Journal of Structural Chemistry最新文献

{"title":"Structure of 2,3,5,6-Tetraiodo-1,4-Benzenedicarboxylic Acid and Features of the Thermolysis of Iodinated Terephthalic Acids","authors":"M. A. Polozov, D. A. Zherebtsov, A. A. Osipov, K. Radzhakumar, S. A. Naifert, D. V. Spiridonova, A. S. Zaguzin, D. A. Vinnik","doi":"10.1134/s0022476624070060","DOIUrl":"https://doi.org/10.1134/s0022476624070060","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The crystal structure of 2,3,5,6-tetraiodo-1,4-benzenedicarboxylic acid dihydrate is described and the following structural features are established by XRD: C₈H₆I₄O₆, <i>M </i>705.73; monoclinic crystal system, <i>P</i>2₁/<i>n</i> space group; unit cell parameters: <i>a</i> = 5.78160(10) Å, <i>b</i> = 15.0976(2) Å, <i>c</i> = 17.3437(3) Å; α = 90°, β = 94.602(2)°, γ = 90°; <i>V</i> = 1509.02(4) Å³, <i>Z</i> = 4, ρ_calc = 3.106 g/cm³. Some features of the thermolysis of terephthalic acid and its iodine derivatives are described. Diiodoterephthalic acid is the least thermally stable, tetraiodoterephthalic acid is the most stable. The iodinated terephthalic acids have similar heats of fusion. The largest amount of carbon residue is formed during the decomposition of 2,3,5,6-tetraiodo-1,4-benzenedicarboxylic acid.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772452","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":"Mixed-Ligand Chloride Complex of Co(II) withE-2-(((4-Iodophenyl)Imino)Methyl)Phenol: Crystal Structure and Features of Halogen Bonding in a Solid","authors":"S. A. Adonin, P. A. Abramov, A. S. Zaguzin, A. S. Novikov","doi":"10.1134/s0022476624070126","DOIUrl":"https://doi.org/10.1134/s0022476624070126","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Neutral complex [L₂CoCl₂] is obtained by the reaction of cobalt(II) chloride with <i>E</i>-(((4-iodophenyl)imino)methyl)phenol (L), and its structure is studied by single crystal X-ray diffraction. The structure contains I⋯Cl halogen bonds whose energies are estimated by quantum chemical calculations.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772433","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 and Conformational Features of Luminescent Phosphoguanidine with a Phenylbenzothiazole Substituent","authors":"M. Y. Afonin, S. N. Konchenko, T. S. Sukhikh","doi":"10.1134/s0022476624070138","DOIUrl":"https://doi.org/10.1134/s0022476624070138","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>We report a three-stage scheme (1) Pbt–NH₂ + CS₂ → (Pbt–NH)₂C=S (<b>1</b>) (Pbt = 4-(1′,3′-benzothiazole-2′-yl)phenyl), (2) <b>1</b> + PPh₃ + I₂ → Pbt–N=C=N–Pbt (<b>2</b>), (3) <b>2</b> + Ph₂PH → (Pbt–N)(Pbt–NH)CPPh₂ (<b>3</b>) for the synthesis of a novel luminescent phosphoguanidine <b>3</b> with an unprecedentedly high yield (90%) at the last catalyst-free stage. It is demonstrated by the density functional theory (DFT) method that high reactivity of <b>2</b>, leading to such an yield, is explained by a high electrostatic potential at the central carbon atom. For <b>3,</b> two polymorphs <b>3α</b>, <b>3β</b> and a solvatomorph <b>3γ</b>·THF are prepared. The structures of <b>2</b>, <b>3α</b>, <b>3β</b>, and <b>3γ</b>·THF are determined by single-crystal XRD. The tendency of crystals of different phenylbenzothiazole derivatives to form different conformations is explained by the computational (DFT) data indicating that the energy change of the molecule of <b>3</b> considered as a function of the torsion angle between phenyl and benzothiazole fragments does not exceed 2 kJ/mol in the –15…30° range. Photophysical properties of <b>3β</b> and <b>3γ</b>·THF phases are studied. It is shown that these compounds exhibit photoluminescence with an emission maximum at 510 nm.