Journal of Structural Chemistry最新文献

{"title":"Synthesis, Structure, and Optical Properties of a Dinuclear Zn(II) Complex Based on a C2-Symmetric Diimine Containing Fragments of Nopinane-Annelated 4,5-Diazafluorene","authors":"Y. A. Bryleva,&nbsp;E. S. Vasilyev,&nbsp;L. A. Glinskaya,&nbsp;A. V. Tkachev","doi":"10.1134/S0022476626080044","DOIUrl":"10.1134/S0022476626080044","url":null,"abstract":"<p>A new complex, [Zn₂Cl₄L]·MeCN, is prepared using an optically active ligand L containing two dipinodiazafluorene fragments connected by a =N–Ph–N= diimine linker. In the binuclear complex [Zn₂Cl₄L], ligand L binds two ZnCl₂ units where Zn atoms occur in a distorted tetrahedral N₂Cl₂ environment (<i>seesaw</i> configuration). The geometry, electronic structure, and optical properties of the complex are studied by the density functional theory method. Experimental absorption and diffuse reflectance spectra of [Zn₂Cl₄L]·MeCN reveal electronic transitions in the 230-600 nm range and agree with the results of quantum chemical calculations.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 8","pages":"1694 - 1703"},"PeriodicalIF":1.5,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903424","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Halogen–Halogen Contacts in Bending Crystals: Limitations of QTAIM and NCI in Describing Sliding Energetics","authors":"I. S. Tretyakova,&nbsp;D. A. Rychkov","doi":"10.1134/S0022476626080068","DOIUrl":"10.1134/S0022476626080068","url":null,"abstract":"<p>The plastic bending behavior of isostructural hexachlorobenzene and hexabromobenzene crystals is governed by anisotropic intermolecular interactions, particularly halogen–halogen (Hal⋯Hal) contacts. This study critically evaluates the reliability of Quantum Theory of Atoms in Molecules (QTAIM) and Non-Covalent Interaction index analyses in capturing the energetic landscape of layer sliding along the bending (001) crystallographic plane. Energy profiles are calculated using periodic Density Functional Theory, gas-phase DFT, and the CrystalExplorer cluster-based approach. While all computational methods confirm the presence of a significant energy barrier to sliding, analysis of the interaction energy contributions computed with CrystalExplorer17 reveals that changes in the dispersion component are minimal (&lt;2%), whereas change in the repulsive and electrostatic components dominate the sliding barrier. Notably, QTAIM-derived interaction energies for Hal⋯Hal contacts spuriously indicate that layer displacement is energetically favorable, in direct contradiction to total energy calculations. Furthermore, NCI analysis shows that steric repulsion is systematically underestimated as halogen–halogen distances decrease. These findings demonstrate that, although QTAIM and NCI methods yield valuable local geometric descriptors, they are insufficient and potentially misleading for quantifying the total energy balance underpinning the mechanical response of these halogen-rich plastic crystals.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 8","pages":"1715 - 1729"},"PeriodicalIF":1.5,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural Elucidation and Computational Reactivity Analysis of (E)-2-bromo-4-methyl-6-[(4-bromophenylimino)methyl]phenol: a Combined XRD, Hirshfeld, FMO, MEP, and Docking Study","authors":"O. R. Yılmaz,&nbsp;Ç. A. Kaştaş,&nbsp;T. Bayın,&nbsp;C. Kazak","doi":"10.1134/S0022476626080135","DOIUrl":"10.1134/S0022476626080135","url":null,"abstract":"<p>In this study, the structure of (<i>E</i>)-2-bromo-4-methyl-6-[(4-bromophenylimino)methyl]phenol is investigated using X-ray diffraction (XRD), and its geometrical features are analyzed in detail. The title compound crystallizes in a monoclinic system with the space group <i>P</i>2₁/<i>n</i>. In salicylaldehyde derivatives, the presence of a strong tautomeric N–H⋯O or O–H⋯N hydrogen bond typically facilitates a nearly parallel orientation between the benzene rings. The angle between the normals of the benzene rings is determined to be 2.84°, confirming the near-parallel geometry. Nonlinear optical (NLO) analysis revealed that the structure exhibits well-defined charge separation with a total dipole moment (μ_tot) of 5.54 D. Additionally, graph set analysis and Hirshfeld surface analysis are employed to elucidate the intermolecular and intramolecular interactions to illustrate crystal growth symmetries. Moreover, the investigation of the title molecule′s reactive sites, possible charge mobility, and hardness is carried out using frontier molecular orbital (FMO) and MEP analyses. This investigation is completed with docking analysis of the possible binding features of the molecule specifically against 5U09 receptor.