Journal of Chemical Crystallography最新文献

{"title":"Synthesis, Crystal Structure and Hirshfeld Surface Analysis of Bis(Benzene-1,2-Diamie)-Bis(2,4-Dihidroxybenzoato)-Nickel, [Ni(C6H8N2)2(C7H5O4)2]","authors":"Abdukadir Kh. Tashkulov,&nbsp;Khayit Kh. Turaev,&nbsp;Jamshid M. Ashurov,&nbsp;Ahatov Alisher Ashur o’g’li,&nbsp;Bekmurod A. Khurramovich,&nbsp;Aziz B. Ibragimov,&nbsp;Changkun Xia,&nbsp;Abul Monsur Showkot Hossain","doi":"10.1007/s10870-025-01046-5","DOIUrl":"10.1007/s10870-025-01046-5","url":null,"abstract":"<div><p>The title compound, [Ni(C₆H₈N₂)₂(C₇H₅O₄)₂] was obtained by dissolving of o-phenylenediamine (OPDA), nickel (II) sulfate and 2,4-dihydroxybenzoic acid (2,4-DHB) separately in 10 mL of ethanol (96%) and reacting with 10 mL of distilled water. The reaction mixture was stirred at room temperature and then slowly evaporated the pale green solution at 55–60 °C. The composition and crystal structure of the [Ni(C₆H₈N₂)₂(C₇H₅O₄)₂], complex was obtained at a constant temperature (30 ± 1 ºC) in 12 days. The complex is formed with two neutral bidentate OPDA ligands and two monodentate DHB ligands as [Ni(C₆H₈N₂)₂(C₇H₅O₄)₂]. The Ni atom is located at the inversion center, exhibiting a slightly octahedrally distorted coordination environment, with four nitrogen atoms of two o -phenylenediamine ligands (Ni–N) positioned in the equatorial plane and two oxygen atoms of 2,4-dihydroxybenzoic acid located in the axial plane. Here, two Ni–N bonds [Ni1 —N1 = 2.110(3), Ni1 —N1 ⁱ = 2.110(3) are exhibited the same bond length but opposite Ni–N bands are different Ni2 —N2 = 2.131(2), Ni2 —N2 ⁱ = 2.131(2)] and a longer axial two Ni—O bonds [2.136(2)]. The metal is located around the inversion center and is almost coplanar with the NiN₄ plane. In the crystal, inter-molecular hydrogen bonding interactions are observed at N1— H1..O1 and N2 — H2…O1 in the periodic network structure. The Hirshfeld surface analysis report indicates that the most important contributions to the crystal packing are H…H (44.6%), H….C/C….H (28.7%), O…H/H….O (23.7%), O…C/C….O (2.5%), C…C (1.7%), O…O(0.8%) interactions.</p><h3>Graphical Abstract</h3><p>The paper is designed by crystal structures of Ni(II) complex containing [Ni(C₆H₈N₂)₂(C₇H₅O₄)₂]. In continuation of our interest in the combination forms of benzene-1,2-diamine (ortho-phenylenediamine = OPDA) and 2,4-dihydroxybenzoic acid (2,4-DHB) with first-line conversion of metals, the authors considered a detailed discussion of the structure analysis of the Ni(II) complex from the mixed ligand of OPDA and 2,4-DHB using X-ray crystallographic technique</p>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"147 - 155"},"PeriodicalIF":0.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949576","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":"Neutral Supramolecular Cluster-Based Nanorods from Direct Assembly of Three Building Units","authors":"JianJun Zhang,&nbsp;H. Andrew Zhou,&nbsp;Ted Grant,&nbsp;Abdessadek Lachgar","doi":"10.1007/s10870-025-01044-7","DOIUrl":"10.1007/s10870-025-01044-7","url":null,"abstract":"<div><p>The reaction between (Me₄N)₄[Nb₆Cl₁₂(CN)₆], [Mn(salen)Cl(H₂O)] (salen = N, N’-bis (salicylidene)ethylenedi-amine dianion), and <i>trans</i>-1,2-bis(4-pyridyl)-ethylene (bpe) led to the formation of {[Mn(salen)(H₂O)](bpe)[Mn(salen)]}₂[Nb₆Cl₁₂(CN)₆]⋅17H₂O (<b>1</b>). <b>1</b> features assemblies of 4.47 nm-long molecular nanorods in each of which two [Mn(salen)]⁺ connects <i>via</i> one bpe linker to form a dimeric unit and two dimeric units are <i>trans</i>-coordinated to one [Nb₆Cl₁₂(CN)₆]⁴⁻<i>via</i> cyanido. Its magnetic properties and thermal stability are also reported.