(Di)-aminoguanidine functionalization through transamination: An avenue to an auspicious class of supramolecular synthons

A.D. Naik, B. Tinant, Quoc Toan Le, J. Marchand-Brynaert, B.-L. Su, Y. Garcia

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

N-4H-1,2,4-Triazol-4-yl-guanidine hydrochloride (L1) and a heterocyclized 3,4-diamino-4H-1,2,4-triazole hydrochloride (L2) were synthesized in good yields thanks to a transamination reaction of aminoguanidine and diaminoguanidine hydrochlorides, whose mechanism is presented. L1 and L2 crystallize in monoclinic (P2 /a) and triclinic (P1̄) space groups, respectively. Hydrogen bonding interactions dictated by H-donor, acceptor rich ligand framework together with lattice chloride ions in L1 and L2 organize the crystal packing into a three-dimensional (3D) supramolecular network. The crystal structure of L1 is the first one for a 1,2,4-triazole ligand constructed from aminoguanidine. Both L1 and L2 that exist in monocationic form were introduced as supramolecular synthons to prepare Zn(II) complexes. Scanning electron microscopy (SEM) images on a bulk sample of [Zn(L1) Cl ]Cl ·H O (1) reveals a spontaneous aggregation of porous balls of coccolith morphology with surface decorated sickle-shaped particles of ∼100 nm thickness, whereas a powder sample of [Zn(L2) Cl ]·H O (2) shows neat rectangular blocks of ∼470 nm thickness. Colorless crystals of 2 crystallize in a monoclinic space group (C2/c). Zn(II) ions bound chloride with NH6B⋯Cl(1) = 2.495(2) Å and N⋯H type bonding (N6⋯H3C3 = 2.743(2) Å; N2⋯H7N7 = 1.989(2) Å) affording a 3D supramolecular network. The degree of pyramidality, ∑N = 38°, observed at one of the terminal amines in L2 is still retained in 2, but "flipping" of orientation of attached protons due to directional H-bonding is observed too. Porosity partitioning by mercury porosimetry measurements on 1 and 2 reveals interparticular porosities between 7 and 15 μm. N and H gas adsorption capacities of 1 and 2 were measured by BET which shows no preference for N but a low irreversible H uptake of 3 cm /g.
langueAnglais
Pages4034-4043
Nombre de pages10
journalCrystal Growth and Design
Volume11
Numéro9
Les DOIs
étatPublié - 7 sept. 2011

Empreinte digitale

hydrochlorides
Chlorides
Porosity
Ligands
Ions
Gas adsorption
Crystals
Guanidine
Mercury
chlorides
Powders
Amines
porosity
guanidines
Protons
Hydrogen bonds
ligands
Agglomeration
Crystal structure
Hydrogen

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Naik, A.D. ; Tinant, B. ; Le, Quoc Toan ; Marchand-Brynaert, J. ; Su, B.-L. ; Garcia, Y. / (Di)-aminoguanidine functionalization through transamination : An avenue to an auspicious class of supramolecular synthons. Dans: Crystal Growth and Design. 2011 ; Vol 11, Numéro 9. p. 4034-4043.
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abstract = "N-4H-1,2,4-Triazol-4-yl-guanidine hydrochloride (L1) and a heterocyclized 3,4-diamino-4H-1,2,4-triazole hydrochloride (L2) were synthesized in good yields thanks to a transamination reaction of aminoguanidine and diaminoguanidine hydrochlorides, whose mechanism is presented. L1 and L2 crystallize in monoclinic (P2 /a) and triclinic (P1̄) space groups, respectively. Hydrogen bonding interactions dictated by H-donor, acceptor rich ligand framework together with lattice chloride ions in L1 and L2 organize the crystal packing into a three-dimensional (3D) supramolecular network. The crystal structure of L1 is the first one for a 1,2,4-triazole ligand constructed from aminoguanidine. Both L1 and L2 that exist in monocationic form were introduced as supramolecular synthons to prepare Zn(II) complexes. Scanning electron microscopy (SEM) images on a bulk sample of [Zn(L1) Cl ]Cl ·H O (1) reveals a spontaneous aggregation of porous balls of coccolith morphology with surface decorated sickle-shaped particles of ∼100 nm thickness, whereas a powder sample of [Zn(L2) Cl ]·H O (2) shows neat rectangular blocks of ∼470 nm thickness. Colorless crystals of 2 crystallize in a monoclinic space group (C2/c). Zn(II) ions bound chloride with NH6B⋯Cl(1) = 2.495(2) {\AA} and N⋯H type bonding (N6⋯H3C3 = 2.743(2) {\AA}; N2⋯H7N7 = 1.989(2) {\AA}) affording a 3D supramolecular network. The degree of pyramidality, ∑N = 38°, observed at one of the terminal amines in L2 is still retained in 2, but {"}flipping{"} of orientation of attached protons due to directional H-bonding is observed too. Porosity partitioning by mercury porosimetry measurements on 1 and 2 reveals interparticular porosities between 7 and 15 μm. N and H gas adsorption capacities of 1 and 2 were measured by BET which shows no preference for N but a low irreversible H uptake of 3 cm /g.",
author = "A.D. Naik and B. Tinant and Le, {Quoc Toan} and J. Marchand-Brynaert and B.-L. Su and Y. Garcia",
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(Di)-aminoguanidine functionalization through transamination : An avenue to an auspicious class of supramolecular synthons. / Naik, A.D.; Tinant, B.; Le, Quoc Toan; Marchand-Brynaert, J.; Su, B.-L.; Garcia, Y.

