Journal of Structural Chemistry

Parimala devi, D.; Praveena, G.; Jeba Beula, R.; Abiram, A.

doi: 10.1134/s0022476622040011pmid: N/A

In this work, intermolecular dihydrogen bonded interactions between cycloalkenes (cyclobutene (C4H6), cyclopentene (C5H8), cyclohexene (C6H10)) and alkali metal hydrides H–M (M = Li, Na and K) complexes have been studied using B3LYP/6-311++G** method. The calculated structural parameters correlate well with the interaction energies and smallest dihydrogen bonded distance is observed for C4H6⋯HK complexes. Infrared vibrational frequency analysis indicates that significant red and blue shifts are occurring in the C–H and H–M bonds of all the complexes. The analyses of natural bond orbital, topological parameters based on the quantum theory of atoms in molecule and molecular electrostatic potential aids to know the nature of dihydrogen bonded interaction. The result shows that H⋯H interaction is strengthened in the C4H6⋯HK than the other complexes and henceforth H–K interacting complexes have better dihydrogen bonded interaction.[graphic not available: see fulltext]

Alekseev, N. V.

doi: 10.1134/s0022476622040023pmid: N/A

A quantum chemical study of tin–substituent bonds in tricoordinated tin compounds is conducted using the PC GAMESS-Firefly package. The structures of the studied molecules are optimized by the DFT method (B3PW91 functional; aug-cc-pVTZ-pp effective core potential basis set for tin; 6-311++(2d,p) basis set for other atoms). The wave functions and the NBOs of tin–substituent bonds are calculated with HF method using the x2c-TZVPall all-electron relativistic basis set for tin and the 6-311G(2d,2p) basis set for other atoms. Topological characteristics of tin–substituent bonds are calculated with the AIM method. It is shown that these bonds can be referred to as “intermediate type” bonds characterized by small contributions of Sn AOs to the bond MOs, large difference between the charges of tin atoms and the substituent, and low populations of bond MOs. The energies of Sn–R bonds are estimated.[graphic not available: see fulltext]

Urkasym kyzy, S.; Rybalova, T. V.; Komarov, V. Yu.; Korolkov, I. V.; Krisyuk, V. V.

doi: 10.1134/s0022476622040035pmid: N/A

New iron(III) complexes with a fluorinated methoxy-substituted β-diketonate L = 1,1,1-trifluoro-5-methoxy-5-methylhexane-2,4-dionate are prepared. Heteroligand complexes with the composition [Fe(OR)L2]2 (R = Et or i-Pr) and the homoligand complex FeL3 are isolated. The crystal structure of these complexes is molecular and is built of binuclear and mononuclear molecules, respectively. Methoxy groups of ligand L are not involved in the coordination. The crystallographic data for fac-FeL3: C24H30F9O9Fe, P21, a = 10.462(2) Å, b = 14.826(3) Å, c = 10.7097(18) Å, β = 114.752(5)°, V = 1508.56 Å3, Z = 2, d = 1.518 g/cm3; for [Fe(OEt)L2]2: C36H50F12O14Fe2, \documentclass[12pt]{minimal}\usepackage{amsmath}\usepackage{wasysym}\usepackage{amsfonts}\usepackage{amssymb}\usepackage{amsbsy}\usepackage{mathrsfs}\usepackage{upgreek}\setlength{\oddsidemargin}{-69pt}\begin{document}$$P\bar{1}$$\end{document}, a = 8.6968(15) Å, b = 10.9946(17) Å, c = 14.019(2) Å, α = 67.435(5)°, β = 82.812(6)°, γ = 80.323(6)°, V = 1217.5(3) Å3, Z = 1, d = 1.427 g/cm3; for [Fe(Oi-Pr)L2]: C38H54F12O14Fe2, Pbca, a = 17.734(1) Å, b = 15.6851(10) Å, c = 17.9767(12) Å, V = 5000.4(5) Å3, Z = 4, d = 1.427 g/cm3. The complexes can be re-sublimated without being decomposed upon heating in a vacuum (~10–2 Torr).[graphic not available: see fulltext]

