Acta crystallographica Section B, Structural science, crystal engineering and materials最新文献

{"title":"Structural and computational studies of new Schiff base ligands derived from 2-(methylamino)- and 2-(ethylamino)benzaldehyde: synthesis, characterization, QTAIM, NCI plot, TD-DFT and energy decomposition analysis.","authors":"Akbar Rostami-Vartooni, Reza Kia, Fereshteh Abbasi, Mostafa Kiamehr, Paul R Raithby","doi":"10.1107/S2052520625008467","DOIUrl":"10.1107/S2052520625008467","url":null,"abstract":"<p><p>Three novel Schiff base ligands were synthesized through the condensation reaction of 2-(methylamino) or 2-(ethylamino)benzaldehyde with ethylenediamine and 4-nitro-1,2-phenylenediamine, respectively. The resulting Schiff bases were thoroughly characterized using FTIR, ¹H NMR and UV-vis spectroscopies, and their crystal structures were elucidated through single-crystal X-ray diffraction. Additionally, computational methods based on noncovalent interaction index and quantum theory of atoms in molecules were employed to investigate the intra- and intermolecular interactions in the molecular structure and crystal packing. The origin of the electronic transitions in UV-vis spectra of the Schiff base ligands were also investigated using time-dependent density functional theory along with the electron density difference map. Furthermore, energy decomposition analysis combined with natural orbitals for chemical valence theory has been performed to estimate the pairwise interaction energies in the dimer associates aggregated by the intermolecular interactions in the Schiff base ligands.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"540-549"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145494471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Probing the local structure of Bi₂O₃ chemical derivatives: the neglected cation sublattice.","authors":"Sikhumbuzo M Masina, Gugulethu C Nkala, Kevin H Stone, Daniel Olds, Caren Billing, David G Billing","doi":"10.1107/S2052520625009400","DOIUrl":"10.1107/S2052520625009400","url":null,"abstract":"<p><p>High-resolution synchrotron X-ray diffraction data confirm the stabilization of the average structure at ambient temperatures as a defect fluorite structure in ternary and quaternary oxides of Bi₂O₃, where some Bi cations are replaced with Dy³⁺ and/or Er³⁺, Nb⁵⁺ and W⁶⁺. Rietveld refinement of the diffraction data indicates that when the larger cation Er³⁺ (0.89 Å) is replaced with smaller cations W⁶⁺ (0.42 Å) and/or Nb⁵⁺ (0.48 Å), the unit-cell parameter a, based on the relative ionic radii of the substituents, counterintuitively increases. Total scattering data show that the identity of the cation substituent is important in determining the positions of some Bi cations in the defect fluorite structure. Er³⁺ and Dy³⁺ cations induce monoclinic-like distortions that extend only locally in the Bi³⁺ sublattice. X-ray absorption spectroscopy provides evidence that some Dy cations, in the δ phases, prefer to keep a similar local environment to that in the parent Dy₂O₃. W cations are found to be predominantly tetrahedrally coordinated in the δ phases explored in this work.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"595-604"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12786384/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145595721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DMSO solvates of tert-butylcalix[6]arene and related multisolvent structures.","authors":"Monika Wanat, Ewelina Zaorska, Maura Malinska","doi":"10.1107/S2052520625008625","DOIUrl":"10.1107/S2052520625008625","url":null,"abstract":"<p><p>tert-Butylcalix[6]arene (TBC6) exhibits a rich crystal energy landscape, with structural diversity driven by macrocycle conformation, guest inclusion and self-assembly. Using multicomponent crystallization mixtures containing DMSO and additional solvents (e.g. DMF, chlorobenzene, 1,2-dichlorobenzene, anisole, THF), we obtained seven new TBC6 solvates. One structure, crystallized in the presence of pyridine, adopts a winged-cone conformation with a bilayer arrangement in the crystal. The remaining six are isostructural and feature a columnar packing of TBC6 in a 1,2,3-alternate conformation stabilized by four strong interactions with DMSO: two hydrogen bonds and two C-H...π interactions. Notably, DMSO in the TBC6 cavity is released at elevated temperatures (∼200°C), consistent with its stronger binding energy as calculated using DFT methods. TBC6-TBC6 interactions, both within and between columns, dominate the crystal packing, with intracolumnar contacts contributing twice as much stabilization as intercolumnar ones, where additional solvent guests are located. Hirshfeld surface analysis supports these findings, highlighting extensive contact areas between TBC6 molecules. This study contributes to understanding how solvent properties, interaction energies, and packing preferences drive the solid-state organization of calixarenes-molecules with broad applications in separation, recognition, and supramolecular chemistry.