</p><h3>Graphic Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>Direct Assembly of {Nb₆} Cluster Units, [Mn(salen)]⁺, and Bpe Leads To Neutral Supramolecular Nanorods of 4.47 nm long</p></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"140 - 146"},"PeriodicalIF":0.4,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949614","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":"Crystallographic and Computational Studies of Semisynthesized 4-Allyl-2-Methoxyphenyl-4-Nitrobenzenesulfonate","authors":"Ayoub Ouaddi,&nbsp;Meriem Khedraoui,&nbsp;Bouchra Es-Sounni,&nbsp;Samir Chtita,&nbsp;Jean-Claude Daran,&nbsp;Ahmed Benharref,&nbsp;Moha Berraho,&nbsp;Lahcen El Ammari,&nbsp;Rabiaa Fdil,&nbsp;Mohamed Bakhouch","doi":"10.1007/s10870-025-01045-6","DOIUrl":"10.1007/s10870-025-01045-6","url":null,"abstract":"<div><p>This work is devoted to the semisynthesis of 4-allyl-2-methoxyphenyl-4-nitrobenzenesulfonate <b>3</b> from naturally occurring eugenol. The structure of the titled compound is established using IR, (¹H and ¹³C) NMR, and mass spectrometry. Single crystal X-ray diffraction is used to corroborate the structure of the compound <b>3</b>. Crystallographic study shows that compound <b>3</b> crystallizes in the monoclinic system with <i>P</i>2₁<i>/n</i> as the space group. DFT studies are carried out to calculate HOMO and LUMO energies. ADMET properties, Molecular docking and dynamic simulation studies are also performed towards the SARS-CoV-2 protein.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>This paper describes a combined crystallographic and computational studies of the 4-allyl-2-methoxyphenyl-4-nitrobenzenesulfonate synthesized from naturally occurring eugenol</p></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"127 - 139"},"PeriodicalIF":0.4,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949646","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, X-ray Structure, DFT, Hirshfeld Surface, QTAIM/RDG and Molecular Docking Analysis of 3-methyl-4-nitro-1,1-biphenyl (3-MNB)","authors":"Neha Kumari,&nbsp;Daljeet Singh,&nbsp;Archana Akaram Yadav,&nbsp;Sandeep Ashok Sankpal,&nbsp;Saminathan Murugavel,&nbsp;Duraiswamy Lakshmanan,&nbsp;Rajni Kant","doi":"10.1007/s10870-025-01043-8","DOIUrl":"10.1007/s10870-025-01043-8","url":null,"abstract":"<div><p>The synthesis of 3-methyl-4-nitro-1,1-biphenyl (3-MNB) and its crystal structure elucidated using experimental and theoretical methods has been reported in this paper. It crystallizes in the orthorhombic crystal system (space group P2₁2₁2₁) with unit cell parameters: a = 7.2918(4) Å, b = 12.0928(6) Å and c = 12.6759(7) Å and Z = 4. The structure has been characterized by FT-IR, NMR (¹H and ¹³C) and X-ray diffraction methods. There exists two C—H⋯O intermolecular hydrogen bond and two π…π interactions. Density functional theory (DFT/B3LYP/6-311 + + G(d, p)) has been employed for the optimization of the structure and the same was compared with the X-ray structure. The HOMO-LUMO energy gap and molecular electrostatic potential maps have been computed. The energy gap of 4.06 eV indicates that the molecule is stable and less reactive. Besides this, the molecular electrostatic potential (MEP) help determine the reactive sites of the molecule. The Hirshfeld surface analysis and 2-D fingerprint plots help explore the nature and percentage contribution of intermolecular interactions. The highest contribution to the total Hirshfeld surface area is from H…H contacts (47.2%) while the contribution of O…H/H…O contacts is 26.4%. The strength and nature of interactions present in the molecule have been characterized by RDG-based NCI and QTAIM analysis. DOS analysis has been performed to investigate the contribution of various orbitals. The molecular docking analysis analysis was performed to determine the binding patterns of 3-MNB with 1CX2, revealing a binding energy of -7.3 Kcal/mol, suggesting its potential as a COX-2 inhibitor.