Journal of Chemical Crystallography最新文献

{"title":"Synthesis, Spectroscopy and Crystal Structure Analysis of N1,N3-dicyclohexyl-N1-(all-trans-retinoyl)urea","authors":"Eleanna Vachlioti,&nbsp;Stefania Kalantzi,&nbsp;Dionissios Papaioannou,&nbsp;Vassilios Nastopoulos","doi":"10.1007/s10870-021-00917-x","DOIUrl":"10.1007/s10870-021-00917-x","url":null,"abstract":"<div><p>The title compound, C₃₃H₅₀N₂O₂, is a side product in the reaction of <i>all-trans</i>-retinoic acid (atRA) with <i>N</i>-hydroxysuccinimide, in the presence of the coupling agent <i>N</i>,<i>N</i>′-dicyclohexylcarbodiimide, which produces the ‘active’ ester succinimidyl <i>all-trans</i>-retinoate as the product. It crystallizes in the orthorhombic <i>Pbca</i> space group. The compound was characterized by ¹H-NMR, ¹³C-NMR, ESI–MS and IR spectroscopy and its structure was determined by single-crystal X-ray diffraction. For example in the ¹³C-NMR spectrum, diagnostic peaks are those of the two amide carbonyl C atoms at <i>δ</i> 169.5 and 154.2 ppm, the ten olefinic C atoms of the unsaturated chain of atRA moiety at <i>δ</i> 149.0, 139.3, 137.7, 137.3, 134.9, 130.2, 130.0, 129.4, 128.5 and 121.5 ppm and the two methine C atoms of the <i>N</i>,<i>N</i>′-dicyclohexylurea moiety at <i>δ</i> 57.9 and 49.5 ppm. Detailed analysis of its molecular and supramolecular structure showed that close-packing principles (elongated shape/large hydrophobic region of the molecule) together with chemical factors (N–H⋯O and C–H⋯O intermolecular interactions) direct the 3D self-assembly process in the crystalline state. Hirshfeld surface analysis was employed, a powerful approach to quickly and easily gain insight into molecular environments in the crystalline state.</p><h3>Graphical Abstract</h3><p>The synthesis and X-ray structure of 1-((2<i>E</i>, 4<i>E</i>, 6<i>E</i>, 8<i>E</i>)-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-1-enyl)nona-2,4,6,8-tetraenoyl)-1,3-dicyclohexylurea, a side product in the synthesis of succinimidyl <i>all-trans</i>-retinoate, is reported; Hirshfeld surface analysis was employed to identify intermolecular interactions.</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"260 - 269"},"PeriodicalIF":0.8,"publicationDate":"2022-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4209435","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 Two 4-Nitro-N-methylaniline Derivatives","authors":"Patricia E. Goettler,&nbsp;Christopher G. Hamaker","doi":"10.1007/s10870-021-00918-w","DOIUrl":"10.1007/s10870-021-00918-w","url":null,"abstract":"<div><p>The two related structures 2,4-dinitro-<i>N</i>-methylaniline (<b>1</b>) and 2-amino-4-nitro-<i>N</i>-methylaniline (<b>2</b>), both differ in the nitrogen substitution in the 2-position. Both structures are very similar with <i>N</i>-methylamino and 4-nitro groups that are nearly coplanar with the benzene ring. In compound <b>1</b>, the <i>ortho</i> nitro group is also nearly coplanar with the benzene ring. In compound <b>2</b>, the <i>ortho</i> nitro group has been reduced to an amino moiety. The amino group in <b>2</b> is pyramidal. Both molecules display intermolecular N–H⋯O and C–H⋯O interactions. Compound <b>1</b> forms chains via N–H⋯O interactions which are linked together to form an extended structure via N–H⋯O and N⋯O interactions. Compound <b>2</b> forms centrosymmetric dimers through N–H⋯O interactions which form 2-dimensional sheets via further hydrogen bonding. Both compounds crystallize in the space group <i>P</i>2₁/<i>c</i> with <i>Z</i> = 4 and have very similar volumes, 799.12(5) ų for <b>1</b> and 749.36(8) ų for <b>2</b>.