen bonding interactions with the ammonium counterions.