Publication: X-ışınları Kırınımı ile O-vanilin Türevi Azo ve Azometin Bileşiklerin Yapı Analizleri
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iÖZETBu çalışmada, Schiff bazı olan (C14H13NO3) ?(Z)-3-hidroksi-6-[(2-metoksifenilamino)metilen]siklohekza-2,4-dienon?, (C15H12F3NO2) ?(E)-2-Metoksi-6-[(2-triflorometilfenilimino)metil]fenol?, (C14H13NO3) ?2-Hidroksi-6-[(2-metoksifenil)aminometilen]siklohekza-2,4-dienon? kristallerinin, azo ve azometin gruplarına sahip(C20H25N3O5) ?(E)-2-[1,3-Dihidroksi-2-(hidroksimetil)propan-2-iliminometilen]-4-[(4-etilfenil)diazenil]-6-metoksisiklohekzanon? kristalinin ve azo boyarmadde olan(C14H11BrN2O3) ?(E)-5-[(3-bromofenil)diazenil]-2-hidroksi-3-metoksibenzaldehit?,(C14H11FN2O3) ?(E)-5-[(2-florofenil)diazenil]-2-hidroksi-3-metoksibenzaldehit?kristallerinin yapıları, tek kristal x-ışınları kırınımı yöntemiyle tayin edilmiştir.Kristallerin verileri, STOE IPDS II difraktometresi ile toplanmıştır. Yapılar, SHELXS-97 (Sheldrick, 1997) programı yardımı ile direkt yöntemler kullanılarak çözülmüş veSHELXL-97 (Sheldrick, 1997) programı yardımı ile en küçük kareler yöntemi ilearıtılmıştır.C14H13NO3, (I), Ortorombik, P212121, a=8.3391(7)Ǻ, b=11.1748(15)Ǻ,3 -3c=13.8056(19)Ǻ, V=1286.5(3)Ǻ , Z=4, Dx=1.256Mgm , λ(MoKα)=0.71073Ǻ,μ=0.089mm-1, T=296K, R=0.0593, wR=0.1919, S=0.973.C14H13NO3 kapalı formülüne sahip Schiff bazının {(Z)-3-hidroksi-6-[(2-metoksifenilamino)metilen]siklohekza-2,4-dienon} keto-amin tautomerik yapıda olduğugörülmüştür. Aromatik halkaların düzlemleri arasındaki dihedral açı 14.3(2)° dir.Yapıda molekül içi N-Hâ ¦O ve moleküller arası O-H...O hidrojen bağları vardır. Ayrıcayapıda moleküller arası Ï -halka etkileşimi de bulunmaktadır.C15H12F3NO2, (II), Ortorombik, P212121, a=5.2070(5)Ǻ, b=14.0918(18)Ǻ,V=1333.5(3)Ǻ3, Dx=1.471Mgm-3,c=18.1737(18)Ǻ, Z=4, λ(MoKα)=0.71073Ǻ,μ=0.13mm-1, T=296K, R=0.054, wR=0.123, S=0.89.C15H12F3NO2 kapalı formülüne sahip Schiff bazının {(E)-2-Metoksi-6-[(2triflorometilfenilimino)metil]fenol} fenol-imin tautomerik yapıda olduğugörülmüştür. Aromatik halkaların düzlemleri arasındaki dihedral açı 17.83(19)° dir.Yapı molekül içi O-Hâ ¦N ve O-Hâ ¦F hidrojen bağlarına sahiptir. Molekülün aynızamanda üç boyutta kristal örgüyü şekillendiren üç tane C-H...F ve iki tane C-Hâ ¦Oiimoleküller arası hidrojen bağı vardır. Ayrıca yapıda moleküller arası Ï -halka