Romanenko, G. V.; Fursova, E. Yu.; Letyagin, G. A.; Tolstikov, S. E.; Ovcharenko, V. I.

doi: 10.1134/s0022476622040047pmid: N/A

The X-ray diffraction analysis of products of the interaction between hexanuclear manganese pivalate [Mn6O2Piv10(THF)4] and 1,3-di(4′-pyridyl)triazene (LH) shows the possibility of forming 3D metal organic frameworks (MOFs), in which LH acts as di- and tritopic linkers. It is found that ROH (R = Me, Et, i-Pr, n-Bu) alcohols used as a solvent and the reaction temperature have a significant effect on the compositions and structures of the products formed.[graphic not available: see fulltext]

Patra, G. K.

doi: 10.1134/s0022476622040059pmid: N/A

Single pot synthesis of a new mixed-ligand iodide bridged dimeric Cu(I) complex, [L2CuI2(μ-I)2(PPh3)2](1) has been carried out by combining copper(I) iodide, an asymmetric Schiff base ligand 2-((pyridin-4-yl)methelenamino)-3-aminomaleonitrile (L) and a co-ligand triphenylphosphine (PPh3). L and 1 have been characterized by 1H NMR, IR and EIMS spectrometry, elemental analysis and DFT studies. The crystal structure of 1 has been determined by single-crystal X-ray analysis and it has been found that it is a dimer with –{CuI–(μ-I2)–CuI}– rhomboid core with the bridged iodide ion. 1 crystallized as 1·CH2Cl2. At room temperature in dichloromethane the ligand L is non-emissive whereas the complex 1 is photoluminescent. The E1/2 value of the CuI–CuII couple of 1 in dichloromethane is 0.46 V (vs. Ag/AgCl in 1 M KCl, scan rate 100 mV/s). The Hirshfeld surface analysis of the complex 1·CH2Cl2 showed H⋯H, N⋯H and I⋯H interactions of 52.3%, 13.1% and 7.4%, respectively, which revealed that the main intermolecular interactions were H⋯H intermolecular interactions.[graphic not available: see fulltext]

Gladysheva, M. V.; Plyusnin, P. E.; Komarov, V. Yu.; Tsygankova, A. R.; Gerasimov, E. Yu.; Shubin, Yu. V.; Korenev, S. V.

doi: 10.1134/s0022476622040060pmid: N/A

New complex salts [Pd(NH3)4][Pd(NH3)3NO2][CrOx3]·H2O I, [Pd(NH3)4][Pd(NH3)3NO2][CoOx3]·H2O II, and a series of solid solutions [Pd(NH3)4][Pd(NH3)3NO2][CoOx3]x[RhOx3]1–x·H2O III–V\documentclass[12pt]{minimal}\usepackage{amsmath}\usepackage{wasysym}\usepackage{amsfonts}\usepackage{amssymb}\usepackage{amsbsy}\usepackage{mathrsfs}\usepackage{upgreek}\setlength{\oddsidemargin}{-69pt}\begin{document}$$(\text{Ox}~=~{{\text{C}}_{\text{2}}}\text{O}_{4}^{2-})$$\end{document} are obtained and characterized. The compounds are studied by powder X-ray diffraction (XRD), elemental analysis, and IR spectroscopy. Crystal structures of complex salts I, II and K5[Pd(NH3)4][CrOx3]2NO3·6H2O VI are determined by single crystal XRD. Complex salts I and II crystallize in the monoclinic crystal system (space group of I and II is P21/n); complex salt VI crystallizes in the triclinic crystal system (space group of VI is \documentclass[12pt]{minimal}\usepackage{amsmath}\usepackage{wasysym}\usepackage{amsfonts}\usepackage{amssymb}\usepackage{amsbsy}\usepackage{mathrsfs}\usepackage{upgreek}\setlength{\oddsidemargin}{-69pt}\begin{document}$$P\bar{1}$$\end{document}). The thermal behavior of compounds I–V is investigated in different gas atmospheres. Final products of the thermolysis of [Pd(NH3)4][Pd(NH3)3NO2][CoOx3]·H2O and [Pd(NH3)4][Pd(NH3)3NO2][CoOx3]x[RhOx3]1–x·H2O solid solutions in the reducing atmosphere are Pd0.7Co0.3, Pd0.7CoxRh0.3–x. The thermolysis of [Pd(NH3)4][Pd(NH3)3NO2][CrOx3]·H2O complex salt under the same conditions results in the formation of a two-phase mixture Pd1–yCry + Сr2O3 where y < 0.1. In the oxidizing atmosphere, the final products are mixtures of oxide phases of initial metals.[graphic not available: see fulltext]

