Crystal Growth & Design最新文献

{"title":"Pharmaceutical Cocrystals and Salt of Ethionamide with Fluorobenzoic Acids for Improved Drug Delivery","authors":"Naveena S. Veeranagaiah,&nbsp;Madhu Rana,&nbsp;Battini Swapna,&nbsp;Raghavaiah Pallepogu* and Ashwini K. Nangia*,&nbsp;","doi":"10.1021/acs.cgd.4c0132310.1021/acs.cgd.4c01323","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01323https://doi.org/10.1021/acs.cgd.4c01323","url":null,"abstract":"<p >Ethionamide (ETH) is a second-line antituberculosis drug, but its aqueous solubility is poor. A cocrystal/salt screen of ETH with fluorobenzoic acid (FBA) coformers afforded four cocrystals and one salt of ETH, namely, ETH-4-fluorobenzoic acid (4FBA, cocrystal), ETH-3,4-difluorobenzoic acid (34DFBA, cocrystal), ETH-2,4,5-trifluorobenzoic acid (245TFBA, cocrystal), ETH-2,3,4,5-tetrafluorobenzoic acid (2345TFBA, cocrystal), and ethionamidium-2-fluoro-6-hydroxybenzoate (2F6HBA, salt). The new crystalline multicomponent cocrystal-salt (MCCS) forms were characterized by powder X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, single crystal X-ray diffraction, and FT-IR analysis. Structural analysis showed that the acid-pyridine, hydroxyl-pyridine, and thioamide dimer synthons stabilize ETH cocrystals/salt structures. The cocrystals/salt exhibit remarkable improvement in solubility, dissolution, and diffusion at pH 7 in phosphate buffer solution. The ability of fluoro compounds to increase membrane diffusion and bioavailability of drugs as MCCS complexes may be of general applicability for poor solubility and permeability drugs.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9824–9837 9824–9837"},"PeriodicalIF":3.2,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Soft Crystal Design for Discriminatory Gate Effect on Inverse Selective CO2/C2H2 Separation","authors":"Tao Jia,&nbsp;Ken-ichi Otake*,&nbsp;Yifan Gu,&nbsp;Yuiga Nakamura,&nbsp;Yoshiki Kubota,&nbsp;Shogo Kawaguchi,&nbsp;Jiang Wu,&nbsp;Fengting Li* and Susumu Kitagawa*,&nbsp;","doi":"10.1021/acs.cgd.4c0086810.1021/acs.cgd.4c00868","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00868https://doi.org/10.1021/acs.cgd.4c00868","url":null,"abstract":"<p >One-step purification of acetylene (C₂H₂) from carbon dioxide (CO₂) using CO₂-selective adsorbents is urgently needed but strategically challenging due to their similar physicochemical properties. In this work, we designed a series of isostructural flexible porous coordination polymers (PCPs) modulating the gate-opening pressure for C₂H₂ through linker substitution, preserving high CO₂ uptake at low pressure, and enabling a customizable inverse selectivity of CO₂/C₂H₂. By exploring both pillar and capping ligand substitutions, we found that pillar-ligand substitution in the PCPs allows rational control of the gate-opening behavior for C₂H₂ to achieve highly selective adsorption of CO₂ while discriminating C₂H₂, achieving high CO₂/C₂H₂ uptake ratio (8.5) and selectivity (232.5), which are comparable to other benchmark materials. Furthermore, dynamic breakthrough experiments suggest that our PCPs effectively achieve an inverse CO₂/C₂H₂ separation at 298 K and 1 bar. Consequently, high-purity C₂H₂ (&gt;99.5%) could be obtained from the CO₂/C₂H₂ mixture through a simple one-step column purification. Combining crystallographic structural analyses, we found that the significant structural deformation differences after pillar-ligand substitution compared with capping ligand substitution can rationally control the gate-opening behavior. This simple design strategy allows for reasonable control of the gating behavior of porous materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9425–9432 9425–9432"},"PeriodicalIF":3.2,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure, Cohesion Energetics, and Hydrogen Bonding Cooperativity in Fumaric Acid and Alkyl Fumarates: Insights from