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 8","pages":"1806 - 1822"},"PeriodicalIF":1.5,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Structure, and Thermal Properties of Ag(I) Complexes with 3H,3H-Perfluorooctane-2,4-Dione","authors":"S. E. Varvarinskaya,&nbsp;E. S. Vikulova,&nbsp;T. S. Sukhikh,&nbsp;N. A. Kryuchkova,&nbsp;D. P. Pishchur,&nbsp;I. Yu. Ilyin,&nbsp;N. B. Morozova,&nbsp;A. A. Zheravin","doi":"10.1134/S0022476626080160","DOIUrl":"10.1134/S0022476626080160","url":null,"abstract":"<p>Silver(I) β-diketonates and their mixed-ligand complexes are used to prepare film materials and nanoparticles via solution- and gas-phase methods. To expand the library of precursors, in the present work, the corresponding derivatives with an extended perfluoroalkyl chain in the ligand, namely, Ag(I) complexes with 3<i>H</i>,3<i>H</i>-perfluorooctane-2,4-dione (Hdfod) is synthesized for the first time. Adducts with water/ether and acetonitrile are obtained along with a mixed-ligand complex with 2,2′-bipyridine [Ag(bipy)(dfod)]₂, for which a simplified synthetic procedure is proposed. All compounds are characterized by NMR spectroscopy. The structure and vibrational spectrum of the mixed-ligand complex are investigated using quantum chemical calculations. The single crystal X-ray diffraction analysis shows that in the structure of this binuclear complex, both types of ligands exhibit chelate coordination (d(Ag–O) = 2.38 Å, 2.31 Å; d(Ag–N) = 2.35 Å, 2.37 Å), and dimerization occurs through Ag⋯Ag (2.95 Å) and Ag⋯N (2.93 Å) contacts, similar to hexafluoroacetylacetonate analogue [Ag(bipy)(hfac)]₂. The structure exhibits incommensurate static modulation, manifested as an Ag atom displacement from its average position and elastic breathing of the coordination core. In this process, the conformationally rigid bipy ligand moves as a whole, whereas the β-diketonate moiety undergoes synchronous deformation. The thermal properties of all compounds are studied by TGA, and the mixed-ligand complex is additionally investigated by DSC. The new complexes with L = dfod have lower melting points than their analogues with L = hfac, while the bipy mixed-ligand complex shows enhanced thermal stability.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 8","pages":"1839 - 1852"},"PeriodicalIF":1.5,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermodynamic Stability, Electronic Properties, and Vibrational Spectra of Cr(VI), Mo(VI), and W(VI) Halides and Oxohalides: a Comparative Density Functional Theory Study","authors":"S. G. Gadzhimuradov,&nbsp;E. O. Drozdov,&nbsp;S. I. Suleimanov,&nbsp;U. M. Damyrov,&nbsp;A. S. Datsiev,&nbsp;A. M. Maksumova,&nbsp;M. G. Shtanchaeva,&nbsp;I. M. Abdulagatov,&nbsp;A. I. Abdulagatov","doi":"10.1134/S002247662608010X","DOIUrl":"10.1134/S002247662608010X","url":null,"abstract":"<p>A comparative quantum chemical study of the thermodynamic stability, electronic structure, and vibrational spectra of chromium(VI), molybdenum(VI), and tungsten(VI) halides and oxohalides are presented. The calculations are performed by the density functional theory methods using PBE, B3LYP, and <i>r</i>²SCAN density functionals in combination with def2-SVP, def2-TZVP, and def2-QZVP basis sets. The influence of the functional choice and the basis set size on the accuracy of describing geometric parameters and vibrational frequencies is analyzed against experimental data. The thermodynamic stability of the studied compounds is shown to decrease in the F → Cl → Br → I series, as well as with increasing coordination number of the central metal atom. At the same time, the polarizability and dipole moments of molecules increase, especially for structures with reduced symmetry. Analysis of frontier molecular orbitals (HOMO–LUMO) allows the identification of more reactive compounds that can be possibly used as precursors for atomic layer deposition and for identifying thermally stable products in atomic layer etching processes.