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"517-527"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12786388/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145470314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Subtle details revealed via powder diffraction and validated by charge flipping.","authors":"Peter W Stephens","doi":"10.1107/S2052520625010601","DOIUrl":"10.1107/S2052520625010601","url":null,"abstract":"<p><p>Lake and Von Dreele [Acta Cryst. (2025), B81, 572-581] provide an informative look at the current state of the art in powder diffraction, and subtleties that can be revealed through its careful application.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"500-501"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 van der Waals layered phosphorus chalcogenide CuVP₂S₆.","authors":"Nur Farhana Hasmuni, Daisuke Urushihara, Ryura Hayashi, Ryo Sato, Koichiro Fukuda, Mohd Zamri Mohd Yusop, Toru Asaka","doi":"10.1107/S2052520625008820","DOIUrl":"10.1107/S2052520625008820","url":null,"abstract":"<p><p>The crystal structure of CuVP₂S₆ is investigated by transmission electron microscopy (TEM) and single-crystal X-ray diffraction. Cu, V and dimerized P₂ are each octahedrally coordinated by S atoms. Each metal ion species forms a triangular lattice, which is interdigitated to form a two-dimensional sheet. Each sheet forms a layered structure with van der Waals gaps between them. The crystal has a rotational twin structure, which is manifested in the form of stacking disorder. Refined structure analysis reveals characteristic rotational distortion of the octahedra. The existence of Cu sites protruding into the van der Waals gap is directly shown by high-resolution scanning TEM.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"565-571"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12786387/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145494520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"OD (order-disorder) interpretation and diffuse scattering analysis of an organic polytype with allotwin character: a detailed how-to.","authors":"David Fröschl, Nicolas Kratena, Berthold Stöger, Alexandr Virovets, Tobias Wolflehner","doi":"10.1107/S205252062500914X","DOIUrl":"10.1107/S205252062500914X","url":null,"abstract":"<p><p>2,3-Dihydroxy-1,3,4-trimethyl-6-oxo-1,4-cyclohexadiene-1-carboxylic acid crystallizes in an order-disorder (OD) structure with a high stacking fault probability. The diffraction pattern features diffuse scattering and broad peaks, which can be attributed to fragments of two polytypes of a maximum degree of order (MDO). Additional weak peaks indicate existence of a non-MDO polytype. A detailed step-by-step instruction is given on how to develop an OD description and interpret the diffuse scattering using a stochastic growth model.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"550-564"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12786389/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145494528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Introduction to the magnetic structures special issue.","authors":"Juan Manuel Perez-Mato, Branton J Campbell, Vasile O Garlea","doi":"10.1107/S2052520625010765","DOIUrl":"10.1107/S2052520625010765","url":null,"abstract":"<p><p>The virtual special issue on Magnetic Structures is introduced. The articles included here were originally published in recent regular issues of Acta Crystallographica Section B.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"498-499"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145653087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel dense crystal structure of high-pressure synthetic K₈Ca₃(CO₃)₇ as described through cation-carbon nets.","authors":"Anna Yu Likhacheva, Sergey V Rashchenko, Mark A Ignatov, Alexandr V Romanenko, Anton F Shatsky","doi":"10.1107/S2052520625007929","DOIUrl":"10.1107/S2052520625007929","url":null,"abstract":"<p><p>K₈Ca₃(CO₃)₇ was synthesized at 1200°C and 6 GPa. Its layered triclinic crystal structure presents a new type characteristic of high-pressure K-Ca carbonates. It is also the second example of K/Ca disorder coupled with orientational disorder of carbonate anions. Descriptions based on the most symmetric (tri/hexagonal) and the densest (krd-type) cation-carbon nets reveal its peculiarities and common features with the crystal structures of chemically related carbonates. The four-layered ABA'B packing in K₈Ca₃(CO₃)₇ is based on hexagonal cation nets, wherein carbon atoms occupy two types of positions. Most of the carbon atoms are localized close to net B, within the centers of triangular loops. This forms a bütschliite layer, which is found in other alkali-bearing carbonates and is composed of alkali cations. Its presence in the K₈Ca₃(CO₃)₇ crystal structure implies that the K/Ca disorder is incomplete. In nets A and A', carbon atoms replace the cations at some nodes, resulting in the aggregation and increased concentration of carbon atoms and their stronger mixing with cations in the densest (krd-type) nets. Thus, a new type of densest mixed net is formed in the K₈Ca₃(CO₃)₇ crystal structure. A quantitative measure of the packing density of high-pressure K-Ca carbonates is the reticular density of the symmetric atomic nets, as well as the distance between the densest nets.