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772434","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":"Effect of the Calcination Temperature on the Properties of MnOx–CuO–ZrO2–CeO2 Catalysts for CO Oxidation","authors":"O. A. Bulavchenko, T. N. Afonasenko, V. P. Konovalova, V. A. Rogov, E. Yu. Gerasimov, E. E. Aidakov, Z. S. Vinokurov","doi":"10.1134/s0022476624070084","DOIUrl":"https://doi.org/10.1134/s0022476624070084","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Four-component oxide catalysts MnO_<i>x</i>–CuO–ZrO₂–CeO₂ are synthesized by co-precipitation with varying the calcination temperature from 400 °C to 800 °C. Formation and decomposition processes in mixed oxides are studied by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The <i>redox</i> properties of the obtained samples are tested by temperature-programmed hydrogen reduction, and the catalytic characteristics are examined in the CO oxidation reaction. At 400-600 °C homogeneous solid solution Mn_<i>x</i>Cu_<i>y</i>Zr_<i>z</i>Ce_<i>q</i>O₂ with the fluorite structure is formed. Temperature elevation to 700-800 °C facilitates the gradual decomposition of initial oxide, with manganese and copper cations leaving its composition in the form of highly dispersed CuO and Cu_<i>x</i>Mn_3–<i>x</i>O₄ particles. The occurrence of different active states in the catalyst and their transitions into each other under the temperature effect is shown to maintain the high activity in the CO oxidation reaction up to 800 °C.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772454","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, Structural Characterization and Hirshfeld Surface Analysis of a Novel Cd(II) Coordination Polymer with Mixed N- and O-donor Linker","authors":"D. Deokar, S. B. Tayade, S. Funde, B. Bhosale, S. Dalvi","doi":"10.1134/s0022476624070163","DOIUrl":"https://doi.org/10.1134/s0022476624070163","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>In the present study, we report the room temperature synthesis of a novel two-dimensional (2D) coordination polymer (CP) having the formula {[Cd(H-PCA)₂(H₂O)]·0.5(H₂O)·0.5(CH₃OH)}_<i>n</i> (<b>CP1</b>), where H-PCA represents 4-pyrazolecarboxylate. The synthesis of <b>CP1</b> was achieved through a one-pot reaction, involving the self-assembly of Cd(OAc)₂·2H₂O and the multitopic mixed N- and O-donor ligand, 4-pyrazolecarboxylic acid (H₂-PCA), in methanol. This method demonstrated high yield and purity, enabling the facile production of multigram quantities of <b>CP1</b> within a short timeframe. Notably, the synthetic procedure selectively deprotonates the carboxylic acid group while retaining the pyrazole moiety in its protonated form. <b>CP1</b> has been thoroughly characterized using various analytical techniques, including single-crystal X-ray diffraction, FTIR spectroscopy, elemental analysis, scanning electron microscopy, thermogravimetric analysis, and powder X-ray diffraction. The structural analysis revealed that <b>CP1</b> features a 3, 5-connected binodal net with the point symbol {4.5.6}{4.5⁵.6³.7}, leading to a unique -ths net topology. Through hydrogen bonding connections between adjacent 2D sheets, <b>CP1</b> further extends into a three-dimensional (3D) supramolecular network due to the presence of coordinated water molecules and the protonated pyrazole group. Additionally, a 3D Hirshfeld Surface analysis accompanied by quantitative 2D fingerprint plots was also investigated to explore the intermolecular interactions.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772437","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 Chloric Acid Hydrates and Equilibrium Composition of the HClO4–H2O System","authors":"V. D. Maiorov, I. S. Kislina, E. G. Tarakanova","doi":"10.1134/s0022476624070059","DOIUrl":"https://doi.org/10.1134/s0022476624070059","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Composition, structure, energy parameters, and existence regions of hydrate complexes formed in the HClO₄–H₂O system are studied by IR spectroscopy and quantum chemical methods. Three concentration-structural regions are determined. The HClO₄–H₂O solutions diluted to the 1:13.3 molar ratio of components contain <span>(text{ClO}^{-}_4)</span> and <span>(text{H}_5text{O}^{+}_2)</span> solvate-separated ions, each hydrated by four water molecules. More concentrated solutions (1:13.3-1:5) contain hydrated ion pairs <span>(text{ClO}^{-}_4cdottext{H}_5text{O}^{+}_2)</span> that are contact ion pairs if the [HClO₄]:[H₂O] ratio falls within the region 1:9-1:5. As the acid concentration increases further up to the transition of the HClO₄–H₂O system into the solid phase, pair complexes are formed. The structure of the latter is formed by a cycle of two contact ion pairs <span>(text{ClO}^{-}_4cdottext{H}_5text{O}^{+}_2)</span> connected by two H-bonds. The solid phase consists of interacting polymer chains formed by <span>(text{ClO}^{-}_4cdottext{H}_5text{O}^{+}_2)</span> and <span>(text{ClO}^{-}_4cdottext{H}_3text{O}^{+})</span> ion pairs.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772450","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 Features of Hydrated Representatives of the Labuntsovite Group: Refinement of Crystal Structures of Intermediate Members of the Tsepinite-Na–“Tsepinite-Ba”–Tsepinite-K Solid Solution","authors":"Yu. A. Vaitieva, N. V. Chukanov, M. F. Vigasina, D. A. Varlamov, S. N. Volkov, R. K. Rastsvetaeva, S. M. Aksenov","doi":"10.1134/s0022476624070072","DOIUrl":"https://doi.org/10.1134/s0022476624070072","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Two mineral species of the labuntsovite group from Khibiny (sample <b>1</b>) and Lovozero (sample <b>2</b>) alkaline massifs are analyzed by single crystal X-ray diffraction and Raman spectroscopy. They are intermediate members of the tsepinite-Na–“tsepinite-Ba”–tsepinite-K solid solution, which are characterized by a high degree of hydration and a low concentration of extra-frame cations. Parameters of monoclinic cells are: <i>a</i> = 14.5086(6) Å, <i>b</i> = 14.2174(6) Å, <i>c</i> = 7.8712(3) Å, β = 117.119(4)°, <i>V</i> = 1444.09(11) Å³ (sample <b>1</b>) and <i>a</i> = 14.2582(4) Å, <i>b</i> = 13.7541(6) Å, <i>c</i> = 7.7770(2) Å, β = 116.893(4)°, <i>V</i> = 1360.20(9) Å³ (sample <b>2</b>). Crystal chemical formulas (<i>Z</i> = 2) are: <i>|</i>^<i>A</i>[Na_0.84K_0.6[(H₂O)₄]_5.2]^<i>B</i>K_0.2^<i>C</i>Ba_0.25^<i>D</i>[Ca_0.35Na_0.15Fe_0.025(H₂O)]| {<i>M</i>1(Ti_1.2Nb_0.8)<i>M</i>2(Ti_1.1Nb_0.9)(O,OH)₄(Si₄O₁₂)₂} for sample <b>1 </b>and <i>|</i>^<i>A</i>[Na_1.6(H₂O,H₃O)_0.4]^<i>B</i>K₂^<i>C</i>(Ba_0.51Sr_0.21)^{<i>D</i> [Mn}_0.3Ca_0.2(H₂O)](H₂O)₄|{<i>M</i>1(Ti_1.94Nb_0.06)<i>M</i>2(Ti_1.88Nb_0.12)(O,OH)₄(Si₄O₁₂)₂} for sample <b>2</b>. The high degree of hydration of sample <b>1</b> is expressed in the presence of proton hydrate complexes and tetrahedral [H₂O]₄-associates. Labuntsovite group minerals (LGMs) are characterized by so-called block isomorphism due to different distributions of <i>D</i> cations. Our analysis of heteropolyhedral <i>MT</i>-frameworks in LGMs allows us to determine the topological features of cation networks.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772451","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 and Structure of a Copper(II) Complex Based on N-2-(2-pyridyl)Ethyl-2-Aminoethanesulfonic Acid","authors":"E. O. Zemlyakova, G. P. Zharkov, Y. S. Petrova, L. K. Neudachina, P. A. Slepukhin, T. V. Aksenova, A. V. Pestov","doi":"10.1134/s0022476624070102","DOIUrl":"https://doi.org/10.1134/s0022476624070102","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>A novel copper(II) complex based on N-2-(2-pyridyl)ethyl-2-aminoethanesulfonic acid is prepared, its structure is studied by XRD (CCDC No. 2215117). The crystal of the complex is formed by monomeric [CuLH₂O]NO₃ units. The metal centers of the units have an octahedral coordination environment formed by nitrogen atoms of pyridine and the amino group, oxygen atoms of the sulfo group, and water molecules located in the equatorial plane. On the axial axis, there are oxygen atoms of the sulfo groups of the neighboring ligands forming a 1D coordination polymer.