etkileşimibulunmaktadır.C14H13NO3, (III), Monoklinik, P21/n, a=7.5517(7)Ǻ, b=11.3022(12)Ǻ,V=1144.5(2)Ǻ3, Dx=1.412Mgm-3,c=13.4646(13)Ǻ, β=95.186(8)°, Z=4,λ(MoKα)=0.71073Ǻ, μ=0.10mm-1, T=296K, R=0.038, wR=0.096, S=0.85.?2-Hidroksi-6-[(2-metoksifenil)aminometilen]siklohekza-2,4-dienon? molekülününneredeyse düzlemsel olduğu görülmüştür. Ayrıca C14H13NO3 kapalı formüllü Schiffbazının keto-amin tautomerik form da olduğu tespit edilmiştir. Yapıda molekül içi N-Hâ ¦O ile moleküller arası O-Hâ ¦O ve C-Hâ ¦O hidrojen bağı gözlenmiştir. Ayrıcayapıda moleküller arası Ï -halka etkileşimi bulunmaktadır.C20H25N3O5, (IV), Monoklinik, P21/c, a=17.0925(16)Ǻ, b=10.6353(6)Ǻ,3Dx=1.345Mgm-3,c=10.6634(9)Ǻ, β=99.263(7)°, V=1913.2(3)Ǻ , Z=4,λ(MoKα)=0.71073Ǻ, μ=0.10mm-1, T=150K, R=0.058, wR=0.174, S=1.05.Kapalı formülü C20H25N3O5 olan azo-azometin bileşiğinin {(E)-2-[1,3-Dihidroksi-2-(hidroksimetil)propan-2-iliminometilen]-4-[(4-etilfenil)diazenil]-6-metoksisiklohekzanon} keto-amin tautomerik yapıda olduğu görülmüştür. N=N çift bağ uzunluğu 1.232(3)Ǻ olarak bulunmuş olup bu değerin literatürle uyumlu olduğu görülmüştür. Kristalyapıda moleküller, molekül içi N-Hâ ¦O ve O-Hâ ¦O, moleküller arasında ise O-H...Ohidrojen bağlarına sahiptir.C14H11BrN2O3, (V), Ortorombik, Pbcn, a=12.5131(6)Ǻ, b=13.2636(6)Ǻ,V=2748.3(2)Ǻ3, Dx=1.620Mgm-3,c=16.5594(7)Ǻ, Z=8, λ(MoKα)=0.71073Ǻ,-1μ=3.00mm , T=296K, R=0.037, wR= 0.091, S=1.03.?(E)-5-[(3-bromofenil)diazenil]-2-hidroksi-3-metoksibenzaldehit? bileşiği transkonfigürasyona sahiptir ve iki fenil halkası arasındaki dihedral açı 8.71(12)° olarakbulunmuştur. N=N çift bağ uzunluğu 1.257(3) Ǻ olarak bulunmuş olup bu değerinliteratürdeki değerlerden yüksek olduğu görülmüştür. Yapıda molekül içi O-Hâ ¦Ohidrojen bağı gözlenmiştir. Ayrıca yapıda moleküller arası Ï -halka ve Ï -Ï etkileşimleribulunmaktadır.iiiC14H11FN2O3, (VI), Monoklinik, Cc, a=10.7956(8)Ǻ, b=13.7521(13)Ǻ,3 -3c=8.3078(6)Ǻ, V=1232.42(17)Ǻ , Z=4, Dx=1.478Mgm , λ(MoKα)=0.71073Ǻ,-1μ=0.12mm , T=296K, R=0.030, wR=0.083, S=1.06.?(E)-5-[(2-florofenil)diazenil]-2-hidroksi-3-metoksibenzaldehit? bileşiği transkonfigürasyona sahiptir ve iki fenil halkası arasındaki dihedral açı 10.13(8)° olarakbulunmuştur. Yapıda molekül içi O-Hâ ¦O hidrojen bağı gözlenmiştir. Ayrıca yapıdamoleküller arası Ï -Ï etkileşimi bulunmaktadır.Anahtar Kelimeler: Schiff bazları, keto-fenol tautomerisi, azo bileşikleri.
