Formaldehyde-aminoguanidine condensation and aminoguanidine self-condensation products: Syntheses, crystal structures and characterization.

Elena A. Buvaylo, Vladimir N. Kokozay, Nataliia Y. Strutynska, Olga Y. Vassilyeva, Brian W. Skelton

Research output: Contribution to journalArticle

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Abstract

Guanidine is the functional group on the side chain of arginine, one of the fundamental building blocks of life. In recent years, a number of compounds based on the aminoguanidine (AG) moiety have been described as presenting high anticancer activities. The product of condensation between two molecules of AG and one molecule of formaldehyde was isolated in the protonated form as the dinitrate salt (systematic name: 2,8-diamino-1,3,4,6,7,9-hexaazanona-1,8-diene-1,9-diium dinitrate), C3H14N8 2+·2NO3 -, (I). The cation lacks crystallographically imposed symmetry and comprises two terminal planar guanidinium groups, which share an N-C-N unit. Each cation in (I) builds 14 N-H.O hydrogen bonds and is separated from adjacent cations by seven nitrate anions. The AG self-condensation reaction in the presence of copper(II) chloride and chloride anions led to the formation of the organic-inorganic hybrid 1,2-bis(diaminomethylidene)hydrazine-1,2-diium tetrachloridocuprate(II), (C2H10N6)[CuCl4], (II). Its asymmetric unit is composed of half a diprotonated 1,2-bis(diaminomethylidene)hydrazine-1,2-diium dication and half a tetrachloridocuprate(II) dianion, with the CuII atom situated on a twofold rotation axis. The planar guanidinium fragments in (II) have their planes twisted by approximately 77.64'(5)° with respect to each other. The tetrahedral [CuCl4]2- anion is severely distorted and its pronounced 'planarity' must originate from its involvement in multiple N-H.Cl hydrogen bonds. It was reported that [CuCl4]2- anions, with a trans-Cl-Cu-Cl angle (Θ) of 140°, are yellow-green at room temperature, with the colour shifting to a deeper green as Θ increases and toward orange as Θ decreases. Brown salt (II), with a Θ value of 142.059'(8)°, does not fit the trend, which emphasizes the need to take other structural factors into consideration. In the crystal of salt (II), layers of cations and anions alternate along the b axis, with the minimum Cu.Cu distance being 7.5408'(3)'Å inside a layer. The structures of salts (I) and (II) were substantiated via spectroscopic data. The endothermic reaction involved in the thermal decomposition of (I) requires additional oxygen. The title salts may be useful for the screening of new substances with biological activity.The ionic salts of diprotonated cations of 2,2′-methylenedihydrazinecarboximidamide and bisguanidine have been prepared for the first time and characterized by X-ray diffraction and spectroscopic methods. The endothermic reaction involved in the thermal decomposition of the high-nitrogen-content (49%) oxygen-containing former material requires additional oxygen.

Original languageEnglish
Pages (from-to)152-158
Number of pages7
JournalActa Crystallographica Section C: Structural Chemistry
Volume74
Issue number2
DOIs
Publication statusPublished - 1 Feb 2018

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formaldehyde
Formaldehyde
Condensation
hydrazine
condensation
Salts
Crystal structure
Anions
Cations
salts
Negative ions
Positive ions
crystal structure
anions
Guanidine
cations
synthesis
products
dinitrates
endothermic reactions