Vorobyeva, S. N.; Baidina, I. A.; Sukhikh, T. S.; Korolkov, I. V.; Belyaev, A. V.

doi: 10.1134/s0022476622040072pmid: N/A

Rhodium nitromonoethylenediamine complexes with compositions K[Rh(en)(NO2)4] (I), (Me4N)[Rh(en)(NO2)4]·2H2O (II), [Rh(en)(H2O)(NO2)3]·H2O (III), [Rh(en)(H2O)(NO2)3]·0.5H2O (IV), [Rh(H2O)5NO2](NO3)2 (V), K2[Rh(en)(NO2)4]NO2 (VI) are prepared and structurally characterized. Unusual lability of rhodium(III) nitroethylenediamine complexes is established upon recrystallization from hot water.[graphic not available: see fulltext]

Grigorieva, V. D.; Rakhmanova, M. I.; Kasimkin, P. V.; Shlegel, V. N.

doi: 10.1134/s0022476622040084pmid: N/A

Alkaline tungstate crystals are promising scintillation materials for rare events search, especially for WIMP investigations. Na2W2O7 single crystals doped with 1.0 mol.% chromium and cerium ions are grown from melt by low-thermal-gradient Czochralski technique (LTG Cz) developed at Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciece (Novosibirsk, Russia) for obtaining large oxide scintillating crystals of high optical quality. Obtained doped Na2W2O7 single crystals 25 mm in length and 30 mm in diameter. The photoluminescence excitation and emission spectra, as well as the decay curves in the temperature range of 77-300 K are measured and colorimetric parameters are estimated. Comparative studies of the photoluminescence properties of Na2W2O7 crystals undoped and doped with Ce3+ and Cr3+ ions in the temperature range of 77-300 K are is carried out. It is shown that while the introduction of cerium and chromium ions in the Na2W2O7 crystal lattice does not significantly a effect the colorimetric parameters and optical properties, it does not increase mechanical hardness of the crystals and decreases the tendency to cracking along cleavage planes. The emission color chromaticity coordinates, сorrelated color temperature and color purity for Na2W2O7:Ce and Na2W2O7:Cr crystals are calculated. The photoluminescence lifetimes are calculated and a strong temperature dependence of the lifetimes in the range 77-300 K is shown.[graphic not available: see fulltext]

Basalaev, Yu. M.; Basalaeva, O. G.; Prosvirkina, E. V.

doi: 10.1134/s0022476622040096pmid: N/A

The electronic structure of BePb–V2 crystals (V = N, P, As, Sb) with chalcopyrite structure is studied. The energy band structure and valence electron deformation density maps are calculated within the generalized gradient approximation (GGA). All the crystals are shown to be direct band gap semiconductors with band gaps Eg < 2 eV and negative crystal-field splitting values (eV): 1.98, –0.23 (BePbN2); 1.53, –0.31 (BePbP2); 1.29, –0.31 (BePbAs2); 0.73, –0.14 (BePbSb2).[graphic not available: see fulltext]

Goncharenko, V. E.; Gudovannyy, A. O.; Lunev, A. M.; Belousov, Yu. A.; Lyssenko, K. A.

doi: 10.1134/s0022476622040102pmid: N/A

The oxidation reaction of 3,3′,5,5′-tetramethyl-1H,1′H-4,4′-bipyrazole in the HNO3–Fe3+ system unexpectedly resulted in the formation of 1Н-pyrazole-3,4,5-tricarboxylic acid (H3PTCA) isolated as the acid sodium salt Na(H2O)2H2PTCA. The compound has a polymeric structure stabilized by rare seven-membered Н-bonded rings.[graphic not available: see fulltext]