Efficient Proton-Templated Synthesis of 18- to 38-Membered Tetraimino(amino)diphenol Macrocyclic Ligands:  Structural Features and Spectroscopic Properties

Dutta, Biswajit; Bag, Pradip; Adhikary, Bibhutosh; Flörke, Ülrich; Nag, Kamalaksha

doi:10.1021/jo049787s

Cited by 74 publications

(47 citation statements)

References 46 publications

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“…The H 2Ll igand was synthesized by following the procedure described previously [1]. Amixture of H2L(0.0412 g, 0.1 mmol), 1,3,5-benzene tricarboxylic acid (0.014 g, 0.07 mmol), Ni(OH) 2 (0.020 g, 0.2 mmol), methanol (5 mL) and water (5 mL) was sealed in a15mLTeflon-lined stainless steel container.…”

Section: Source Of Materialsmentioning

confidence: 99%

Crystal structure of diaqua[μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo- [19.3.1.19,13]tetracosa-1(24),9(25),10,12,21,23-hexaene-25,26-diol]- (hydrogen 1,3,5-benzenetricarboxylato)dinickel(II) sesquihydrate, Ni2(H2O)2(C24H34N4O2)(C9H4O6) · 1.5H2O

Chen¹,

Liu²

2010

Zeitschrift Für Kristallographie - New Crystal Structures

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C 33H45N4Ni2O11.5,m onoclinic, P121/c1(no. 14), a =10.531(5) Å, b =20.032(5) Å, c =17.057(5) Å, b =101.778(5)°, V =3522.6 Å 3 , Z =4,R gt (F) =0.055, Source of materialThe H 2Ll igand was synthesized by following the procedure described previously [1]. Amixture of H2L(0.0412 g, 0.1 mmol), 1,3,5-benzene tricarboxylic acid (0.014 g, 0.07 mmol), Ni(OH) 2 (0.020 g, 0.2 mmol), methanol (5 mL) and water (5 mL) was sealed in a15mLTeflon-lined stainless steel container. The container was heated to 120°Ca nd held at this temperature for 3days. The reaction system was then slowly cooled to room temperature at arate of 10°C/ h. Green crystals were obtained in a 30 %yield. Experimental detailsAll Hatoms on Catoms were generated geometrically and refined as riding atoms with d(C-H) =0.93 Å and U iso(H) =1.2 Ueq(C). The nitrogen Hatoms, carboxyl Hatom and water Hatoms were located from difference Fourier map and refined with U iso (H) = 1.5 U eq(O). DiscussionIn recent years, nickel(II) complexes of polyaza macrocyclic ligands, especially those of tetraaza macrocycles, have received more attention [2]. The title compound is adinuclear nickel complex. Each of the two Ni(II) ions is six-coordinated by two oxygen atoms and two nitrogen atoms from the L 2-ligand, one oxygen atom from the hydrogen 1,3,5-benzenetricarboxylate ligand, and one coordinated water molecule in ad istorted octahedral manner. Two Ni(II) atoms are bridged by two phenolate Oatoms to form aNi 2 O 2 ring with the Ni···Ni distance of 3.009 Å.The Ni-Oand Ni-Ndistances are similar to the reported values [3]. The water molecules and hydrogen 1,3,5-benzenetricarboxylate anion interact through O-H···Oh ydrogen bonding to form at hree-dimensional supramolecular network structure.

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Section: Source Of Materialsmentioning

confidence: 99%

Crystal structure of diaqua[μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo- [19.3.1.19,13]tetracosa-1(24),9(25),10,12,21,23-hexaene-25,26-diol]- (hydrogen 1,3,5-benzenetricarboxylato)dinickel(II) sesquihydrate, Ni2(H2O)2(C24H34N4O2)(C9H4O6) · 1.5H2O

Chen¹,

Liu²

2010

Zeitschrift Für Kristallographie - New Crystal Structures

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“…The macrocyclic ligand H 2Lwas prepared as reported earlier [1]. Amethanol solution (30 mL) containing H 2L( 0.44 g, 1mmol) was heated to boiling and then slowly treated with amethanol solution (20 mL) of 4-methyl-2,6-diformyl (0.33 g, 2mmol).…”

Section: Source Of Materialsmentioning

confidence: 99%

Crystal structure of 7,15,23,31-tetramethyl-3,11,19,27-tetraazopentacyclo[ 27.16.1611.27.4.411.27.3.35.9.313.17.321.25.1.15.9.113.17.121.25]triaconta- 1(32),5,7,9(34),13,15,17(35),21,23,25(36),29(33),30-dodecaarene- 33,34,35,36-tetraol, C44H56N4O4