Experiment and Theory","authors":"António O. L. Évora,&nbsp;Daniel F. Valente-Matias,&nbsp;Carlos E. S. Bernardes*,&nbsp;Cláudio M. Lousada,&nbsp;M. Fátima M. Piedade,&nbsp;Matteo Lusi,&nbsp;Hermínio P. Diogo and Manuel E. Minas da Piedade*,&nbsp;","doi":"10.1021/acs.cgd.4c0089410.1021/acs.cgd.4c00894","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00894https://doi.org/10.1021/acs.cgd.4c00894","url":null,"abstract":"&lt;p &gt;Fumaric acid and alkyl fumarates are a family of structurally related compounds with a wide spectrum of potential or effective therapeutic applications. The series consisting of fumaric acid (FA), monomethyl fumarate (MMF), dimethyl fumarate (DMF), monoethyl fumarate (MEF), and diethyl fumarate (DEF) was studied in this work to address the following main questions: how does the number of OH···O hydrogen bonds that may be established due to systematic differences in molecular structure impacts on the molecular packing and lattice energetics? Is there evidence of a cooperative hydrogen bond strengthening when infinite 1D chains sustained by OH···O hydrogen bonds are formed? How well can the structural and energetic features of this series of related molecules be predicted by state-of-the art force field and periodic DFT procedures that are used in the rationalization or prediction of crystal structures and physical properties of molecular organic solids? By combining results from a variety of experimental (X-ray diffraction, Raman spectroscopy, DSC, Calvet drop-sublimation calorimetry) and theoretical (quantum mechanical, molecular dynamics simulations) methods, it was found that (&lt;i&gt;i&lt;/i&gt;) in all cases, the molecular packing leads to layered solids, where each layer consists of 1D chain motifs linked to each other through C–H···O interactions. (&lt;i&gt;ii&lt;/i&gt;) The 1D arrangements are determined by two main motifs: the &lt;i&gt;R&lt;/i&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;2&lt;/sup&gt;(8) carboxyl dimer, typically found in mono- and di-&lt;i&gt;n&lt;/i&gt;-alkyl carboxylic acids, and the staggered CH&lt;sub&gt;3&lt;/sub&gt;···H&lt;sub&gt;3&lt;/sub&gt;C synthon, which is present in mono-&lt;i&gt;n&lt;/i&gt;-alkyl carboxylic acids and &lt;i&gt;n&lt;/i&gt;-alkanes. This leads to the formation of carboxyl–carboxyl and alkyl–alkyl domains that are structurally isolated from each other. (&lt;i&gt;iii&lt;/i&gt;) The lattice energy, as measured by the enthalpy of sublimation (Δ&lt;sub&gt;sub&lt;/sub&gt;&lt;i&gt;H&lt;/i&gt;&lt;sub&gt;m&lt;/sub&gt;&lt;sup&gt;o&lt;/sup&gt;), varies according to FA &gt; MMF ∼ MEF &gt; DMF ∼ DEF and is linearly correlated with the number of OH···O hydrogen bonds present in the structures. (&lt;i&gt;iv&lt;/i&gt;) The larger enthalpy of sublimation of FA compared to MMF and MEF is linked to the number of OH···O hydrogen bonds but does not seem to be related to their individual strength. Examination of O···O distance and C═O stretching frequency as well as theoretically computed dissociation energies of dimeric FA, MMF, and MEF species suggests that the OH···O interaction is weaker in FA than in MMF and MEF. As such, the present study showed no evidence of a cooperative OH···O bond strengthening in FA, relative to MMF and MEF, due to the presence of infinite 1D chains sustained by carboxylic acid dimers. (&lt;i&gt;v&lt;/i&gt;) No evident connection between Δ&lt;sub&gt;sub&lt;/sub&gt;&lt;i&gt;H&lt;/i&gt;&lt;sub&gt;m&lt;/sub&gt;&lt;sup&gt;o&lt;/sup&gt; and compactness indicators such as density or Kitaigorodski packing index was also found. Finally, (&lt;i&gt;vi&lt;/i&gt;) MD simulations and periodic DFT calculations were both able to reproduce the above-mentioned Δ&lt;s","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9465–9481 9465–9481"},"PeriodicalIF":3.2,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Self-Assembly of a Fully Protected l-Dopa from Different