Dans: Crystal Growth and Design, Vol 11, Numéro 9, 07.09.2011, p. 4034-4043.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - (Di)-aminoguanidine functionalization through transamination

T2 - Crystal Growth and Design

AU - Naik, A.D.

AU - Tinant, B.

AU - Le, Quoc Toan

AU - Marchand-Brynaert, J.

AU - Su, B.-L.

AU - Garcia, Y.

PY - 2011/9/7

Y1 - 2011/9/7

N2 - N-4H-1,2,4-Triazol-4-yl-guanidine hydrochloride (L1) and a heterocyclized 3,4-diamino-4H-1,2,4-triazole hydrochloride (L2) were synthesized in good yields thanks to a transamination reaction of aminoguanidine and diaminoguanidine hydrochlorides, whose mechanism is presented. L1 and L2 crystallize in monoclinic (P2 /a) and triclinic (P1̄) space groups, respectively. Hydrogen bonding interactions dictated by H-donor, acceptor rich ligand framework together with lattice chloride ions in L1 and L2 organize the crystal packing into a three-dimensional (3D) supramolecular network. The crystal structure of L1 is the first one for a 1,2,4-triazole ligand constructed from aminoguanidine. Both L1 and L2 that exist in monocationic form were introduced as supramolecular synthons to prepare Zn(II) complexes. Scanning electron microscopy (SEM) images on a bulk sample of [Zn(L1) Cl ]Cl ·H O (1) reveals a spontaneous aggregation of porous balls of coccolith morphology with surface decorated sickle-shaped particles of ∼100 nm thickness, whereas a powder sample of [Zn(L2) Cl ]·H O (2) shows neat rectangular blocks of ∼470 nm thickness. Colorless crystals of 2 crystallize in a monoclinic space group (C2/c). Zn(II) ions bound chloride with NH6B⋯Cl(1) = 2.495(2) Å and N⋯H type bonding (N6⋯H3C3 = 2.743(2) Å; N2⋯H7N7 = 1.989(2) Å) affording a 3D supramolecular network. The degree of pyramidality, ∑N = 38°, observed at one of the terminal amines in L2 is still retained in 2, but "flipping" of orientation of attached protons due to directional H-bonding is observed too. Porosity partitioning by mercury porosimetry measurements on 1 and 2 reveals interparticular porosities between 7 and 15 μm. N and H gas adsorption capacities of 1 and 2 were measured by BET which shows no preference for N but a low irreversible H uptake of 3 cm /g.

AB - N-4H-1,2,4-Triazol-4-yl-guanidine hydrochloride (L1) and a heterocyclized 3,4-diamino-4H-1,2,4-triazole hydrochloride (L2) were synthesized in good yields thanks to a transamination reaction of aminoguanidine and diaminoguanidine hydrochlorides, whose mechanism is presented. L1 and L2 crystallize in monoclinic (P2 /a) and triclinic (P1̄) space groups, respectively. Hydrogen bonding interactions dictated by H-donor, acceptor rich ligand framework together with lattice chloride ions in L1 and L2 organize the crystal packing into a three-dimensional (3D) supramolecular network. The crystal structure of L1 is the first one for a 1,2,4-triazole ligand constructed from aminoguanidine. Both L1 and L2 that exist in monocationic form were introduced as supramolecular synthons to prepare Zn(II) complexes. Scanning electron microscopy (SEM) images on a bulk sample of [Zn(L1) Cl ]Cl ·H O (1) reveals a spontaneous aggregation of porous balls of coccolith morphology with surface decorated sickle-shaped particles of ∼100 nm thickness, whereas a powder sample of [Zn(L2) Cl ]·H O (2) shows neat rectangular blocks of ∼470 nm thickness. Colorless crystals of 2 crystallize in a monoclinic space group (C2/c). Zn(II) ions bound chloride with NH6B⋯Cl(1) = 2.495(2) Å and N⋯H type bonding (N6⋯H3C3 = 2.743(2) Å; N2⋯H7N7 = 1.989(2) Å) affording a 3D supramolecular network. The degree of pyramidality, ∑N = 38°, observed at one of the terminal amines in L2 is still retained in 2, but "flipping" of orientation of attached protons due to directional H-bonding is observed too. Porosity partitioning by mercury porosimetry measurements on 1 and 2 reveals interparticular porosities between 7 and 15 μm. N and H gas adsorption capacities of 1 and 2 were measured by BET which shows no preference for N but a low irreversible H uptake of 3 cm /g.

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U2 - 10.1021/cg200612j

DO - 10.1021/cg200612j

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SN - 1528-7483

IS - 9

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