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@article{0c0f438894cb4bfebb9d21fe1a7b8853,
title = "Formaldehyde-aminoguanidine condensation and aminoguanidine self-condensation products: Syntheses, crystal structures and characterization.",
abstract = "Guanidine is the functional group on the side chain of arginine, one of the fundamental building blocks of life. In recent years, a number of compounds based on the aminoguanidine (AG) moiety have been described as presenting high anticancer activities. The product of condensation between two molecules of AG and one molecule of formaldehyde was isolated in the protonated form as the dinitrate salt (systematic name: 2,8-diamino-1,3,4,6,7,9-hexaazanona-1,8-diene-1,9-diium dinitrate), C3H14N8 2+·2NO3 -, (I). The cation lacks crystallographically imposed symmetry and comprises two terminal planar guanidinium groups, which share an N-C-N unit. Each cation in (I) builds 14 N-H.O hydrogen bonds and is separated from adjacent cations by seven nitrate anions. The AG self-condensation reaction in the presence of copper(II) chloride and chloride anions led to the formation of the organic-inorganic hybrid 1,2-bis(diaminomethylidene)hydrazine-1,2-diium tetrachloridocuprate(II), (C2H10N6)[CuCl4], (II). Its asymmetric unit is composed of half a diprotonated 1,2-bis(diaminomethylidene)hydrazine-1,2-diium dication and half a tetrachloridocuprate(II) dianion, with the CuII atom situated on a twofold rotation axis. The planar guanidinium fragments in (II) have their planes twisted by approximately 77.64'(5)° with respect to each other. The tetrahedral [CuCl4]2- anion is severely distorted and its pronounced 'planarity' must originate from its involvement in multiple N-H.Cl hydrogen bonds. It was reported that [CuCl4]2- anions, with a trans-Cl-Cu-Cl angle (Θ) of 140°, are yellow-green at room temperature, with the colour shifting to a deeper green as Θ increases and toward orange as Θ decreases. Brown salt (II), with a Θ value of 142.059'(8)°, does not fit the trend, which emphasizes the need to take other structural factors into consideration. In the crystal of salt (II), layers of cations and anions alternate along the b axis, with the minimum Cu.Cu distance being 7.5408'(3)'{\AA} inside a layer. The structures of salts (I) and (II) were substantiated via spectroscopic data. The endothermic reaction involved in the thermal decomposition of (I) requires additional oxygen. The title salts may be useful for the screening of new substances with biological activity.The ionic salts of diprotonated cations of 2,2′-methylenedihydrazinecarboximidamide and bisguanidine have been prepared for the first time and characterized by X-ray diffraction and spectroscopic methods. The endothermic reaction involved in the thermal decomposition of the high-nitrogen-content (49{\%}) oxygen-containing former material requires additional oxygen.",
keywords = "Aminoguanidine, carboximidamide, condensation reaction, crystal structure, hydrogen bonding, tetrachloridocuprate(II), thermogravimetric analysis",
author = "Buvaylo, {Elena A.} and Kokozay, {Vladimir N.} and Strutynska, {Nataliia Y.} and Vassilyeva, {Olga Y.} and Skelton, {Brian W.}",
year = "2018",
month = "2",
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language = "English",
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pages = "152--158",
journal = "Acta Crystallographica Section C: Structural Chemistry",
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Formaldehyde-aminoguanidine condensation and aminoguanidine self-condensation products : Syntheses, crystal structures and characterization. / Buvaylo, Elena A.; Kokozay, Vladimir N.; Strutynska, Nataliia Y.; Vassilyeva, Olga Y.; Skelton, Brian W.

In: Acta Crystallographica Section C: Structural Chemistry, Vol. 74, No. 2, 01.02.2018, p. 152-158.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Formaldehyde-aminoguanidine condensation and aminoguanidine self-condensation products

T2 - Syntheses, crystal structures and characterization.

AU - Buvaylo, Elena A.

AU - Kokozay, Vladimir N.

AU - Strutynska, Nataliia Y.

AU - Vassilyeva, Olga Y.

AU - Skelton, Brian W.

