Syntheses and Characterization of Anti-inflammatory Dinuclear and Mononuclear Zinc Indomethacin Complexes. Crystal Structures of [Zn2(Indomethacin)4(L)2] (L = N,N
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- 作者：Qingdi Zhou ; Trevor W. Hambley ; Brendan J. Kennedy ; Peter A. Lay ; Peter Turner ; Barry Warwick ; John R. Biffin ; and Hubertus L. Regtop
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：August 21, 2000
- 年：2000
- 卷：39
- 期：17
- 页码：3742 - 3748
- 全文大小：124K
- 年卷期：v.39,no.17(August 21, 2000)
- ISSN：1520-510X
文摘
The syntheses and spectral and structural characterizations of Zn(II) indomethacin [1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid = IndoH] complexes, as different solvent adducts, have been studied. Thecomplexes are unusual in that both monomeric and dimeric complexes are formed and that this is the first exampleof the same carboxylato ligand binding via both carboxylate oxygen atoms in monomeric and dimeric Zn(II)complexes. The crystal structures of Zn-Indo complexes with N,N-dimethylacetamide (DMA), pyridine (Py),1-methyl-2-pyrrolidinone (NMP), EtOH, and MeOH as solvent ligands, [Zn2(Indo)4(DMA)2]·2DMA, 1, [Zn2(Indo)4(Py)2]·2H2O, 2b, [Zn2(Indo)4(NMP)2], 3, cis-[Zn(Indo)2(EtOH)2], 4, and cis-[Zn(Indo)2(MeOH)2], 5, weredetermined. Complexes 1, 2b, and 3 crystallize in the triclinic space group P
(No. 2): a = 13.628(2) Å, b =17.462(2) Å, c = 11.078(1) Å, 
= 99.49(1)
deg.gif">, 
ddle"> = 108.13(1)deg.gif">, 
= 110.10(1)deg.gif"> for 1; a = 13.347(3) Å, b =16.499(5) Å, c = 10.857(1) Å, = 99.48(2)deg.gif">, ddle"> = 108.25(2)deg.gif">, = 106.24(2)deg.gif"> for 2; a = 14.143(3) Å, b =14.521(2) Å, c = 11.558(2) Å, = 109.07(1)deg.gif">, ddle"> = 90.80(2)deg.gif">, = 116.40(1)deg.gif"> for 3. The three complexesexhibit dinuclear paddle-wheel structures with a Zn···Zn distance of 2.9686(6) Å, Zn-ORCOO distances of 2.035(2)-2.060(2) Å, and a Zn-ODMA distance of 1.989(2) Å in 1, a Zn···Zn distance of 2.969(1) Å, Zn-ORCOOdistances of 2.020(3)-2.049(3) Å, and a Zn-NPy distance of 2.036(3) Å in 2, and a Zn···Zn distance of 2.934(1)Å, Zn-ORCOO distances of 2.009(3)-2.051(3) Å, and a Zn-ONMP distance of 1.986(3) Å in 3. In these cases, thezinc ions are offset along the z direction such that the L-Zn···Zn-L moiety is nonlinear, unlike the Cu analogues.Each Zn has a square-pyramidal geometry bridged by four carboxylato ligands in the basal plane with the solventligands containing an O- or N-donor atom at the apex. Complexes 4 and 5 are isostructural, with space groupC2/c (No. 15). For 4, a = 30.080(2) Å, b = 5.3638(6) Å, c = 24.739(2) Å, ddle"> = 90.342(7)deg.gif">, and for 5, a =29.419(2) Å, b = 5.320(2) Å, c = 24.461(2) Å, ddle"> = 90.840(4)deg.gif">. The Zn resides on a 2-fold axis and the complexeshave a distorted cis octahedral structure with Zn-ORCOO bond lengths of 2.183(3) and 2.169(3) Å, a Zn-OEtOHbond length of 2.015(3) Å in 4, Zn-ORCOO bond lengths of 2.195(2) and 2.151(2) Å, and a Zn-OMeOH bondlength of 2.022(3) Å in 5.
(No. 2): a = 13.628(2) Å, b =17.462(2) Å, c = 11.078(1) Å, = 99.49(1)deg.gif">, ddle"> = 108.13(1)deg.gif">, = 110.10(1)deg.gif"> for 1; a = 13.347(3) Å, b =16.499(5) Å, c = 10.857(1) Å, = 99.48(2)deg.gif">, ddle"> = 108.25(2)deg.gif">, = 106.24(2)deg.gif"> for 2; a = 14.143(3) Å, b =14.521(2) Å, c = 11.558(2) Å, = 109.07(1)deg.gif">, ddle"> = 90.80(2)deg.gif">, = 116.40(1)deg.gif"> for 3. The three complexesexhibit dinuclear paddle-wheel structures with a Zn···Zn distance of 2.9686(6) Å, Zn-ORCOO distances of 2.035(2)-2.060(2) Å, and a Zn-ODMA distance of 1.989(2) Å in 1, a Zn···Zn distance of 2.969(1) Å, Zn-ORCOOdistances of 2.020(3)-2.049(3) Å, and a Zn-NPy distance of 2.036(3) Å in 2, and a Zn···Zn distance of 2.934(1)Å, Zn-ORCOO distances of 2.009(3)-2.051(3) Å, and a Zn-ONMP distance of 1.986(3) Å in 3. In these cases, thezinc ions are offset along the z direction such that the L-Zn···Zn-L moiety is nonlinear, unlike the Cu analogues.Each Zn has a square-pyramidal geometry bridged by four carboxylato ligands in the basal plane with the solventligands containing an O- or N-donor atom at the apex. Complexes 4 and 5 are isostructural, with space groupC2/c (No. 15). For 4, a = 30.080(2) Å, b = 5.3638(6) Å, c = 24.739(2) Å, ddle"> = 90.342(7)deg.gif">, and for 5, a =29.419(2) Å, b = 5.320(2) Å, c = 24.461(2) Å, ddle"> = 90.840(4)deg.gif">. The Zn resides on a 2-fold axis and the complexeshave a distorted cis octahedral structure with Zn-ORCOO bond lengths of 2.183(3) and 2.169(3) Å, a Zn-OEtOHbond length of 2.015(3) Å in 4, Zn-ORCOO bond lengths of 2.195(2) and 2.151(2) Å, and a Zn-OMeOH bondlength of 2.022(3) Å in 5.