Acta Crystallographica Section C Structural Chemistry最新文献

{"title":"Synthesis, crystal structure elucidation, theoretical characterization and thermochemistry analysis of the potential anticancer drug BFS.","authors":"Marta Hoelm, Kinga Wzgarda-Raj, Zdzislaw Kinart, Bartlomiej Kost, Marek Brzezinski, Paulina Staniec","doi":"10.1107/S2053229625001299","DOIUrl":"10.1107/S2053229625001299","url":null,"abstract":"<p><p>The potential anticancer drug for leukemia, butane-1,4-diyl bis(2,2,2-trifluoroethane-1-sulfonate) (BFS), C₈H₁₂F₆O₆S₂, a fluorine analogue of busulfan, was synthesized and analyzed for the first time using various experimental and theoretical techniques, including NMR spectroscopy, single-crystal X-ray diffraction, thermochemistry and computational methods. Crystallographic analysis revealed that BFS crystallizes in the monoclinic space group P2₁/n, with its structure stabilized by covalent bonding, torsional flexibility and hydrogen bonding. Efficient packing and symmetry interactions balance density and stability. Theoretical calculations, using molecular mechanics, semi-empirical methods and density functional theory (DFT), with functionals such as M06-2X-D3, M08-HX-D3, CAM-B3LYP-D3 and B97D3, confirmed that BFS adopts a compact geometry stabilized by intramolecular hydrogen bonds, consistent with spectroscopic measurements. Gravimetric analysis was used to estimate the solubility of BFS in water at room temperature.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"156-164"},"PeriodicalIF":0.7,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447687","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":"Magnesium and potassium scorpionate complexes based on dihydrobis(pyrazolyl)borate.","authors":"Marcos A Loroño-González, Daniel J Loroño-González","doi":"10.1107/S2053229625000750","DOIUrl":"10.1107/S2053229625000750","url":null,"abstract":"<p><p>The first X-ray crystal structure is reported for [dihydrobis(pyrazol-1-yl)borato-κ²N,N']tris(tetrahydrofuran-κO)magnesium(II) tetrabenzylborate, [Mg(C₆H₈BN₄)(C₄H₈O)₃][B(C₇H₇)₄)], (I), which was obtained by reacting crude [K(C₆H₈BN₄)] with an equimolar amount of (PhCH₂)MgCl in tetrahydrofuran at room temperature and was isolated as a side product. The crystal structure analysis reveals the existence of a pronounced boat-shaped central Mg(N-N)₂B moiety with a weak pseudo-axial B-H...Mg interaction. The existence of a novel counter-ion, [B(C₇H₇)₄)]^-, has been demonstrated by the first evidence of reactivity between KBH₄ and (PhCH₂)MgCl (in a 1:4 molar ratio) to give a polymeric potassium tetrabenzylborate, poly[[μ₄-dihydrobis(pyrazol-1-yl)borato-κ²N,N']potassium(I)], [K{B(C₇H₇)₄}]_n, (II), with predominant (η⁶-C₆H₅)...K, and (η³-C₆H₅)...K interactions. Density functional theory (DFT) calculations were conducted to determine the energy, the frontier molecular orbitals (HOMO and LUMO) and the molecular electrostatic potential (MEP) in order to explain the stability of the structures in the experimental results for complexes (I) and (II).</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"131-139"},"PeriodicalIF":0.7,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254317","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":"Two nonlinear optically responsive crown ether inclusion compounds based on a sulfonimide anion assembly.","authors":"Yao Zhang, Yan Juan Wang, Yuan Yuan Tang, Xiao Gang Chen","doi":"10.1107/S2053229625000294","DOIUrl":"10.1107/S2053229625000294","url":null,"abstract":"<p><p>Organic amine crown ether supramolecular compounds, based on crystal engineering design, have already made significant research progress in functional devices such as ferroelectrics, ferroelastics and nonlinear optical materials, especially those involving anilinium cations, which have attracted widespread attention. In comparison, benzylammonium cations have been less studied and most counter-ions are inorganic metal salt anions, crystallizing in centrosymmetric space groups without nonlinear optical (NLO) response. By changing the