Organic Solvents and the Relationship Between Gel and Crystal Structures","authors":"Fabia Cenciarelli,&nbsp;Claudia Tomasini,&nbsp;Simone d’Agostino* and Demetra Giuri*,&nbsp;","doi":"10.1021/acs.cgd.4c0124410.1021/acs.cgd.4c01244","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01244https://doi.org/10.1021/acs.cgd.4c01244","url":null,"abstract":"<p >We report here the self-assembly of a fully protected <span>l</span>-3,4-dihydroxyphenylalanine (Boc-<span>l</span>-Dopa(Bn)₂-OMe) under several conditions. Depending on the organic solvent or solvent mixture, this simple molecule self-assembles into different supramolecular structures, sometimes behaving as a low-molecular-weight gelator. Indeed, we observed the formation of organogels in alcohols, as confirmed by rheological analyses. In contrast, in solvent mixtures, long crystalline fibers were formed, and we could obtain single crystals suitable for X-ray diffraction analysis through a vapor diffusion technique. The deep X-ray diffraction analyses allowed us to determine the structure of the crystals, of the gels, and of the fiber-like aggregates and to deduce that the molecule always self-assembles like antiparallel β-sheets, driven by intermolecular hydrogen bonding and π–π stacking interactions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9331–9336 9331–9336"},"PeriodicalIF":3.2,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Formal Metal-Dependent (M = Pt, Pd) Switching between Arene π-Hole and σ-(Te)-Hole in the Arenetellurium(II) Noncovalent Binding","authors":"Anton V. Rozhkov*,&nbsp;Sergi Burguera,&nbsp;Antonio Frontera and Vadim Yu. Kukushkin*,&nbsp;","doi":"10.1021/acs.cgd.4c0110410.1021/acs.cgd.4c01104","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01104https://doi.org/10.1021/acs.cgd.4c01104","url":null,"abstract":"<p >The diketonate complexes M(acac)₂ (M = Pd (<b>1</b>), Pt (<b>2</b>)) were cocrystallized with bis(perfluoropyridin-4-yl)tellane (Py^F₂Te). Single-crystal X-ray studies of the resulting adducts revealed that the binding mode and stoichiometry between the coformers dramatically depend on the identity of metal sites. Pd(acac)₂ formed adduct <b>1</b>₃·(Py^F₂Te)₂ where Te···C_acac and π_hole···Pd noncovalent interactions were detected. In contrast to <b>1</b>, Pt(acac)₂ formed adduct <b>2</b>·Py^F₂Te where the Te···Pt metal-involving chalcogen bond was observed. Various DFT methods, including the calculation of fully optimized dimeric assemblies and their mutated dimers, allowed for a detailed examination of the corresponding metal-involving noncovalent interactions. Our findings support the notion that metal-involving interactions are the primary structure-determining factors, and the formal transition to the Te···Pt chalcogen bond can be attributed to the increased <i>d</i>_<i>z</i>²-nucleophilicity of the platinum atom compared to the palladium site.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9581–9589 9581–9589"},"PeriodicalIF":3.2,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of Br···O Bonding on the Chiral Assembly of Brominated Amides in the Crystalline Phase","authors":"Shoko Kikkawa*,&nbsp;Miho Takeno,&nbsp;Taku Nakayama,&nbsp;Daiki Koike,&nbsp;Yuuki Saito,&nbsp;Masako Tashiro,&nbsp;Yu Aoyama,&nbsp;Hidemasa Hikawa and Isao Azumaya*,&nbsp;","doi":"10.1021/acs.cgd.4c0109210.1021/acs.cgd.4c01092","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01092https://doi.org/10.1021/acs.cgd.4c01092","url":null,"abstract":"<p >A cyclic triamide of 2,5-dibromo-4-ethylaminobenzoic acid, which has a fixed axial chirality, was prepared in racemic and enantiopure forms. The structures of the corresponding crystals and homochiral molecular assembly formation were analyzed from the viewpoint of intermolecular interactions. Although the packing arrangements in the two types of crystals were similar, the packing difference suggested the