Quantum-chemical simulations of charge-transfer complexes of 2,4,7-trinitro-9
H
-fluoren-9-one with eight donor molecules differing in size and structure of the π-aromatic system have been performed ...in the scope of the density functional theory approximation, and data on the structure and properties of the complexes have been obtained. The electronic and energy characteristics of the acceptor, donors and the complexes, the average interplanar distances, and the values of charge transfer in the complexes have been obtained, and regularities in the change of these quantities have been elucidated. The crystal and molecular structure of the 1 : 1 complex of 2,4,7-trinitro-9
H
-fluoren-9-one with anthracene (C
13
H
5
N
3
O
7
·C
14
H
10
) have been determined by means of X-ray diffraction analysis.
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•Krieselite was synthesized at 600 °C and 100 MPa by hydrothermal method.•Single crystal structure was refined by XRD.•The assignment of Ag bands in non-polarized Raman spectra was ...carried out.•Lattice dynamic calculations agree with experimental Raman data.•Krieselite Raman spectra are obtained as function of pressure up to 30 GPa.
Spontaneous crystals of krieselite (Ge analogue of topaz) with the chemical formula Al2(Ge0.75Si0.25)O4(F1.63OH0.37) were synthesized using a thermo-gradient hydrothermal method at a temperature of 600/650 °C and pressure of 100 MPa. The unit cell parameters are: a = 8.9732(8) Å, b = 8.4823(7) Å, c = 4.7379(5) Å, V = 360.62(6) Å3, space group Pnma. The F-/OH– content of the samples was refined by FTIR spectroscopy method. Raman spectroscopy showed the main differences between the spectra of krieselite and topaz at the ambient conditions. The assignment of observed and calculated Ag bands (cm−1) for non-polarized Raman spectra was carried out. Using in situ Raman spectroscopy at high pressures, the dependence of the shift in the position of the main bands of the krieselite Raman spectrum on the pressure was established, and the corresponding paths of pressure induced distortion of crystal structure was assumed. According to the data of Raman spectroscopy, it was revealed that krieselite does not undergo the phase transitions up to 30 GPa. The probable way of crystal structure distortion within the space group Pnma was proposed based on simulation of high-pressure Raman spectra.
Single crystals of two new inclusion compounds based on porous europium(III)
trans
-thienothiophenedicarboxylate are obtained by norbornadiene or
trans
-cinnamyl alcohol substitution for ...N,N-dimethylformamide (DMF). Their structures and compositions are determined by the single crystal X-ray diffraction analysis. The structure of Eu
2
(DMF)
4
(ttdc)
3
·3.3nbd ·1.2H
2
O (H
2
ttdc -
trans
-thienothiophenedicarboxylic acid; nbd - norbornadiene) contains directly localized nbd guest molecules. The π–π stacking interactions are found between the double bonds of norbornadiene and the heterocyclic core of the bridging ligand. The Eu
2
(H
2
O)
2
(cinol)
2
(ttdc)
3
·cinol compound contains both coordinated and guest molecules of cinnamyl alcohol (cinol). The strongest guest - host contacts without significant stacking interactions appear to be hydrogen bonds between coordinated water molecules and alcohol OH groups.
A three-dimensional coordination polymer was synthesized by the reaction of zinc(
ii
) nitrate with 4,7-(4-carboxyphenyl)-2,1,3-benzoxadiazole and di(imidazol-1-yl)methane. The crystal structure of ...the new compound was determined by single-crystal X-ray diffraction. In the structure of the metal-organic framework, the trinuclear secondary building units are connected to each other to form a uninodal eight-connected net with the symbol {3
3
.4
18
.5
5
.6
2
}. This topology has not been previously found in coordination polymers. The framework contains channels with dimensions of 7×8 Å
2
. The solvent-accessible volume is 24%. The compound exhibits emission with a maximum at 524 nm upon excitation at 395 nm. The photoluminescence quantum yield is 19%.
The multicomponent condensation of cyclopentylidene- or cyclohexylidenemalononitrile, cyanoacetic acid amides or thioamides, and alkylating agents affords 4-spirocyclopentane- and ...4-spirocyclohexanenicotinic acid nitriles and amides. The structures of several reaction products were determined by X-ray diffraction.