anion, we have obtained two types of crown ether inclusion compounds, namely, benzylammonium bis(methanesulfonyl)azanide-1,4,7,10,13,16-hexaoxacyclooctadecane (1/1), C₇H₁₀N⁺·C₂H₆NO₄S₂^-·C₁₂H₂₄O₆ or [(BA)(18-crown-6)][DMSA] [BA = benzylammonium and DMSA = bis(methanesulfonyl)azanide] and benzylammonium (methanesulfonyl)(trifluoromethylsulfonyl)azanide-1,4,7,10,13,16-hexaoxacyclooctadecane (1/1), C₇H₁₀N⁺·C₂H₃F₃NO₄S₂^-·C₁₂H₂₄O₆ or [(BA)(18-crown-6)][TfNMs] [TfNMs = (methylsulfonyl)(trifluoromethylsulfonyl)azanide]. Both compounds crystallize in the polar chiral space group P2₁ at 100 K and exhibit a clear second harmonic generation (SHG) active characteristic, showing potential for use in quadratic nonlinear optical fields. Moreover, this work is the first to report crown-ether-based compounds using TfNMs as the counter-ion, enriching the choice of counter-anion for crown-ether-based compounds.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"140-145"},"PeriodicalIF":0.7,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143405048","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":"Polymorphism in a secondary phosphine.","authors":"Mo Liu, Keith Izod, Paul G Waddell","doi":"10.1107/S2053229625000555","DOIUrl":"10.1107/S2053229625000555","url":null,"abstract":"<p><p>Two crystal structures of bis(2,3,5,6-tetramethylphenyl)phosphine, C₂₀H₂₇P, are reported constituting the first recorded case of polymorphism in a secondary phosphine (R₂PH). The two structures differ in their conformation and, as a result, the steric hindrance experienced at the phosphorus centre is observed to be dependent on the packing environment. Each polymorph exhibits a distinct supramolecular structure; in polymorph I the molecules are arranged in columns in two directions, whereas polymorph II forms layers. There is a distinct lack of significant intermolecular interactions in either form, with the exception of some weak Me...π interactions observed in polymorph II. These interactions are likely the cause of the variation in the C-P-C angles observed between the two structures.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":"81 Pt 2","pages":"109-113"},"PeriodicalIF":0.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11795654/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187909","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":"Conformational versatility among crystalline solids of L-phenylalanine derivatives.","authors":"Federico Movilla, Juan Manuel Rey, María Del Rosario López Borda, Florencia Di Salvo","doi":"10.1107/S2053229625000269","DOIUrl":"10.1107/S2053229625000269","url":null,"abstract":"<p><p>In this study, we present a new N-derivative of L-phenylalanine with 2-naphthaldehyde (PN), obtained by the Schiff base formation procedure and its subsequent reduction. This compound was crystallized as a zwitterion {2-[(naphthalen-2-ylmethyl)azaniumyl]-3-phenylpropanoate, C₂₀H₁₉NO₂}, as an anion in a sodium salt (catena-poly[[diaquasodium(I)-di-μ-aqua] 2-[(naphthalen-2-ylmethyl)amino]-3-phenylpropanoate monohydrate], {[Na(H₂O)₄](C₂₀H₁₈NO₂)·H₂O}_n), as a cation in a chloride salt [(1-carboxy-2-phenylethyl)(naphthalen-2-<!?tlsb=-0.2pt>ylmethyl)azanium chloride acetic acid monosolvate, C₂₀H₂₀NO₂⁺·Cl^-·CH₃COOH], and additionally acting as a ligand in the pentacoordinated zinc compound aquabis{2-[(naphthalen-2-ylmethyl)amino]-3-phenylpropanoato-κO}zinc(II), [Zn(C₂₀H₁₈NO₂)₂(H₂O)] or [Zn(PN)₂(H₂O)], denoted (PN-Zn), with the amino acid derivative in its carboxylate form. Interestingly, both enantiomers of the zinc complex co-exist within the crystalline structure, one constructed by the ligands with the L (or S) configuration and the other with the ligands having the D (or R) configuration, represented as L,L-PN-Zn and D,D-PN-Zn, respectively. Also, in the structure of the zwitterion, the racemate L,D is observed. These results imply that chirality inversion of the amino acid derivative synthesized from enantiomerically pure L-phenylalanine is taking place, a phenomenon known as oscillatory transenantiomerization. The