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"466-472"},"PeriodicalIF":1.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184464","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"EuPdSn₂: magnetic structures in view of resonant X-ray Bragg diffraction.","authors":"Stephen W Lovesey","doi":"10.1107/S2052520625006134","DOIUrl":"10.1107/S2052520625006134","url":null,"abstract":"<p><p>The magnetic properties of materials hosting Eu²⁺ (J = 7/2, 4f⁷) ions have attracted much attention in the science of strongly correlated electrons. In part because crystal electric field effects are impoverished for an S-state ion, as with Gd³⁺ intermetallics, and Eu²⁺ substitution in biological and optically active materials is resourceful. The magnetic structure of EuPdSn₂ is not wholly resolved. Ferromagnetic and antiferromagnetic structures coexist in powder neutron diffraction patterns, and compete in the ground state. Moreover, the specific heat as a function of temperature is enigmatic and indicative of J = 5/2. We present symmetry-informed analytic magnetic structure factors for single crystal resonant X-ray Bragg diffraction using Eu atomic resonances that reveal significant potential for the technique. Europium ions use Wyckoff positions that are not centres of inversion symmetry in magnetic space groups inferred from neutron diffraction. In consequence, axial and polar Eu multipoles are compulsory components of both magnetic neutron and resonant X-ray Bragg diffraction patterns. The proposed antiferromagnetic phase of EuPdSn₂ supports anapoles (magnetic polar dipoles) already observed in magnetic neutron diffraction patterns presented by Gd-doped SmAl₂, and several resonant X-ray diffraction patterns.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"440-444"},"PeriodicalIF":1.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12517053/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144854137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigation of thermal behavior of monoclinic ludwigite-type oxoborate Cu₂FeO₂(BO₃) in the range 300-1273 K.","authors":"Yaroslav P Biryukov, Rimma S Bubnova, Andrey P Shablinskii, Yulia S Gokhfeld, Natalya V Kazak, Margarita S Avdontceva, Maria G Krzhizhanovskaya, Sergey N Vereshchagin","doi":"10.1107/S2052520625007413","DOIUrl":"10.1107/S2052520625007413","url":null,"abstract":"<p><p>The crystal structure of synthetic ludwigite-type oxoborate Cu₂FeO₂(BO₃) was first determined using in situ high-temperature single-crystal X-ray diffraction data collected at 300, 800 and 950 K. The structure is described as a heteropolyhedral framework composed of edge- and vertex-sharing [MO₆]^n- (M = Cu²⁺, Fe³⁺) octahedra that form extended zigzag chains in the bc plane with isolated trigonal planar [BO₃]^3- located in triangular cavities of the cationic framework. Oxo-centered [OM₄]ⁿ⁺ tetrahedra and [OM₅]ⁿ⁺ tetragonal pyramids are observed and described for the first time. The structure is disordered: the Cu1 and Cu3 sites are fully occupied by the Cu²⁺ ions, while the M2 and M4 sites are occupied by the Cu²⁺ and Fe³⁺ ions in ratios of 0.59:0.41 and 0.20:0.80, respectively. The O4 site is split into two sites, O4A and O4B, which leads to the formation of distorted [M2O₆]^n-, Cu3O₆]^n- and [M4O₆]^n- polyhedra. Thermal behavior of Cu₂FeO₂(BO₃) was investigated using in situ high-temperature single-crystal and powder X-ray diffraction, simultaneous thermal analysis and high-temperature heat capacity measurements. Unusual behavior of the unit-cell parameters and specific heat is observed at ∼690 K. The borate is stable up to ∼1040 K, when an incomplete solid-phase decomposition begins with the formation of CuO and (Cu,Fe)₃O₄ phases. The anisotropy of thermal expansion is weak and it is explained by (i) the preferable orientation of the most chemically rigid [BO₃]^3- units, (ii) the theory of shear deformations of the monoclinic ac plane and (iii) an arrangement of the oxo-centered [O₂M₇]ⁿ⁺ and [O₂M₈]ⁿ⁺ double chains. Volume expansion increases with an increase in temperature from 24.6 × 10^-6 K^-1 (at 300 K) to 35.4 × 10^-6 K^-1 (at 1000 K). The degree of anisotropy of the expansion of Cu₂FeO₂(BO₃) is similar to that of orthorhombic ludwigite-type oxoborates.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"457-465"},"PeriodicalIF":1.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}