Crystalline and molecular structure of 2,4-diamino-6-dinitromethyl-1,3,5-triazine potassium salt

An X-ray diffraction study of 2,4-diamino-6-dinitromethyl-1,3,5-triazine potassium salt is reported. Crystals are monoclinic: a = 7.697(2) Å, b = 11.147(2) Å, c = 12.612(4) Å, β = 117.95(2)°, V = 955.9(4) ų, space group P2₁/c; Z = 4, ρ_calc = 1.885 g/cm³. The compound crystallizes as a crystalline hydrate with one molecule of water. Anion consists of two planar fragments: dinitromethyl and diamino-1,3,5-triazine, the geometrical parameters of which were analyzed. The coordination of potassium cations and multiple hydrogen bonds leading to the formation of a complex three-dimensional skeleton has been detected.     

Poly[2,4-bis(chloroamino)-6-vinyl-1,3,5-triazine] as a recyclable oxidizing agent of alcohols

A polymer containing dichlorotriazine moiety was prepared readily by the reaction of poly(2,4-diamino-6-vinyl-1,3,5-triazine) with tert-butyl hypochlorite. This polymer oxidizes various primary and secondary alcohols to the corresponding carbonyl compounds under mild conditions, while the reaction of the monomeric analogue N,N′-dichloroacetoguanamine with alcohols does not proceed. The polymer reagent can be handled easily and recycled for further use.     

Herbizide,VI [1] kernfluorierte 2,4-dianilino-6-(dihexylamino)-1,3,5-triazine

The nucleophilic substitution of the chlorine atoms in 2,4-dichloro- 6-(dihexylamino)-1,3,5-triazine by aniline leads to 2,4-dianilino-6-(dihexylamino)- 1,3,5-triazine and by fluorinated amines to (dihexylamino)- 1,3,5-triazines bearing groupings as follows: (2-fluoroanilino)-, (3-fluoroanilino)-, (4-fluoroanilino)-, (2,4-difluoroanilino)-, (2,5-difluoroanilino)-, and (2,6-difluoroanilino)-. The new compounds are characterized by IR, ¹-NMR, and mass spectroscopy. 2,4-Bis-(2,4-difluoroanilino)- 6-(dihexylamino)-1,3,5-triazine in particular shows herbicidal and anti- diabetic activity.     

Crystal and molecular structure of 7-phenyl-1,2,4-triazolo[1,5-a]-1,3,5-triazine

The crystal and molecular structure of 7-phenyl-1,2,4-triazolo[1,5-a]-1,3,5-triazine were determined. It was shown that the amine nitrogen atom (N¹) of the triazole ring acts as a nucleophilic center in the cyclization of N-(1,2,4-triazol-5-yl)amidines with electrophilic reagents.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1386–1389, June, 1992.     

Synthesis and crystal structure of yttrium(III) and lanthanide(III) complexes with a new terpyridine-like ligand 2,4-bis(3,5-dimethylpyrazol-1-yl)- 6-diethylamino-1,3,5-triazine

A new planar aromatic tridentate terpyridine-like ligand, 2,4-bis(3,5-dimethylpyrazol-1-yl)-6-diethylamino-1,3,5-triazine (L), has been synthesized and the structures of its complexes [YL(NO₃)₃] (1) and [LnL(NO₃)₃(H₂O)]L [Ln?=?La (2), Ce (3), Pr (4), Nd (5), Eu (6)] have been determined by X-ray crystal structural analysis. The structures of the five lanthanoid complexes are isomorphous and isostructural but different from the crystal structure of the yttrium complex [YL(NO₃)₃]. The latter shows a nine-coordinate metal center whereas the crystal structure of the lanthanoid complexes [LnL(NO₃)₃(H₂O)]L show a 10-coordinate metal center. The?π–π?stacking and hydrogen bonding between the coordinated and uncoordinated L molecules sensitized the Ln luminescence. The thermal behavior of the ligand and its complexes is discussed.     

Crystal structure of the high-pressure phase of hexahydro-1,3,5-trinitro-1,3,5-triazine (gamma-RDX)

The crystal structure of the high-pressure phase of hexahydro-1,3,5-trinitro-1,3,5-triazine (gamma-RDX), which is stable above 4 GPa at room temperature, was investigated by using infrared spectroscopy and powder X-ray diffraction measurements followed by Rietveld refinements using a diamond anvil cell (DAC). Although gamma and alpha phases were found to belong to the same space group Pbca, they exhibited a different crystal packing. The molecular structure of the gamma phase exhibited the same conformation as that of the alpha phase; however, the torsion angles of N-NO2 changed marginally.     