ivABSTRACTIn this study, the Schiff base crystals of (C14H13NO3) ?(Z)-3-hydroxy-6-((2-methoxyphenylamino)methylene)cyclohexa-2,4-dienone?, (C15H12F3NO2) ?(E)-2-methoxy-6-((2-(trifluoromethyl)phenylimino)methyl)phenol?, (C14H13NO3) ?2-Hydroxy-6-[(2-methoxy-phenylamino)-methylene]-cyclohexa-2,4-dienone?, the azo andazometin containing crystal of (C20H25N3O5) ?(E)-2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino]methyl}-4-[(4-ethylphenyl)diazenyl]-6-methoxycyclohexanone? and crystals of (C14H11BrN2O3) ?(E)-5-[(3-bromophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde?, (C14H11FN2O3) ?(E)-5-[(2-fluorophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde? which contain only azo group have beendetermined by single crystal x-ray diffraction technique. The structure determination ofall crystals have been carried out using the method of single crystal x-ray diffraction.The data of crystals were collected with a STOE IPDS II diffractometer. The structureshave been solved by direct methods with the program SHELXS-97 (Sheldrick, 1997)and refined using least squares refinement with the program SHELXL-97 (Sheldrick,1997).C14H13NO3, (I), Orthorhombic, P212121, a=8.3391(7)Ǻ, b=11.1748(15)Ǻ,3 -3c=13.8056(19)Ǻ, V=1286.5(3)Ǻ , Z=4, Dx=1.256Mgm , λ(MoKα)=0.71073Ǻ,μ=0.089mm-1, T=296K, R=0.0593, wR=0.1919, S=0.973.Schiff base crystal of (C14H13NO3) ?(Z)-3-hydroxy-6-((2-methoxyphenylamino)methylene)cyclohexa-2,4-dienone? has keto-amine tautomeric structure with the angleof 14.3(2)° between the planes of the aromatic rings. In the structure, intramolecular N-Hâ ¦O and intermolecular O-Hâ ¦O hydrogen bonding were observed. There is alsointermolecular Ï -ring interaction in the structure.C15H12F3NO2, (II), Orthorhombic, P212121, a=5.2070(5)Ǻ, b=14.0918(18)Ǻ,V=1333.5(3)Ǻ3, Dx=1.471Mgm-3,c=18.1737(18)Ǻ, Z=4, λ(MoKα)=0.71073Ǻ,μ=0.13mm-1, T=296K, R=0.054, wR=0.123, S=0.89.Schiff base crystal of (C15H12F3NO2) ?(E)-2-methoxy-6-[(2-(trifluoromethyl)phenylimino)methyl]phenol? has fenol-imine tautomeric structure with the angle ofv17.83(19)° between the planes of the aromatic rings. In the structure, intramolecular O-Hâ ¦N and O-Hâ ¦F hydrogen bonding were observed. The structure has also three C-Hâ ¦F and two C-Hâ ¦O intermolecular hydrogen bonds and intermolecular Ï -ringinteraction.C14H13NO3, (III), Monoclinic, P21/n, a=7.5517(7)Ǻ, b=11.3022(12)Ǻ,V=1144.5(2)Ǻ3, Dx=1.412Mgm-3,c=13.4646(13)Ǻ, β=95.186(8)°, Z=4,λ(MoKα)=0.71073Ǻ, μ=0.10mm-1, T=296K, R=0.038, wR=0.096, S=0.85.?2-Hydroxy-6-[(2-methoxy-phenylamino)-methylene]-cyclohexa-2,4-dienone?complex has an almost planar structure. In addition to this feature it was determined tobe in keto-amin tautomeric form. In the structure, intramolecular N-Hâ ¦O andintermolecular O-Hâ ¦O and C-Hâ ¦O hydrogen bonding were observed. It has also seenthat there is intermolecular Ï -ring interaction in the structure.C20H25N3O5, (IV), Monoclinic, P21/c, a=17.0925(16)Ǻ, b=10.6353(6)Ǻ,V=1913.2(3)Ǻ3, Dx=1.345Mgm-3,c=10.6634(9)Ǻ, β=99.263(7)°, Z=4,λ(MoKα)=0.71073Ǻ, μ=0.10mm-1, T=150K, R=0.058, wR=0.174, S=1.05.Azo and azometin containing crystal of (C20H25N3O5) ?