analysis of these crystal structures reveals that they are primarily stabilized through electrostatic interactions assisted by hydrogen bonds. An interesting finding is that the conformation of PN varies along this family: it is unfolded in the zwitterionic and cationic forms, and folded in the anionic form. To evaluate such conformational differences, we propose the use of a dimensionless Shape Factor quantity defined as the Structural Aspect Ratio (SA_R), computed from the geometrical features of the parallelepiped that tightly encloses a conformer constructed by rigid spheres. This parameter provides a simple but useful tool to distinguish conformational differences, providing insights that complement traditional structural analyses. The study of the structural features, conformational diversity, chirality and supramolecular properties of these compounds is also supported by density functional theory (DFT) calculations.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"64-76"},"PeriodicalIF":0.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031730","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":"Where are the lone pairs? QC and QCT.","authors":"Fernando Cortés-Guzmán","doi":"10.1107/S2053229624012488","DOIUrl":"10.1107/S2053229624012488","url":null,"abstract":"<p><p>The article by Guzmán-Hernández & Jancik [(2024). Acta Cryst. C80, 766-774] is an excellent example of how QC-QCT (quantum crystallography-quantum chemical topology) methodology can extract structural information from a crystal.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"54-55"},"PeriodicalIF":0.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142930333","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 investigations of benzoyl fluoride and the benzoacyl cation of low-melting compounds and reactive intermediates.","authors":"Valentin Bockmair, Martin Regnat, Huu Khanh Trinh Tran, Andreas J Kornath","doi":"10.1107/S2053229625000476","DOIUrl":"10.1107/S2053229625000476","url":null,"abstract":"<p><p>Acyl fluorides and acyl cations represent typical reactive intermediates in organic reactions, such as Friedel-Crafts acylation. However, the comparatively stable phenyl-substituted compounds have not been fully characterized yet, offering a promising backbone. Attempts to isolate the benzoacylium cation have only been carried out starting from the acyl chloride with weaker chloride-based Lewis acids. Therefore, only adducts of 1,4-stabilized acyl cations could be obtained. Due to the low melting point of benzoyl fluoride, together with its volitality and sensitivity toward hydrolysis, the structures of the acyl fluoride and its acylium cation have not been determined. Herein, we report the first crystal structure of benzoyl fluoride, C₇H₅FO or PhCOF (monoclinic P2₁/n, Z = 8) and the benzoacylium undecafluorodiarsenate, C₇H₅O⁺·As₂F₁₁^- or [PhCO]⁺[As₂F₁₁]^- (monoclinic P2₁/n, Z = 4). The compounds were characterized by low-temperature vibrational spectroscopy and single-crystal X-ray analysis, and are discussed together with quantum chemical calculations. In addition, their specific π-interactions were elucidated.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"93-101"},"PeriodicalIF":0.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11795653/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031732","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":"On the deprotonation of chlorothiazide.","authors":"Rowan K H Brydson, Morven L Gray, Alan R Kennedy, Benjamin C O'Hara, Michael W Reid, Ifeka Ugbolue","doi":"10.1107/S2053229625000701","DOIUrl":"10.1107/S2053229625000701","url":null,"abstract":"<p><p>Three alkali metal salt forms of the diuretic chlorothiazide (systematic name: 6-chloro-1,1-dioxo-2H-1,2,4-benzothiazine-7-sulfonamide, HCTZ) are described. When crystallized from aqueous solution, the Na and K salts, namely, poly[[μ-aqua-aqua(μ₃-6-chloro-1,1-dioxo-7-sulfamoyl-2H-1,2,4-benzothiadiazin-2-ido)sodium] hemihydrate], {[Na(C₇H₅ClN₃O₄S₂)(H₂O)₂]·0.5H₂O}_n, and