importance of the C═O···Br–C contact for the chiral assembly. A statistical analysis of amides with the above contact revealed a correlation between the molecular assembly type (hetero- or homochiral) and the contact angle of adjacent molecules interacting through C═O···Br bonding. Specifically, in the absence of aryl groups, the O···Br–C angles closer to 180° facilitated the assembly of molecule pairs into a chiral arrangement. In contrast, the opposite trend was observed in the presence of one or more aryl groups. Furthermore, the chiral and racemic crystals displayed different preferences for the C═O···Br angle, indicating its importance in determining crystal chirality. Our approach extended the scope of the previously reported method and demonstrated its applicability to compounds with other skeletons.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9564–9570 9564–9570"},"PeriodicalIF":3.2,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Formation of Planar π-Conjugated Sheets in Cocrystals of Bis(iodoethynyl)pyridines and Bipyrimidylalkynes: Cooperative C–H···N Hydrogen Bonds and sp-C–I···N Halogen Bonds","authors":"Lydia B. Lang,&nbsp;Nathan P. Bowling and Eric Bosch*,&nbsp;","doi":"10.1021/acs.cgd.4c0126410.1021/acs.cgd.4c01264","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01264https://doi.org/10.1021/acs.cgd.4c01264","url":null,"abstract":"<p >The cocrystallization of the ditopic halogen bond donors 2,5-, 2,6-, 3,5-bis(iodoethynyl)pyridines with the dipyrimidyls 1,2-bis(5-pyrimidyl)ethyne and 1,4-bis(5-pyrimidyl)butadiyne is explored. The cocrystal components have complementary shapes and functional groups so that the noncovalent C–I···N halogen bonding and C–H···N hydrogen bonding interactions are complementary resulting in 1:1 cocrystals with the ditopic halogen bond accepting bipyrimidyls. The cocrystals feature π-stacked planar sheets of alternating bis(iodoalkynes) and bipyrimidyls held together in one direction by I···N halogen bonds and in the roughly orthogonal direction by pyridine–pyridine and pyrimidine–pyrimidine C–H···N hydrogen bonds.</p><p >Cooperative C–H···N hydrogen bonding and sp-C–I···N halogen bonding in a series of bis(iodoalkynyl)pyridines and bipyrimidines results in the formation of planar conjugated sheets within the cocrystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9727–9734 9727–9734"},"PeriodicalIF":3.2,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01264","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671473","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study on Triflumezopyrim Solid Forms: Crystal Structure Analysis and Suspension Concentrate Application Insights","authors":"Mingxia Wang,&nbsp;Xiaoyan Li,&nbsp;Bin Zhu,&nbsp;Guo-Bin Ren,&nbsp;Ming-Hui Qi*,&nbsp;Zhong Li and Xiaoyong Xu*,&nbsp;","doi":"10.1021/acs.cgd.4c0113410.1021/acs.cgd.4c01134","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01134https://doi.org/10.1021/acs.cgd.4c01134","url":null,"abstract":"<p >Polymorphism in solid molecules is increasingly recognized in the field of agriculture. Triflumezopyrim (TFM) is a pioneering mesoionic insecticide that has played a pivotal role in the control of resistant rice hoppers, yet studies of its polymorphs are scarce. This study systematically investigated the polymorphism of Triflumezopyrim, identifying four new polymorphs (Forms II–V), a hydrate (Form H), and an amorphous form. The crystal structures of Forms III, V, and H were identified by single-crystal X-ray diffraction analysis for the first time. Solubility, dissolution, and stability tests were conducted. Thermal analysis, solvent-mediated transformation experiments, and lattice energy calculations clarified the transformation relationships among the different forms, identifying Form V as the most thermodynamically stable polymorph with the lowest solubility. Furthermore, Forms I, II, V, and H were formulated as suspension concentrates, and their formulation capabilities and bioactivity were tested. Moreover, the fluorescence change of different solid polymorphs was observed. The analysis of the weak interaction in the single-crystal structure revealed that the change in the π–π packing pattern was the possible reason for the observed fluorescence change. These findings significantly enrich our understanding of the solid-state properties of Triflumezopyrim and provide substantial guidance for future processing and formulation selection.