(E)-2-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yliminomethyl]-4-[(4-ethylphenyl)diazenyl]-6-methoxycyclohexanone? has keto-amine tautomeric form with the N=N bond length of 1.232(3) Ǻand this value is in a good agreement with the reported values. The crystal packing isstabilized by intramolecular [N-Hâ ¦O and O-Hâ ¦O] and intermolecular [O-Hâ ¦O]hydrogen bonding interactions.C14H11BrN2O3, (V), Orthorhombic, Pbcn, a=12.5131(6)Ǻ, b=13.2636(6)Ǻ,V=2748.3(2)Ǻ3, Dx=1.620Mgm-3,c=16.5594(7)Ǻ, Z=8, λ(MoKα)=0.71073Ǻ,μ=3.00mm-1, T=296K, R=0.037, wR= 0.091, S=1.03.?(E)-5-[(3-bromophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde? complexhas a trans configuration and the dihedral angle between the two phenyl rings is8.71(12)°. The N=N bond length is 1.257(3) Ǻ and this value is longer than the reportedvalues. In the structure, intramolecular O-Hâ ¦O hydrogen bonding was observed. It hasalso seen that there are intermolecular Ï -ring and Ï -Ï interactions in the structure.viC14H11FN2O3, (VI), Monoclinic, Cc, a=10.7956(8)Ǻ, b=13.7521(13)Ǻ,3 -3c=8.3078(6)Ǻ, V=1232.42(17)Ǻ , Z=4, Dx=1.478Mgm , λ(MoKα)=0.71073Ǻ,μ=0.12mm-1, T=296K, R=0.030, wR=0.083, S=1.06.?(E)-5-[(2-fluorophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde? complexhas a trans configuration and the dihedral angle between two phenyl rings is 10.13(8)°.In the structure, intramolecular O-Hâ ¦O hydrogen bonds and intermolecular Ï -Ï interactions were observed.Key Words: Schiff bases, keto-fenol tautomeric form, azo complexes.
ivABSTRACTIn this study, the Schiff base crystals of (C14H13NO3) ?(Z)-3-hydroxy-6-((2-methoxyphenylamino)methylene)cyclohexa-2,4-dienone?, (C15H12F3NO2) ?(E)-2-methoxy-6-((2-(trifluoromethyl)phenylimino)methyl)phenol?, (C14H13NO3) ?2-Hydroxy-6-[(2-methoxy-phenylamino)-methylene]-cyclohexa-2,4-dienone?, the azo andazometin containing crystal of (C20H25N3O5) ?(E)-2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino]methyl}-4-[(4-ethylphenyl)diazenyl]-6-methoxycyclohexanone? and crystals of (C14H11BrN2O3) ?(E)-5-[(3-bromophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde?, (C14H11FN2O3) ?(E)-5-[(2-fluorophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde? which contain only azo group have beendetermined by single crystal x-ray diffraction technique. The structure determination ofall crystals have been carried out using the method of single crystal x-ray diffraction.The data of crystals were collected with a STOE IPDS II diffractometer. The structureshave been solved by direct methods with the program SHELXS-97 (Sheldrick, 1997)and refined using least squares refinement with the program SHELXL-97 (Sheldrick,1997).C14H13NO3, (I), Orthorhombic, P212121, a=8.3391(7)Ǻ, b=11.1748(15)Ǻ,3 -3c=13.8056(19)Ǻ, V=1286.5(3)Ǻ , Z=4, Dx=1.256Mgm , λ(MoKα)=0.71073Ǻ,μ=0.089mm-1, T=296K, R=0.0593, wR=0.1919, S=0.973.Schiff base crystal of (C14H13NO3) ?(Z)-3-hydroxy-6-((2-methoxyphenylamino)methylene)cyclohexa-2,4-dienone? has keto-amine tautomeric structure with the angleof 14.3(2)° between the planes of the aromatic rings. In the structure, intramolecular N-Hâ ¦O and intermolecular O-Hâ ¦O hydrogen bonding were observed. There is alsointermolecular Ï -ring interaction in the structure.C15H12F3NO2, (II), Orthorhombic, P212121, a=5.2070(5)Ǻ, b=14.0918(18)Ǻ,V=1333.5(3)Ǻ3, Dx=1.471Mgm-3,c=18.1737(18)Ǻ, Z=4, λ(MoKα)=0.71073Ǻ,μ=0.13mm-1, T=296K, R=0.054, wR=0.123, S=0.89.Schiff base crystal of (C15H12F3NO2) ?