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 8","pages":"1758 - 1777"},"PeriodicalIF":1.5,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structures and Vibrational Spectra of Potassium and Ammonium Fluoridozirconates","authors":"E. I. Voit,&nbsp;N. A. Didenko","doi":"10.1134/S0022476626070097","DOIUrl":"10.1134/S0022476626070097","url":null,"abstract":"<p>The effect is considered of the nature of monovalent potassium and ammonium cations on the structure of complex zirconium(IV) fluorides at different F/Zr ratios. It is shown that <span>(text{NH}_{4}^{+})</span> and K⁺ fluoridozirconates with the stoichiometric F/Zr ratio of 7-5 form series of compounds with the same composition: M₃ZrF₇–M₂ZrF₆–MZrF₅·H₂O–MZrF₅ (M–K⁺, <span>(text{NH}_{4}^{+}))</span>. The formula analogues differ in structure from each other. Vibrational (IR, Raman) spectra of potassium and ammonium fluoridozirconates are systematized, analyzed, and compared. The characteristic spectral features describing the structural features of compounds in the mentioned series are discussed and identified. The results of the study can be useful for the synthesis and structure determination of both new fluoridometallates (zirconates, hafnates, terbates, etc.) and composite materials based on them.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 7","pages":"1526 - 1539"},"PeriodicalIF":1.5,"publicationDate":"2026-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148614999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preparation, Crystallographic Characterization, Synthon Investigation and Hirshfeld Surface Analysis of 4-bromobenzamide and its Cocrystals with Phenylacetic Acid and 2,3-Dibromosuccinic Acid","authors":"R. Wu,&nbsp;S. Jin,&nbsp;R. Hong,&nbsp;H. Hong,&nbsp;Y. Ni,&nbsp;Z. Jiao,&nbsp;C. Liang,&nbsp;Z. Li,&nbsp;R. Gao,&nbsp;D. Wang","doi":"10.1134/S0022476626070048","DOIUrl":"10.1134/S0022476626070048","url":null,"abstract":"<p>The crystalline solids 4-bromobenzamide (bbm) and its two new cocrystals with phenylacetic acid and 2,3-dibromosuccinic acid are featured through using the XRD analysis, IR, mp, and elemental analysis. Although the structure of the bbm is reported, we redetermine its crystal structure in order to make some comparison in the geometric parameters between bbm and its cocrystals discussed in the following text. The bbm (<b>1</b>) applies the monoclinic, space group <i>P</i>2(1)/<i>c</i>, with <i>a</i> = 4.9735(4) Å, <i>b</i> = 5.4545(5) Å, <i>c</i> = 28.178(3) Å, β = 93.6180(10)°,<i> V</i> = 762.90(12) Å³, <i>Z</i> = 4. Cocrystal (<b>2</b>) crystallizes into the triclinic, space group <span>(Pbar{1})</span>, with <i>a</i> = 5.6582(4) Å, <i>b</i> = 10.1682(8) Å, <i>c</i> = 12.9486(9) Å, α = 102.781(2)°, β = 94.8340(10)°, γ = 92.3000(10)°, <i>V</i> = 722.61(9) Å³, <i>Z</i> = 2. Cocrystal (<b>3</b>) belongs to the monoclinic, space group <i>P</i>2(1)/<i>c</i>, with <i>a</i> = 8.8220(7) Å, <i>b</i> = 9.2241(8) Å, <i>c </i>= 13.7529(11) Å, β = 92.6640(10)°, <i>V</i> = 1117.93(16) Å³, <i>Z</i> = 4. All of the three compounds <b>1-3</b> set up the multiple N–H⋯O H-bonds together with the other non-covalent linkages. Apart from the conventional H-bonds, the secondary linkages of the CH–O, CH–Br, Br–O, and Br–Br also show the essential roles in the spatial expansion. The role of these non-covalent linkages in the crystal packing is assured. Study by the Hirshfeld surface analysis (HSA) supplies the extra views into the nature of the various short contacts in the crystal structures. The synthons within these assemblies are analyzed. On account of the synergism of the conventional H-bonds and the various non-covalent contacts, they exhibited the 1D and 3D motifs. In conclusion, we have demonstrated that the high dimensional supramolecules can be manufactured by the collective non-covalent connections.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 7","pages":"1473 - 1487"},"PeriodicalIF":1.5,"publicationDate":"2026-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Structure, and Luminescence of a Binuclear Copper(I) Complex Based on 1,3-Diaza-5-Phosphacyclohexane","authors":"K. D. Akhmadgaleev,&nbsp;A. G. Shmelev,&nbsp;L. V. Frantsuzova,&nbsp;I. A. Litvinov,&nbsp;I. D. Strelnik,&nbsp;A. A. Karasik","doi":"10.1134/S0022476626070061","DOIUrl":"10.1134/S0022476626070061","url":null,"abstract":"<p>We report syntheses of two new 1,3-diaza‑5‑phosphacyclohexanes bearing a pyridine-2-yl or pyridine-2-ylethyl substituent at the phosphorus atom and biphenyl groups at the nitrogen atoms. A binuclear copper(I) complex with iodide bridges is prepared on the basis of the ligand with a pyridine-2-ylethyl substituent at the phosphorus atom. Single crystal X-ray diffraction analysis reveals that the ligand in the crystalline state adopts an asymmetric heterocycle