</p></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"115 - 126"},"PeriodicalIF":0.4,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949492","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":"Correction: Polymorphism and Whole-Molecule Disorder of an Antitubercular 8-Nitrobenzothiazinone","authors":"Rüdiger W. Seidel,&nbsp;Richard Goddard,&nbsp;Tom U. Schlegel,&nbsp;Adrian Richter,&nbsp;Ines Rudolph,&nbsp;Peter Imming","doi":"10.1007/s10870-025-01042-9","DOIUrl":"10.1007/s10870-025-01042-9","url":null,"abstract":"","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 1","pages":"66 - 66"},"PeriodicalIF":0.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10870-025-01042-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143668068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ring-chain Tautomerism Trends in 3-(4’-alkyl-2’-oxobut-4’-yl)-4-hydroxycoumarins: Substituent Steric Bulk Controls Solution Composition and Equilibrium Thermodynamics of Alkyl Warfarin Analogs; Structural and Computational Analysis","authors":"Daniel A. Osborne,&nbsp;Jonathan O. Deridal,&nbsp;Jennifer Winarta,&nbsp;Margaret G. Batek,&nbsp;Sharalyn Sentinella,&nbsp;Edward J. Valente","doi":"10.1007/s10870-025-01040-x","DOIUrl":"10.1007/s10870-025-01040-x","url":null,"abstract":"&lt;div&gt;&lt;p&gt;As for warfarin, alkyl analogs of 3-(2’-oxo-4’-alkylbut-4’-yl)-4-hydroxycoumarins in solution display equilibria between &lt;i&gt;trans&lt;/i&gt; hemiketal ⇋ open, and open ⇋ &lt;i&gt;cis&lt;/i&gt; hemiketal tautomers. A steric trend is observed for the reactions by variable temperature NMR in CDCl&lt;sub&gt;3&lt;/sub&gt;, with ΔG (kJ/mol, 298 K) for &lt;i&gt;trans&lt;/i&gt; ⇋open, open ⇋ &lt;i&gt;cis&lt;/i&gt; and alkyl substituents: methyl (+ 0.3, -0.3), &lt;i&gt;n&lt;/i&gt;-pentyl (-2.6, + 3.0), isopropyl (-2.8, + 5.0), cyclohexyl (-4.3, + 7.2), neopentyl (-6.3, + 5.7) and &lt;i&gt;t&lt;/i&gt;-butyl (&lt;-13, &gt;+13) in CDCl&lt;sub&gt;3&lt;/sub&gt;. The &lt;i&gt;trans&lt;/i&gt; ⇋ open reactions typically are entropically favored but decreasingly enthalpically favored with substituent size. For the open ⇋ &lt;i&gt;cis&lt;/i&gt; reactions, enthalpic terms increasingly favor ring opening, while entropic contributions favoring open forms are moderated by greater conformational flexibility in the cyclic forms. Similar results were observed in d&lt;sub&gt;6&lt;/sub&gt;-dmso. In the solid state, (R)-3-(2’-oxopent-4’-yl)-4-hydroxycoumarin crystallizes in the monoclinic system (&lt;i&gt;P&lt;/i&gt; 2&lt;sub&gt;1&lt;/sub&gt;, Z = 6) with one &lt;i&gt;trans&lt;/i&gt; and two &lt;i&gt;cis&lt;/i&gt; hemiketal tautomers comprising the asymmetric unit. Racemic (±)-3-(2’-oxonon-4’-yl)-4-hydroxycoumarin crystallizes in the triclinic system (&lt;i&gt;P&lt;/i&gt; -1) as the &lt;i&gt;cis&lt;/i&gt; (2R,4R / 2 S,4 S) hemiketals. Though the alkyl warfarins typically crystallize as their cyclic hemiketals (&lt;i&gt;cis&lt;/i&gt; or &lt;i&gt;trans&lt;/i&gt;) even with substituents as bulky as neopentyl, the &lt;i&gt;t&lt;/i&gt;-butyl analog, racemic 3-(2’-oxo-5’,5’-dimethylhex-4’-yl)-4-hydroxycoumarin crystallizes in the monoclinic system (&lt;i&gt;P&lt;/i&gt; 2&lt;sub&gt;1&lt;/sub&gt;/&lt;i&gt;c&lt;/i&gt;) as the open coumarin tautomer, and its solutions also contain only the open form. These structures, augmented by literature determinations of alkyl warfarins and derivatives alkyl ketals, include (2 S,4 S)-&lt;i&gt;trans&lt;/i&gt;-2-ethoxy-2-methyl-3,4-dihydro-4-cyclohexyl-2 H,5 H-pyrano[3,2-c] (1)benzopyran-5-one (&lt;i&gt;P&lt;/i&gt; 2&lt;sub&gt;1&lt;/sub&gt;2&lt;sub&gt;1&lt;/sub&gt;2&lt;sub&gt;1&lt;/sub&gt;). From 23 determinations including six reported here, embedded dihydropyran ring conformations provide a structural basis for the steric interactions in the cyclic forms. Alkyl groups in &lt;i&gt;trans&lt;/i&gt; isomers distort the nearby coumarin carbonyl oxygen toward the opposite side of the coumarin ring. Computations (DFT) corroborate the relative stabilities of the cyclic hemiketals with the smaller substituents, but underestimate the importance of solvent on stabilization of the open tautomers. Sterimol analysis of the ΔΔGs for the open – cyclic reactions, relative to the methyl substituent, support a general steric model for the alkyl substituent-related changes in the tautomeric equilibria.