(E)-2-methoxy-6-[(2-(trifluoromethyl)phenylimino)methyl]phenol? has fenol-imine tautomeric structure with the angle ofv17.83(19)° between the planes of the aromatic rings. In the structure, intramolecular O-Hâ ¦N and O-Hâ ¦F hydrogen bonding were observed. The structure has also three C-Hâ ¦F and two C-Hâ ¦O intermolecular hydrogen bonds and intermolecular Ï -ringinteraction.C14H13NO3, (III), Monoclinic, P21/n, a=7.5517(7)Ǻ, b=11.3022(12)Ǻ,V=1144.5(2)Ǻ3, Dx=1.412Mgm-3,c=13.4646(13)Ǻ, β=95.186(8)°, Z=4,λ(MoKα)=0.71073Ǻ, μ=0.10mm-1, T=296K, R=0.038, wR=0.096, S=0.85.?2-Hydroxy-6-[(2-methoxy-phenylamino)-methylene]-cyclohexa-2,4-dienone?complex has an almost planar structure. In addition to this feature it was determined tobe in keto-amin tautomeric form. In the structure, intramolecular N-Hâ ¦O andintermolecular O-Hâ ¦O and C-Hâ ¦O hydrogen bonding were observed. It has also seenthat there is intermolecular Ï -ring interaction in the structure.C20H25N3O5, (IV), Monoclinic, P21/c, a=17.0925(16)Ǻ, b=10.6353(6)Ǻ,V=1913.2(3)Ǻ3, Dx=1.345Mgm-3,c=10.6634(9)Ǻ, β=99.263(7)°, Z=4,λ(MoKα)=0.71073Ǻ, μ=0.10mm-1, T=150K, R=0.058, wR=0.174, S=1.05.Azo and azometin containing crystal of (C20H25N3O5) ?(E)-2-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yliminomethyl]-4-[(4-ethylphenyl)diazenyl]-6-methoxycyclohexanone? has keto-amine tautomeric form with the N=N bond length of 1.232(3) Ǻand this value is in a good agreement with the reported values. The crystal packing isstabilized by intramolecular [N-Hâ ¦O and O-Hâ ¦O] and intermolecular [O-Hâ ¦O]hydrogen bonding interactions.C14H11BrN2O3, (V), Orthorhombic, Pbcn, a=12.5131(6)Ǻ, b=13.2636(6)Ǻ,V=2748.3(2)Ǻ3, Dx=1.620Mgm-3,c=16.5594(7)Ǻ, Z=8, λ(MoKα)=0.71073Ǻ,μ=3.00mm-1, T=296K, R=0.037, wR= 0.091, S=1.03.?(E)-5-[(3-bromophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde? complexhas a trans configuration and the dihedral angle between the two phenyl rings is8.71(12)°. The N=N bond length is 1.257(3) Ǻ and this value is longer than the reportedvalues. In the structure, intramolecular O-Hâ ¦O hydrogen bonding was observed. It hasalso seen that there are intermolecular Ï -ring and Ï -Ï interactions in the structure.viC14H11FN2O3, (VI), Monoclinic, Cc, a=10.7956(8)Ǻ, b=13.7521(13)Ǻ,3 -3c=8.3078(6)Ǻ, V=1232.42(17)Ǻ , Z=4, Dx=1.478Mgm , λ(MoKα)=0.71073Ǻ,μ=0.12mm-1, T=296K, R=0.030, wR=0.083, S=1.06.?(E)-5-[(2-fluorophenyl)diazenyl]-2-hydroxy-3-methoxybenzaldehyde? complexhas a trans configuration and the dihedral angle between two phenyl rings is 10.13(8)°.In the structure, intramolecular O-Hâ ¦O hydrogen bonds and intermolecular Ï -Ï interactions were observed.Key Words: Schiff bases, keto-fenol tautomeric form, azo complexes.
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Tez (yüksek lisans) -- Ondokuz Mayıs Üniversitesi, 2006
Libra Kayıt No: 17078
Libra Kayıt No: 17078
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