PY - 2018/2/1

Y1 - 2018/2/1

N2 - Guanidine is the functional group on the side chain of arginine, one of the fundamental building blocks of life. In recent years, a number of compounds based on the aminoguanidine (AG) moiety have been described as presenting high anticancer activities. The product of condensation between two molecules of AG and one molecule of formaldehyde was isolated in the protonated form as the dinitrate salt (systematic name: 2,8-diamino-1,3,4,6,7,9-hexaazanona-1,8-diene-1,9-diium dinitrate), C3H14N8 2+·2NO3 -, (I). The cation lacks crystallographically imposed symmetry and comprises two terminal planar guanidinium groups, which share an N-C-N unit. Each cation in (I) builds 14 N-H.O hydrogen bonds and is separated from adjacent cations by seven nitrate anions. The AG self-condensation reaction in the presence of copper(II) chloride and chloride anions led to the formation of the organic-inorganic hybrid 1,2-bis(diaminomethylidene)hydrazine-1,2-diium tetrachloridocuprate(II), (C2H10N6)[CuCl4], (II). Its asymmetric unit is composed of half a diprotonated 1,2-bis(diaminomethylidene)hydrazine-1,2-diium dication and half a tetrachloridocuprate(II) dianion, with the CuII atom situated on a twofold rotation axis. The planar guanidinium fragments in (II) have their planes twisted by approximately 77.64'(5)° with respect to each other. The tetrahedral [CuCl4]2- anion is severely distorted and its pronounced 'planarity' must originate from its involvement in multiple N-H.Cl hydrogen bonds. It was reported that [CuCl4]2- anions, with a trans-Cl-Cu-Cl angle (Θ) of 140°, are yellow-green at room temperature, with the colour shifting to a deeper green as Θ increases and toward orange as Θ decreases. Brown salt (II), with a Θ value of 142.059'(8)°, does not fit the trend, which emphasizes the need to take other structural factors into consideration. In the crystal of salt (II), layers of cations and anions alternate along the b axis, with the minimum Cu.Cu distance being 7.5408'(3)'Å inside a layer. The structures of salts (I) and (II) were substantiated via spectroscopic data. The endothermic reaction involved in the thermal decomposition of (I) requires additional oxygen. The title salts may be useful for the screening of new substances with biological activity.The ionic salts of diprotonated cations of 2,2′-methylenedihydrazinecarboximidamide and bisguanidine have been prepared for the first time and characterized by X-ray diffraction and spectroscopic methods. The endothermic reaction involved in the thermal decomposition of the high-nitrogen-content (49%) oxygen-containing former material requires additional oxygen.

AB - Guanidine is the functional group on the side chain of arginine, one of the fundamental building blocks of life. In recent years, a number of compounds based on the aminoguanidine (AG) moiety have been described as presenting high anticancer activities. The product of condensation between two molecules of AG and one molecule of formaldehyde was isolated in the protonated form as the dinitrate salt (systematic name: 2,8-diamino-1,3,4,6,7,9-hexaazanona-1,8-diene-1,9-diium dinitrate), C3H14N8 2+·2NO3 -, (I). The cation lacks crystallographically imposed symmetry and comprises two terminal planar guanidinium groups, which share an N-C-N unit. Each cation in (I) builds 14 N-H.O hydrogen bonds and is separated from adjacent cations by seven nitrate anions. The AG self-condensation reaction in the presence of copper(II) chloride and chloride anions led to the formation of the organic-inorganic hybrid 1,2-bis(diaminomethylidene)hydrazine-1,2-diium tetrachloridocuprate(II), (C2H10N6)[CuCl4], (II). Its asymmetric unit is composed of half a diprotonated 1,2-bis(diaminomethylidene)hydrazine-1,2-diium dication and half a tetrachloridocuprate(II) dianion, with the CuII atom situated on a twofold rotation axis. The planar guanidinium fragments in (II) have their planes twisted by approximately 77.64'(5)° with respect to each other. The tetrahedral [CuCl4]2- anion is severely distorted and its pronounced 'planarity' must originate from its involvement in multiple N-H.Cl hydrogen bonds. It was reported that [CuCl4]2- anions, with a trans-Cl-Cu-Cl angle (Θ) of 140°, are yellow-green at room temperature, with the colour shifting to a deeper green as Θ increases and toward orange as Θ decreases. Brown salt (II), with a Θ value of 142.059'(8)°, does not fit the trend, which emphasizes the need to take other structural factors into consideration. In the crystal of salt (II), layers of cations and anions alternate along the b axis, with the minimum Cu.Cu distance being 7.5408'(3)'Å inside a layer. The structures of salts (I) and (II) were substantiated via spectroscopic data. The endothermic reaction involved in the thermal decomposition of (I) requires additional oxygen. The title salts may be useful for the screening of new substances with biological activity.The ionic salts of diprotonated cations of 2,2′-methylenedihydrazinecarboximidamide and bisguanidine have been prepared for the first time and characterized by X-ray diffraction and spectroscopic methods. The endothermic reaction involved in the thermal decomposition of the high-nitrogen-content (49%) oxygen-containing former material requires additional oxygen.

KW - Aminoguanidine

KW - carboximidamide

KW - condensation reaction

KW - crystal structure

KW - hydrogen bonding

KW - tetrachloridocuprate(II)

KW - thermogravimetric analysis

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U2 - 10.1107/S2053229617018514

DO - 10.1107/S2053229617018514

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SP - 152

EP - 158

JO - Acta Crystallographica Section C: Structural Chemistry

JF - Acta Crystallographica Section C: Structural Chemistry

SN - 1600-5759

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