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ABSTRACT: Five Cu(II)/benzoate/4,4¢-bipy complexes, namely, [Cu(H2O)(benzoate)2(4,4¢-bipy)2](benzoic acid)2â(4,4¢-bipy) (1),
[Cu2(H2O)2(benzoate)4(4,4¢-bipy)3]â(H2O)9 (2), [Cu2(benzoate)4(4,4¢-bipy)3] (3), [Cu3(H2O)4(benzoate)6(4,4¢-bipy)4.5]â(4,4¢-bipy)â
(H2O)5 (4), and [Cu3(OH)2(H2O)2(benzoate)4(4,4¢-bipy)2] (5) (4,4¢-bipy ) 4,4¢-bipyridine), have been synthesized through hydrothermal
reaction of copper(II) nitrate, benzoic acid, and 4,4¢-bipyridine under different pH conditions. The diverse product structures show
the marked sensitivity of the structural chemistry of the aromatic carboxylate ligand to synthesis conditions. Complex 1, which
exhibits a zero-dimensional (0D) structure of mononuclear copper(II), is formed at pH ) 5.5. At pH ) 6.0, dimeric copper(II)
complexes of 2 and 3 are formed. Reaction at pH ) 7 leads to a one-dimensional (1D) structure of 4. A further increase of the pH
to 8.0 results in a two-dimensional (2D) structure of 5. Crystal data are monoclinic, space group P2/n, a ) 13.992(4) Å, b )
5.7153(14) Å, c ) 31.126(8) Å, â ) 100.513(5)°, Z ) 2 for 1, monoclinic, space group C2/c, a ) 30.283(5) Å, b ) 15.139(2) Å,
c ) 14.457(2) Å, â ) 112.776(3)°, Z ) 4 for 2, monoclinic, space group P21/c, a ) 5.8317(12) Å, b ) 21.157(4) Å, c ) 20.679(4)
Å, â ) 94.343(3)°, Z ) 2 for 3, triclinic, space group P1h, a ) 14.016(3) Å, b ) 18.492(4) Å, c ) 19.353(4) Å, R ) 66.220(3)°,
â ) 79.948(4)°, ç ) 88.390(3)°, Z ) 2 for 4, and monoclinic, space group P21/c, a ) 5.6880(16) Å, b ) 17.917(5) Å, c )
20.904(6) Å, â ) 92.959(5)°, Z ) 2 for 5. |
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