The syntheses and structures of '3+2' and '2+2+1' oxorhenium mixed-ligand complexes employing 8-hydroxy-5-nitroquinoline as the bidentate N,O donor ligand.
The syntheses and structural characterizations of a series of novel '3+2' and '2+2+1' mixed-ligand complexes carrying 8-hydroxy-5-nitroquinoline (HL) as the bidentate N,O donor atom system are reported. Thus one-pot reactions of [ReOCl(3)(PPh(3))(2)] with dianionic tridentate ligands H(2)L(n) (where H(2)L(1)=HOC(6)H(4)-2-CH=NC(6)H(4)-2-OH; H(2)L(2)=HOC(6)H(4)-2-CH=N-C(6)H(4)-2-SH; H(2)L(3)=HOC(6)H(4)-2-CH=NN=C(NHC(6)H(5))-SH; H(2)L(4)=2-CH(2)OH-C(5)H(3)N-6-CH(2)SH; and H(2)L(5)=2-CO(2)H-C(5)H(3)N-6-CO(2)H) and HL afforded a series of '3+2' oxorhenium complexes of the type [ReO(H(2)L(n))(L)] 2-6, which exhibit distorted octahedral geometries. Crystals of 1 are monoclinic space group C2/c, a=16.702(1), b=14.275(1), c=22.363(2) A, beta=108.083(1) degrees V=5068.2(7) A(beta) and Z=8; those of 2 are monoclinic space group P2(1)/n, a=8.5093(4) b=38.518(2), c=11.6092(5) A, beta=97.708(1) degrees , V=3770.7(3) A(3) and Z=8; those of 5 are triclinic, space group P1-, a=7.5899(8), b=10.322(1), c=11.905(1) A, alpha=78.636(2) degrees , beta=74.229(2) degrees , gamma=71.391(2) degrees , V=844.3(2) A(3), and Z=2. Upon reaction of 2,6-pyridinedimethanol (H(2)L(6)) with the intermediate complex [ReOCl(2)(L)(PPh(3))] (1), only one of the two methylene hydroxy group was deprotonated and a new '2+2+1' complex [ReO(OCH(3))(HL(6))(L)].CH(3)OH (7) was obtained. Crystal data for 7: monoclinic P2(1)/n, a=12.0579(6), b=11.0993(6), c=14.9262(8) A, beta=107.872(1) degrees , V=1901.2(2) A(3), and Z=8. In the preparation of complex 3, cleavage of the C=N bond of the Schiff base H(2)L(2) was observed and the '2+2+1' complex 8 [ReO(PPh(3))(eta(2)-NHC(6)H(4)-2-S)(L)].CH(2)Cl(2) having 2-aminothiophenol as a dianionic bidentate ligand was isolated. Crystals of 8 are monoclinic space group C2/c, a=25.627(2), b=8.1305(6) c=31.404(2) A beta=96.147(1) degrees , V=6505.7(8) A(3), and Z=8. Reduction of HL to 8-hydroxy-5-aminoquinoline was realized during the formation of complex 6, and a new complex 9 was thus isolated involving the coordination of two sets of N,O donor atoms from L and 8-hydroxy-5-aminoquinoline while a methoxy oxygen atom completes the octahedral coordination geometry. Crystals of 9 are monoclinic space group P2(1)/n, a=7.5330(6), b=15.095(1), c=16.394(1) A, beta=99.690(2) degrees , V=1837.7(3) A(3), and Z=4.
Chen
Xiaoyuan
X
Department of Chemistry Syracuse University, Syracuse, NY 13244, USA.
Femia
Frank J
FJ
Babich
John W
JW
Zubieta
Jon
J