Crystal structure and theoretical investigation of the configurations of 1,3-dichloro-1,3-diazetidine-2,4-dione and 1,3-bis(trimethylsilyl)-1,3-diazetidine-2,4-dione

Crystal structures of 1,3-dichloro-1,3-diazetidine-2,4-dione ( 1 ) and the hitherto unknown compound 1,3-bis(trimethylsilyl)-1,3-diazetidine-2,4-dione ( 2 ) have been determined by X--ray crystallography: 1 : (CINCO)₂, M_r = 154.94, T = 295 K, orthorhombic, Pbca, a = 7.699(1), b = 6.706(1), c = 10.598(2) Å, V = 547.2(2) ų, Z = 4, d_x = 1.881 g/cm³, μ = 10.9 cm⁻¹, R = 3.14%, R_w = 2.82% (660 observations, 38 parameters). 2 : [(CH₃)₃SiNCO]₂, M_r = 230.41, T = 100 K, monoclinic, I2/a, a = 20.257(2), b = 6.416(1), c = 21.260(3) Å, β = 101.29(1)°, V = 2709.7(6) ų, Z = 8, d_x = 1.130 g/cm³, μ = 2.4 cm⁻¹, R = 4.86%, R_w = 4.39% (2375 observations, 151 parameters). In both compounds, the symmetry of the (XNCO)₂ framework (X = Cl, Si) was determined to be nearly C_2h with trans configuration of the exocyclic X atoms. Extreme values were observed for the angles between the ring plane and the exocyclic N–X bonds: 32.5(1)° in 1 and 2.5(2)° and 0.8(2)° in 2 , respectively. Quantum chemical procedures at various levels of theory (ab initio SCF and semi-empirical PM3) applied to 1 revealed the possible appearance of two isomers, a lower energy trans form and a higher energy cis form (approx. 2.4 kcal/mol above trans) differing mainly in the spatial arrangement of the chlorine atoms. The calculations excluded a planar heavy-atom configuration by missing a local energy minimum.     

Crystal and molecular structure of 4,6-bis(nitroimino)-1,3,5-triazinan-2-one: theoretical and X-ray studies

This paper provides an overview of recent progress on structural data on the title compound. Theoretical work based on quantum mechanical calculations was performed to gain some understanding on the heterocyclic tautomerism potentially exhibited by the compound. The computational studies encompassed a wide range of tautomers/conformers, allowing the determination of the most probable molecular structure. In the gas phase, the nitroimine tautomers are computed to be substantially more stable than the nitramine tautomers. Among three plausible nitroimine forms, special attention was given to 4,6-bis(nitroimino)-1,3,5-triazinan-2-one, whose crystal structure was unequivocally solved by X-ray diffraction. The crystals are orthorhombic, space group Pnma with a = 6.187(2)A, b = 13.252(5)A, c = 8.802(4)A, and Z = 4. The structure was solved by direct methods and refined to a final R = 0.0326. The molecule has an approximate mirror plane relating the two symmetry related halves. The nitroimine groups are positioned in a syn-syn conformation. The least-squares (LS) plane of the heterocyclic ring and the nitroimine ([double bond]N-NO2) substituent LS plane make an angle of 10.05(11) degrees. The crystal structure is held together via hydrogen bonds that assemble the molecules in chains running along the b-axis. Every H-atom is involved in bifurcated hydrogen bonds.     

2,4-diamino-6-(acetohydrazidomethylsulfinylmethyl)-1,3,5-triazine. State in solution, acid-base and complexing properties

Solutions of a new drug, 2,4-diamino-6-(acetylhydrazidomethylsulfonylmethyl)-1,3,5-triazine, exhibiting tuberculocidal activity were studied using the methods of pH-metry, spectrophotometry, mathematical simulation of equilibria (CPESSP software), and molecular mechanics. Protolytic properties of the compound in the medium of aqueous dimethylsulfoxide (40 vol % of DMSO) were characterized. The composition of the copper(II) complex of this compound was determined and its stability constants were calculated. Based on the absorption spectra in the UV and visible regions the complexing ability of 2,4-diamino-6-(acetylhydrazidomethylsulfonylmethyl)-1,3,5-triazine toward nickel(II) and cobalt(II) were characterized in comparison with copper(II) under the same conditions.     