Yang¹

2010

Zeitschrift Für Kristallographie - New Crystal Structures

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C 44 H 56 N 4 O 4 ,monoclinic, C12/c1(no. 15), a =23.216(2) Å, b =14.0445(9) Å, c =13.064(1) Å, b =118.413(9)°, V =3746.5 Å 3 , Z =4,Rgt(F) =0.076, wRref (F 2 ) =0.186, T =293 K. Source of materialThe macrocyclic ligand H 2Lwas prepared as reported earlier [1]. Amethanol solution (30 mL) containing H 2L( 0.44 g, 1mmol) was heated to boiling and then slowly treated with amethanol solution (20 mL) of 4-methyl-2,6-diformyl (0.33 g, 2mmol). After stirring for 1h ,a no range precipitate was obtained. Then a amount of solid NaBH 4 was added to the solution. The solid material gradually went into solution, and ultimately an almost colorless solution was obtained over ap eriod of 0.5 h. This was filtered, and to the filtrate was added slowly 30 mL of water with stirring. The resulting solution was allowed to stand overnight, during which period the product separated out as colorless crystals. The product was collected by filtration and recrystallized from methanol/water (yield 35 %ormore). The product (0.077 g, 0.1 mmol) and Ni(OAc) 2. · . 6H 2 O(0.050 g, 0.2 mmol) were dissolved in DMF (5 mL) and water (5 mL). The mixture sealed in a 15 mL Teflon-lined stainless steel autoclave, and heated at 100°C for 4d ays under autogenous pressure. Afterward, the reaction system was gradually cooled to room temperature at ar ate of 10°C/h. Light green crystals were obtained in a34 . %yield. Experimental detailsAll Ha toms on Ca toms were generated geometrically and refined as riding atoms with d(C-H) =0.93 Å and U iso (H) =1.2 or 1.5 U eq (C). The hydroxy Ha tom were located from difference Fourier map and refined with U iso (H) =1 .5 U eq (O). The huge residual values are caused by the vibration of the terminal C21 and C22 atoms at room temperature. DiscussionRecently, the study of metal complexes with phenol-based macrocyclic compartmental ligands has become important in view of their significance as biomimetric catalysts in the process of oxygenation [2]. Several classes of macrocyclic ligands have been synthesized [3]. In the title crystal structure, the intramolecular hydrogen bonds involving the phenolic oxygens are of particular importance because the macrocyclic cation is stabilized by these bonds. The N···Odistances are in the range 2.738 (5) -3.04 (1) Å,while the O-H···Nangles vary between 135°and 140°,which indicates that the intramolecular hydrogen bonds are quite strong. The C-O and C-Nbond lengthes are in the range of 1.37 to 1.45 Å,respectively. The bond distances and bond angles are all in normal range.

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“…The H 2Lligand was synthesized by following the procedures [1]. Am ixture of H 2 L( 0.0412 g, 0.1 mmol), CuCO 3 (0.0248 g, 0.2 mmol) and terephthalic acid (0.0166 g, 0.1 mmol) in methanol (15 ml) and water (5 ml) was stirred for 10 min.…”

Section: Source Of Materialsmentioning

confidence: 99%

Crystal structure of aqua[μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo- [19.3.1.19,13]tetracosa-1(24),-9(25),10,12,21,23-hexaene-25,26-diol]- dicopper(II) carbonate — terephthalic acid —methanol —water (1:0.5:1:1), [Cu2(C24H34N4O2)(H2O)][CO3] · 0.5C8H6O4 · CH3OH · H2O

Chen¹,

Yang²

2010

Zeitschrift Für Kristallographie - New Crystal Structures

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C 30H45Cu2N4O10,t riclinic, P1 (no. 2), a =11.657(5) Å, b =12.172(5) Å, c =13. Source of materialThe H 2Lligand was synthesized by following the procedures [1]. Am ixture of H 2 L( 0.0412 g, 0.1 mmol), CuCO 3 (0.0248 g, 0.2 mmol) and terephthalic acid (0.0166 g, 0.1 mmol) in methanol (15 ml) and water (5 ml) was stirred for 10 min. The green precipitate was collected and dissolved by dropwise addition of an aqueous solution of NH 3 (14 M). Green single crystals were obtained by slow evaporation of the ammonia solution at room temperature (yield 45 %). Experiemtal detailsAll Hatoms on Catoms were generated geometrically and refined as riding atoms with d(C-H) =0.93 Å and U iso(H) =1.2 Ueq(C). The carboxyl Hatoms, nitrogen Hatoms, and water Hatoms were located from difference Fourier map and refined with U iso(H) = 1.5 U eq(O,N).

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Efficient Proton-Templated Synthesis of 18- to 38-Membered Tetraimino(amino)diphenol Macrocyclic Ligands: Structural Features and Spectroscopic Properties

Cited by 74 publications

References 46 publications

Crystal structure of diaqua[μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo- [19.3.1.19,13]tetracosa-1(24),9(25),10,12,21,23-hexaene-25,26-diol]- (hydrogen 1,3,5-benzenetricarboxylato)dinickel(II) sesquihydrate, Ni2(H2O)2(C24H34N4O2)(C9H4O6) · 1.5H2O

Crystal structure of diaqua[μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo- [19.3.1.19,13]tetracosa-1(24),9(25),10,12,21,23-hexaene-25,26-diol]- (hydrogen 1,3,5-benzenetricarboxylato)dinickel(II) sesquihydrate, Ni2(H2O)2(C24H34N4O2)(C9H4O6) · 1.5H2O

Crystal structure of 7,15,23,31-tetramethyl-3,11,19,27-tetraazopentacyclo[ 27.16.1611.27.4.411.27.3.35.9.313.17.321.25.1.15.9.113.17.121.25]triaconta- 1(32),5,7,9(34),13,15,17(35),21,23,25(36),29(33),30-dodecaarene- 33,34,35,36-tetraol, C44H56N4O4

Crystal structure of aqua[μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo- [19.3.1.19,13]tetracosa-1(24),-9(25),10,12,21,23-hexaene-25,26-diol]- dicopper(II) carbonate — terephthalic acid —methanol —water (1:0.5:1:1), [Cu2(C24H34N4O2)(H2O)][CO3] · 0.5C8H6O4 · CH3OH · H2O

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