poly[[diaqua(μ₅-6-chloro-1,1-dioxo-7-sulfamoyl-2H-1,2,4-benzothiadiazin-2-ido)potassium] hemihydrate], {[K(C₇H₅ClN₃O₄S₂)(H₂O)₂]·0.5H₂O}_n, are both found to have stoichiometry MCTZ·2.5H₂O, with CTZ deprotonated at a heterocyclic ring N atom. Both the stoichiometry and the deprotonation site are different to those described in previously published versions of these structures. The Cs salt form is found to be the monohydrate CsCTZ·H₂O, namely, poly[[aqua(μ₅-6-chloro-1,1-dioxo-7-sulfamoyl-2H-1,2,4-benzothiadiazin-2-ido)caesium], [Cs(C₇H₅ClN₃O₄S₂)(H₂O)]_n. As with the Na and K cognates, this structure is also deprotonated at the heterocyclic ring. NaCTZ is found to be a two-dimensional coordination polymer with bridges between Na centres formed by H₂O and SO₂ groups, and by links through the length of the coordinated CTZ anions. Water ligands in KCTZ and CsCTZ are terminal, rather than bridging between metal centres, but both compounds form structures where M-Cl interactions link two-dimensional motifs formed via M-O bonds (and in CsCTZ, M-N bonds) into three-dimensional coordination polymers.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":"81 Pt 2","pages":"102-108"},"PeriodicalIF":0.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11795655/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187908","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":"Crystal structure of submicron-sized sulfur particles using 3D ED obtained in atmospheric conditions.","authors":"Sepideh Rahimisheikh, Amirhossein Hajizadeh, Matthias Quintelier, Sander Stulens, An Hardy, Joke Hadermann","doi":"10.1107/S2053229625000130","DOIUrl":"10.1107/S2053229625000130","url":null,"abstract":"<p><p>Lithium-sulfur batteries are a promising candidate for the next generation of rechargeable batteries. Despite extensive research on this system over the last decade, a complete understanding of the phase transformations has remained elusive. Conventional in-situ powder X-ray diffraction has struggled to determine the unit cell and space group of the polysulfides formed during charge and discharge cycles due to the high solubility of these solid products in the liquid electrolyte. With the improvement in in-situ electrochemical set-ups dedicated to transmission electron microscopes, three-dimensional electron diffraction (3D ED) has the potential to capture the crystal structures of the polysulfides during cycling. In this work, the structure solution and refinement from 3D ED data of elemental sulfur, known to sublimate in the vacuum of transmission electron microscopes, is enabled through the use of an environmental cell with a micro-electromechanical system. This work represents the first step in characterizing sulfur's transformation into lithium polysulfides using in-situ 3D ED.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"56-63"},"PeriodicalIF":0.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051346","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":"Monoprotonated species of 2-aminomalonyl difluoride, [C₃H₄F₂NO₂][H₂F₃].","authors":"Dirk Hollenwäger, Dominik Leitz, Valentin Bockmair, Andreas J Kornath","doi":"10.1107/S2053229624012452","DOIUrl":"10.1107/S2053229624012452","url":null,"abstract":"<p><p>The monoprotonated species of 2-aminomalonyl difluoride, namely, 1,3-difluoro-1,3-dioxopropan-2-aminium dihydrogen trifluoride, [C₃H₄F₂NO₂][H₂F₃], was synthesized from sulfur tetrafluoride in anhydrous hydrogen fluoride (aHF) with [NH₄][C₃H₅NO₄] as the starting material. The solvent was removed and the salt was dissolved in aHF and crystallized. In the solid state, the three-dimensional network is built by medium-strong N-H...F hydrogen bonds and C...F contacts. This is the first structure determination of an aminoacyl difluoride and the second of an aminoacyl fluoride.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"77-81"},"PeriodicalIF":0.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11795652/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142942363","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}