Six new metal-organic frameworks based on magnesium(II) ions of various dimensionality were synthesized: chain-like Mg(Hazdc)2(nmp)2 (
1
, H
2
azdc is 4,4′-azobenzenedicarboxylic acid, nmp is
N
...-methylpyrrolidone), layered Mg(H2btc)(nmp)2 (
2
, H
4
btc is 1,2,4,5-benzene-tetracarboxylic acid), Mg3(sdc)3(def)4 •3DEF (
3
, H2sdc is 4,4’-stilbenedicarboxylic acid, def or DEF is
N
,
N
-diethylformamide), Mg3(azdc)3(dma)4 • 3DMA (
4
, dma or DMA is
N,N-di-
methylacetamide), Mg3(azdc)3(dmf)4 (
5
, dmf is
N
,
N
-dimethylformamide), and doubly-interpenetrated three-dimensional Mg3(azdc)3(nmp)4 •NMP (
6
, NMP is
N
-methylpyrrolidone). According to the single-crystal X-ray dif raction data, compounds
1
and
2
are built from mononuclear carboxylate units {Mg(RCOOH)2(RCOO)2(nmp)2}. Compounds
3
-
6
are composed on trinuclear carboxylate units {Mg
3
(RCOO)6}. In isostructural compounds
3
-
5
, these units are linked to each other through carboxylate bridges to form polymer layers; in compound
6
, these units are linked together to form a doubly-interpenetrated three-dimensional metal-organic framework.
Single-crystal XRD structure of binuclear tetranitrosyliron complex Fe
2
(SR)
2
(NO)
4
(1), R = 4-aminothiophenyl, has been described. The properties of 1 were studied by IR, Mössbauer, mass ...spectroscopy, and amperometry. Complex 1 was shown to form long-living nitrosyl intermediates in solution, which underlies its prolonged NO donor activity. In HeLa cells, 1 caused accumulation of NF-κB p50 but decreased the levels of NF-κB p65 in the nucleus, which led to inhibition of NF-κB dependent genes. The complex also induced increase of p53 protein levels and p21 gene activity, which led to the apoptotic cell death after G2/M cell cycle phase.
The coordination properties of 3,4-bis(diphenylphosphinyl)-2,5-dimethylhexa-2,4-diene (L
2
) were studied in relation to manganese(II) chloride and perchlorate complexes. Manganese(II) chloride forms ...1 : 1 complex with bis-phosphine oxide L
2
, while the composition of the manganese(II) perchlorate complex is 2 : 1. The crystal structures of bis-phosphine oxide L
2
complexes with manganese dichloride (CCDC no. 2165179) and manganese perchlorate (CCDC no. 2165180) were determined by X-ray diffraction.
New Synthesis of Tetrahydroisoquinolines Dyachenko, I. V.; Dyachenko, V. D.; Dorovatovskii, P. V. ...
Russian journal of organic chemistry,
05/2022, Volume:
58, Issue:
5
Journal Article
Peer reviewed
The reaction of cyclohexylidenecyanothioacetamide with
N
,
N
-dimethylformamide dimethyl acetal was studied. This transformation, depending on the reaction conditions, leads to different results: ...when the starting reagents are refluxed without a solvent, 3-(methylsulfanyl)-5,6,7,8-tetrahydroisoquinoline-4-carbonitrile is formed, and refluxing in benzene leads to 2-cyano-3-(dimethylamino)prop-2-enethioamide. The structure of these products was studied by XRD analysts.
The reaction of cobalt(ɪɪ) chloride with
p
-Br-benzoyl-β-(piperidin-1-yl)propioamid-oxime (L
init
) in methanol leads to the hydrolysis of the ligand at the -OCO- ester bond and the formation of the ...mixed-valence hexanuclear ionic complex Co
II
2
Co
III
4
(HL)
4
(L)
2
(O)-(Cl)
4
Cl
2
•4CH
3
OH (
1
) (L is β-(piperidin-l-yl)propioamidoxime). According to the X-ray diffraction data, the ligand (L) in
1
is coordinated to the complexing agent in different modes: the μ
3
-bridging-chelating mode (involving deprotonated amino groups) and the μ
2
- and μ
3
-bridging-chelating modes in the case of a coordinated amino group. Two cobalt atoms of the hexanuclear metal core have a tetrahedral coordination geometry (Co
II
N
2
Cl
2
; CN
Co
II
= 4), whereas the other four cobalt atoms are in an octahedral coordination environment of nitrogen and oxygen atoms forming the polyhedra of composition Co
III
O
3
N
3
and Co
III
O
4
N
2
(CN
Co
III
= 6). The evaluation of the
in vitro
biological activity of
1
against the non-pathogenic (virulent H37Rv model) mycobacterial strain of
Mycolicibacterium smegmatis
showed an increase in the efficiency of complex
1
by more than 4–12 times compared to the previously studied Co
II,III
complexes.