&lt;/p&gt;&lt;h3&gt;Graphical Abstract&lt;/h3&gt;&lt;div&gt;&lt;figure&gt;&lt;div&gt;&lt;div&gt;&lt;picture&gt;&lt;img&gt;&lt;/picture&gt;&lt;/div&gt;&lt;div&gt;&lt;p&gt;As alkyl groups (substituted for the phenyl in warfarin) increase in bulk from methyl to &lt;i&gt;t&lt;/i&gt;-butyl, solutions increasingly favor the open tautomer over the cyclic hemiketals, and “&lt;i&gt;t&lt;/i&gt;-butyl warfar","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"97 - 114"},"PeriodicalIF":0.4,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949515","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":"The X-ray Structure of [Fe(CO)3(η4-6-exo-(4-biphenylamino)cyclohepta-2,4-dien-1-one]","authors":"Ian S. Leiby,&nbsp;Eric W. Reinheimer,&nbsp;Daniel R. Griffith,&nbsp;Chip Nataro","doi":"10.1007/s10870-025-01039-4","DOIUrl":"10.1007/s10870-025-01039-4","url":null,"abstract":"<div><p>The structure of [Fe(CO)₃(η⁴-6-<i>exo</i>-(4-biphenylamino)cyclohepta-2,4-dien-1-one] [monoclinic, <i>a</i> = 20.368 (1), <i>b</i> <b>=</b> 6.2757(4), <i>c</i> = 29.5214(14), <i>β</i> = 101.024(5), space group C2/c] has been determined. There is a moderate hydrogen-bond between the amine proton and the oxygen atom of the ketone in another molecule. There is no significant π-stacking of the phenyl rings, but the nitrogen atom is fairly planar likely due to interaction with the π-system of the 4-biphenyl group and the hydrogen-bonding.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>Addition of two equivalents of 4-biphenylamine to [Fe(CO)₃(η⁵-cyclohepta-2,4-dien-5-yl-1-one)][BF₄] results in <i>exo</i>- attack at the coordinated ring forming the [Fe(CO)₃(η⁴-6-<i>exo</i>-(NH(4-biphenyl)))cyclohepta-2,4-dien-1-one], which was structurally characterized</p></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"92 - 96"},"PeriodicalIF":0.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10870-025-01039-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Rare Example of Manganese Aminopyridinate – Synthesis and Structure","authors":"Awal Noor","doi":"10.1007/s10870-024-01038-x","DOIUrl":"10.1007/s10870-024-01038-x","url":null,"abstract":"<div><p>Lithiated N-(2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)-pyridine-2-yl]-amine (ApH) undergoes a salt metathesis reaction with MnBr₂ in tetrahydrofuran (THF) at 50 °C in the presence of two equivalents of 4-<i>tert</i>-butylpyridine (^<i>t</i>BuPy) to yield only the second example of mononuclear manganese aminopyridinates, [Mn(Ap)₂(^<i>t</i>BuPy)]. The compound [C₅₉H₇₁MnN₅], crystallized in the monoclinic space group, <i>P</i>2₁/<i>c</i> with unit cell parameters: a = 11.9650(5) b = 17.9530(7) c = 24.3110(10) Å, β = 95.081(3)°, V = 5201.7(4) A³, Z = 4. Hirshfeld analyses show that H⋯H (89.1%) and H⋯C/C⋯H (10.9%) interactions are the two main contributors that lead to intermolecular stabilization in the solid-state structure.</p></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"85 - 91"},"PeriodicalIF":0.