conformation with one biphenyl substituent occupying an axial position, thereby leading to pyramidalization of one of the endocyclic nitrogen atoms due to 1,3-syn-axial repulsion. Regardless of the reaction stoichiometry, the interaction of the N-biphenyl‑substituted ligand with CuI exclusively affords a centrosymmetric dimeric complex of composition Cu₂I₂L₂ with a planar four‑membered Cu₂I₂ core, in which the ligand acts as a chelating P,N-donor. The resulting complex exhibits two-band luminescence in the solid state, with each band being selectively excitable owing to different excitation spectra. The long (microsecond) luminescence lifetimes indicate a triplet origin for both emission bands.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 7","pages":"1494 - 1505"},"PeriodicalIF":1.5,"publicationDate":"2026-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure of Diethylamine Complexes with Methanesulfonic Acid in Solutions According to IR Spectroscopy Data and Quantum Chemical Calculations","authors":"E. G. Tarakanova,&nbsp;V. D. Maiorov,&nbsp;I. S. Kislina","doi":"10.1134/S0022476626070127","DOIUrl":"10.1134/S0022476626070127","url":null,"abstract":"<p>Structural and energy parameters and existence regions of hydrogen-bonded complexes determining the properties of solutions in the diethylamine (DEA)–methanesulfonic acid (MSA) system are established by IR spectroscopy and quantum chemistry. Four concentration–structural zones can be distinguished in the component ratio ranging from 0:1 to 1:1. The first zone is pure MSA (which, as shown previously, contains 3MSA complexes and small amounts of 2MSA and 4MSA complexes). In the second zone (from 0:1 to 1:3), DEA·3MSA complexes are formed in addition to MSA self-associates. In the remaining zones, two types of structural solution species coexist. In the third zone (from 1:3 to 1:2), the observed complexes are DEA·3MSA and DEA·2MSA, and those in the fourth zone (from 1:2 to 1:1) are DEA·2MSA and 2DEA·2MSA. All <i>m</i>DEA·<i>n</i>MSA complexes (<i>m</i> = 1-2, <i>n</i> = 1-4) include <span>(text{C}{{text{H}}_{3}}text{SO}_{3}^{-}cdot {{({{text{C}}_{2}}{{text{H}}_{5}})}_{2}}text{NH}_{2}^{+})</span> contact ion pairs serving as structure-forming and stabilizing elements of DEA solutions in MSA. The most energetically favorable complex, 2DEA·2MSA, consists of two ion pairs interacting with each other in such a way that all four of its N–H⋯O bridges are equivalent. The DEA–MSA and TEA–MSA systems exhibit similarities in their complexation processes. The obtained results complement the general scheme of acid–base interactions in acid solutions and expand the database for predicting the catalytic activity of acid–base systems of arbitrary composition.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 7","pages":"1563 - 1572"},"PeriodicalIF":1.5,"publicationDate":"2026-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of 5-Bromodiffractaic Acid and its Antiviral Properties Against Respiratory Syncytial Virus Strain A2","authors":"A. A. Diveikina,&nbsp;A. S. Filimonov,&nbsp;O. A. Luzina,&nbsp;A. A. Shtro,&nbsp;A. V. Galochkina,&nbsp;A. M. Klabukov,&nbsp;D. N. Razgulyaeva,&nbsp;N. F. Salakhutdinov","doi":"10.1134/S0022476626070152","DOIUrl":"10.1134/S0022476626070152","url":null,"abstract":"<p>Natural hydroxy acids, in particular lichen depsides, are of considerable interest to medicinal chemistry due to their broad spectrum of biological activity. Diffractaic acid is a secondary lichen metabolite belonging to the class of depsides. Its structure contains two positions available for aromatic substitution, and modification by introducing substituents at these positions has not been previously studied. Two benzene rings of diffractaic acid bear slightly different sets of substituents, so the possibility of performing regioselective introduction of new substituents is not obvious. It is shown that the <i>N</i>-bromosuccinimide based bromination of diffractaic acid is regioselective at the ring bearing a free carboxy group. The structure of 5-bromodiffractaic acid is established by two-dimensional NMR spectroscopy. Introduction of a bromine atom into the diffractaic acid structure significantly increases both the activity against respiratory syncytial virus strain A2 and the chemotherapeutic index, the latter by a factor of six.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"67 7","pages":"1588 - 1594"},"PeriodicalIF":1.5,"publicationDate":"2026-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}