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141785305","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":"Crystal Growth from Supersaturated Aqueous Salt Solutions on a Polymer Nafion Substrate","authors":"N. F. Bunkin, Y. V. Novakovskaya, P. N. Bolotskova, V. V. Voronov, V. A. Kozlov, S. L. Timchenko, M. T. Khoung, E. N. Baranova","doi":"10.1134/s0022476624070023","DOIUrl":"https://doi.org/10.1134/s0022476624070023","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Features of the crystallization of various compounds on the Nafion polymer substrate from supersaturated aqueous solutions is studied by XRD. The solutions are prepared from natural deionized and deuterium-depleted water. It was earlier established that the swelling of Nafion in natural deionized water clearly demonstrates effects caused by the partial uncoiling of polymer fibers into the liquid volume, but no such effects were observed in deuterium-depleted water. The ab initio calculations performed in the present work show that the uncoiling of lateral Nafion chains with terminal –SO₃H groups and the dissociation of these groups with subsequent formation of hydronium ions and <span>(-text{SO}_3^{-})</span> structural anionic residues are energetically favorable in the case of the contact with a sufficient amount of water molecules. The influence of these factors on the process of crystal formation on polymer substrates is studied. It is established that the effect of partial uncoiling of polymer chains indeed affects the crystallization, and does it in different ways, depending on the crystal structure. Thus, no differences between XRD patterns of crystals grown on smooth and polymer substrates are observed for the monoclinic lattice of sodium acetate trihydrate. In the case of copper sulfate (with either CuSO₄·5H₂O pentahydrate crystals (triclinic crystal system) or CuSO₄·3H₂O trihydrate crystals (monoclinic crystal system)), copper sulfate trihydrate and pentahydrate are formed on the polymer and smooth substrates, respectively. None of the studied crystals exhibited differences between smooth and polymer substrates for the supersaturated solutions based on deuterium-depleted water, and in both cases a triclinic crystal system of the CuSO₄·5H₂O pentahydrate precipitate is identified for the CuSO₄ aqueous solution. For sucrose, the precipitate amorphization upon the deposition onto the Nafion plate is detected. A theoretical model is proposed to explain the effect of partial polymer chain uncoiling on the growth of crystals, depending on their crystal system, unit cell parameters, and the volumetric ratio of hydrophilic and hydrophobic fragments in the molecular structure.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141786043","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 Parameters of Ion Coordination in Aqueous Solutions of Cerium Nitrate According to the X-Ray Diffraction Analysis","authors":"P. R. Smirnov, O. V. Grechin","doi":"10.1134/s0022476624070096","DOIUrl":"https://doi.org/10.1134/s0022476624070096","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Based on the experimental data of the X-ray diffraction analysis, radial distribution functions are calculated in a wide concentration range of aqueous cerium nitrate solutions under standard conditions. Different models of the structural organization of systems are elaborated. By the calculation of theoretical functions for each model and their comparison with the experimental ones the optimal variants are revealed. Quantitative characteristics of the structure of the nearest environment of Ce³⁺ and <span>(text{NO}^{-}_3)</span> ions, such as coordination numbers and interparticle distances, are determined along with the types of ionic pairs. The structure of the saturated solution is found to be governed by non-contact ion triples. A decrease in the concentration leads to their transformation into ionic pairs.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.8,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141772453","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}