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9631–9648 9631–9648"},"PeriodicalIF":3.2,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Topochemical Fluorination of Epitaxial Thin Films of Barium-Doped Bismuth Iron Oxyfluoride","authors":"Mizuho Sano,&nbsp;Akiko Kamigaito,&nbsp;Yusuke Wakayama,&nbsp;Kei Shigematsu,&nbsp;Tsukasa Katayama,&nbsp;Yasushi Hirose and Akira Chikamatsu*,&nbsp;","doi":"10.1021/acs.cgd.4c0055210.1021/acs.cgd.4c00552","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00552https://doi.org/10.1021/acs.cgd.4c00552","url":null,"abstract":"<p >Topochemical fluorination of epitaxial transition-metal oxide thin films is one of the superior methods for producing single-crystalline transition-metal oxyfluoride thin films with fascinating physical and chemical properties. In this study, we explore the topochemical fluorinations using polyvinylidene difluoride for epitaxial thin films of Ba-doped bismuth ferrite, a multiferroic related material, at different fluorination temperatures. Epitaxial thin films of perovskite-type bismuth iron oxyfluoride (Bi_0.8Ba_0.2FeO_{2.9–<i>x</i>}F_2<i>x</i>) were obtained with different F contents through fluorination at 200–300 °C. Increasing the fluorination temperature to 350 °C yielded an Aurivillius-type epitaxial film with partial iron oxide byproducts. Additionally, while BiFeO₃ has been proposed for various optical applications due to its visible optical bandgap (2.2–2.7 eV), we observed a further reduction in the bandgap upon fluorination: 2.0, 2.0, and 1.6 eV for the as-grown oxide, perovskite-type oxyfluoride, and Aurivillius-type oxyfluoride films with partial iron oxide byproducts, respectively. These findings demonstrate the significant influence of fluorination conditions on the crystal structure and electronic states of Ba-doped bismuth ferrite, offering a pathway for tailored tuning of its properties.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9344–9349 9344–9349"},"PeriodicalIF":3.2,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Formation of Planar π-Conjugated Sheets in Cocrystals of Bis(iodoethynyl)pyridines and Bipyrimidylalkynes: Cooperative C-H···N Hydrogen Bonds and sp-C-I···N Halogen Bonds.","authors":"Lydia B Lang, Nathan P Bowling, Eric Bosch","doi":"10.1021/acs.cgd.4c01264","DOIUrl":"10.1021/acs.cgd.4c01264","url":null,"abstract":"<p><p>The cocrystallization of the ditopic halogen bond donors 2,5-, 2,6-, 3,5-bis(iodoethynyl)pyridines with the dipyrimidyls 1,2-bis(5-pyrimidyl)ethyne and 1,4-bis(5-pyrimidyl)butadiyne is explored. The cocrystal components have complementary shapes and functional groups so that the noncovalent C-I···N halogen bonding and C-H···N hydrogen bonding interactions are complementary resulting in 1:1 cocrystals with the ditopic halogen bond accepting bipyrimidyls. The cocrystals feature π-stacked planar sheets of alternating bis(iodoalkynes) and bipyrimidyls held together in one direction by I···N halogen bonds and in the roughly orthogonal direction by pyridine-pyridine and pyrimidine-pyrimidine C-H···N hydrogen bonds.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9727-9734"},"PeriodicalIF":3.2,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11583210/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142708565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}