Crystal and molecular structure of 1,1-bis(hydroxyphenyl)-3-ketoisoindoline

The structure of the condensation product of phthalonitrile and phenol is found by x-ray structure analysis. The structure of a new class of polyheteroarylenes, polhydroxyphenylisoindazenes, is defined using the data obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2792–2796, December, 1991.     

Crystal and molecular structure of 2,5-bis(fluorodinitromethyl)-1,3,4-oxadiazole

An X-ray structural study of 2,5-bis(fluorodinitromethyl)-1,3,4-oxadiazole (1), one of the representatives of azoles with strong electron-withdrawing substituents, has been carried out. It has been found that in the orthorhombic modification of1 the conformations of the fluorodinitromethyl groups are different. Intermolecular contacts in the crystal are realized through the heterocycles arranged at large angles to each other. The presence of strong electron-withdrawing substituents results in shortening of the C-O bonds and in a certain increase in the OCN angle in the 1,3,4-oxadiazole ring.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 639–641, April, 1994.     

Trisubstituted 1,3,5-triazines. 4. Synthesis of 2-nitroamino-4,6-bis(trinitromethyl)-1,3,5-triazine

The nitration, at the amino group, of 2-amino-4,6-bis(trinitromethyl)-1,3,5-triazine and its derivatives has been studied.For Communication 3, see [1].n. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Institute of Chemical Physics in Chernoglovka, Chernoglovka, Moscow Oblast, 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 79–81, January, 1999.     

Tautomerism of bis(2,4-benzyloxy)-6-(5H)-one-1,3,5-triazine: A combined crystallographic and quantum-chemical investigation

In order to study the keto and enol forms of cyanuric acid derivatives in the solid state, we have synthesized bis(2,4-benzyloxy)-6-(5H)-one-1,3,5-triazine, 1. Computational investigations indicate that keto form is more stable than enol form in both gas phase and solution phase by 9.69–11.18 kcal mol⁻¹ IR and crystallographic analysis shows that 1 exists in keto form in the solid state also. To obtain the enol form in the solid state, we adopted co-crystallization with an organic base. The crystal structures of both keto/amine and the enol/imine forms (in a co-crystal) are reported. IICT Communication No. 2505/CMM-0022.     

Synthesis and structure of 6-azido-2,4-bis(2,2,2-trinitroethylamino)-1,3,5-triazine and its <Emphasis Type="Italic">N</Emphasis>-nitro derivatives

Methods were developed for the synthesis of 6-azido-2,4-bis(2,2,2-trinitroethylamino)- 1,3,5-triazine and its N-nitro derivatives (6-azido-2,4-bis(2,2,2-trinitroethyl)nitramino-1,3,5-triazine and 6-azido-2-(2,2,2-trinitroethylamino)-4-(2,2,2-trinitroethyl)nitramino-1,3,5-triazine) containing combinations of azido, trinitroethyl, and nitramine groups. These compounds are of interest as components of energetic composites. The molecular and crystal structures of 6-azido-2,4-bis(2,2,2-trinitroethylamino)-1,3,5-triazine and 6-azido-2,4-bis(2,2,2-trinitroethyl) nitramino-1,3,5-triazine were studied by X-ray diffraction and NMR spectroscopy.     

Synthesis and Crystal Structure Analysis of 2-Amino-4,6-bis（diphenoxyl phosphoramide）-1,3,5-triazine

A disubstituted triazine compound, namely, 2-amino-4,6-bis(diphenoxyl phosphorramide)-1,3,5-triazine, which is an inherent flame retardant monomer, was synthesized specifically, and its structure was characterized by using NMR spectrum and X-ray single-crystal diffraction. Unit cell parameters: space group P21/c, Z=4, a=8.7494(15), b=27.518(5), c=12.511(2),β=109.323(16) , Z=4, V=2842.7(9)β3 , Dc=1.380 g/cm3 , F(000)=1224 and Mr=590.46. All the atoms are in the general positions.