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949415","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 Structure Analysis of Four 2-Pyridineformamide Thiosemicarbazone Derivatives Using Non-Spherical Atomic Form Factors","authors":"Bhushan Shakya,&nbsp;Kuldeep Mahiya,&nbsp;Ramina Maharjan Shrestha,&nbsp;Hari Bhakta Oli,&nbsp;Paras Nath Yadav","doi":"10.1007/s10870-024-01037-y","DOIUrl":"10.1007/s10870-024-01037-y","url":null,"abstract":"<div><p>The crystal structures of four 2-pyridineformamide thiosemicarbazone derivatives <i>viz</i>, (<i>Z</i>,<i> Z’</i>)-4-methyl-<i>N</i>’-(morpholine-4-carbonothioyl)picolinohydrazonamide (<b>1</b>), (<i>Z</i>,<i> Z’</i>)-4-methyl-<i>N</i>’-(thiomorpholine-4-carbonothioyl) picolinohydrazonamide (<b>2</b>), (<i>Z</i>,<i> Z’</i>)-6-methyl-<i>N</i>’-(thiomorpholine-4-carbonothioyl)picolinohydrazonamide (<b>3</b>) and (<i>Z</i>,<i> Z’</i>)-<i>N</i>’-(azepane-1-carbonothioyl)-4-methylpicolinohydrazonamide (<b>4</b>) has been determined by single crystal X-ray diffraction analysis. Combined quantum mechanical methods (ORCA) and computation of non-spherical scattering form factors (NoSpherA2) were used for the refinement with anisotropic hydrogen atoms. The results of using independent atom model (IAM) and Hirshfield atom refinement (HAR) method based R2SCAN/ def2-TZVP functional were compared. All compounds show an improvement in the model after HAR refinement compared to independent atom model (IAM). There is a significant decrease in the residual factors with the use of anisotropic hydrogen refinement. HAR refinement provides a clearer understanding of electron delocalization, lone pairs, and the accumulation and depletion of electron density. The information obtained came from standard resolution single crystal X-ray diffraction data, indicating that high-quality structural analysis can now be performed without the need for neutron or synchrotron facilities.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>Structural studies of four 2-pyridineformamide thiosemicarbazone derivatives using non-spherical atomic form factors</p></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 2","pages":"75 - 84"},"PeriodicalIF":0.4,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949480","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 of 1,4,2-dithiazolidine 1,1-dioxide and 1,2,4-thiadiazolidin-3-one 1,1-dioxide heterocycles formed from N-benzyl-1-chloromethanesulfonamide and either phenyl isothiocyanate or 3,5-dimethylphenyl isocyanate","authors":"Noah Forrest,&nbsp;Edward J. Valente,&nbsp;Warren J. L. Wood","doi":"10.1007/s10870-024-01034-1","DOIUrl":"10.1007/s10870-024-01034-1","url":null,"abstract":"<div><p>Reaction of <i>N</i>-benzyl-1-chloromethanesulfonamide with phenyl isothiocyanate formed <i>N</i>-benzyl-3-phenylimino-1,4,2-dithiazolidine 1,1-dioxide. Crystals of this compound occurred in the monoclinic system, space group <i>P</i> 2(1), <i>a</i> = 26.7099(16) Å, <i>b</i> = 13.2518(5) Å, <i>c</i> = 8.2769(4) Å, <i>β</i> = 97.099(5)^o, Z = 8, with four molecules in the asymmetric unit. The structure confirms a prior assignment that the C = S bond of the isothiocyanate was the reactive moiety. Using the same reaction conditions, 3,5-dimethylphenyl isocyanate was reacted <i>N</i>-benzyl-1-chloromethanesulfonamide to produce a product in 81% yield, which was determined to be 2-benzyl-4-(3’,5’-dimethylphenyl)-1,2,4-thiadiazolidin-3-one 1,1-dioxide. Crystals of this compound are monoclinic, space group <i>P</i> 2(1)/<i>n</i>, <i>a</i> = 5.2243(11) Å, <i>b</i> = 15.844(5) Å, <i>c</i> = 18.628(3) Å, <i>β</i> = 96.72(2)^o, and Z = 4. This product demonstrated that the C = N bond of the aryl isocyanate reacted to form the 1,2,4-thiadiazolidin-3-one 1,1-dioxide ring system.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>Heterocyclic rings formed from <i>N</i>-benzyl-1-chloromethanesulfonamide and phenyl isothiocyanate via the C = S bond (structure on the left) or 3,5-dimethylphenyl isocyanate via the C = N bond (structure on the right)</p></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"55 1","pages":"67 - 73"},"PeriodicalIF":0.4,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143668150","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}