</p><h3>Graphical Abstract</h3><p>Two related 4-nitro-<i>N</i>-methylaniline derivatives, 2,4-dinitro-<i>N</i>-methylaniline (<b>1</b>) and 2-amino-4-nitro-<i>N</i>-methylaniline (<b>2</b>), have been analyzed by X-ray crystallography. The shapes of the molecules are very similar, but they have very different intermolecular interactions.</p>\u0000 <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\u0000 </div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"251 - 259"},"PeriodicalIF":0.8,"publicationDate":"2022-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10870-021-00918-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4123505","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":"Interhalogen 1,2,3-Triazolium Ionic Liquid: Synthesis, Crystal Structure, Hirshfeld Surface Analysis and Photophysical Properties","authors":"Siyabonga G. Mncube,&nbsp;Sizwe J. Zamisa,&nbsp;Muhammad D. Bala","doi":"10.1007/s10870-021-00912-2","DOIUrl":"10.1007/s10870-021-00912-2","url":null,"abstract":"<div><p>A new interhalogen ionic liquid [C₁₇H₂₅N₃Br]⁺[IBr₂]⁻ (<b>IL-1</b>) was synthesized from its triazolium iodide precursor [C₁₇H₂₆N₃⁺I⁻] in THF under cold and basic conditions. X-ray diffraction data showed that <b>IL-1</b> is composed of two moieties contained in a triclinic unit cell; the five-membered triazolium cation and an almost linear iodidobromide anion, IBr₂⁻. The Br atoms of the anion form quadfurcated C–H···Br hydrogen bonds with neighbouring cationic halo-1,2,3-triazolium H-species. Intermolecular Br···Br halogen bonds and I···π_triazole interactions form a distinctive ring-like pattern that links together four molecular units in the crystal packing. Hirshfeld surface analysis revealed that the most significant <i>d</i>_norm surface contribution at 59% is due to H···H and reciprocal C···H contacts, while the Br···Br contacts only contributed 3%. The prevalence of extensive H···H and C···H contacts is potentially due to the linear aliphatic chain, the <i>N</i>-octyl wingtip substituent of the triazolyl moiety. The Hirshfeld surface mapping also shows the contribution of intermolecular C–H···Br interactions at 26% of all contacts. The title compound (<b>IL-1</b>) showed interesting photophysical properties in MeCN solution, with an absorption band at 254 nm and two-shoulder emission bands due to strong π → π^∗ transitions from the triazolium moiety, indicating the presence of two energetically associated species.</p><h3>Graphical Abstract</h3><p>Structural and photophysical studies on a new ionic liquid compound containing a mixed halide anion [C₁₇H₂₅N₃Br]⁺[IBr₂]⁻ have yielded important results on intermolecular interactions between the triazolium cation and the iodidobromide counterion.</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"242 - 250"},"PeriodicalIF":0.8,"publicationDate":"2021-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4624969","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":"Preparation, Properties and Crystal Structure of syn-Isomer of 2,6-Dichlorophenyl-cyanoxime, H(2,6-diCl-PhCO): Potent Carbonyl Reductase Inhibitor","authors":"Seth Adu Amankrah,&nbsp;Oleksandr Hietsoi,&nbsp;Sergiy Tyukhtenko,&nbsp;Nikolay Gerasimchuk,&nbsp;Henry Charlier","doi":"10.1007/s10870-021-00905-1","DOIUrl":"10.1007/s10870-021-00905-1","url":null,"abstract":"<p>The oximino(2,6-dichlorophenyl)acetonitrile, H(2,6-diCl-PhCO) has been synthesized in a reasonably high yield of 60%, and characterized using a variety of physical, electrochemical, spectroscopic methods and X-ray analysis. This compound belongs to the family of cyanoximes; a new subclass of oximes with the general formula NC–C(=N–OH)–R (where R is an electron-withdrawing group) which recently emerged as new biologically active compounds. This cyanoxime represents a disubstituted arylcyanoxime that was found to be a powerful inhibitor of the <i>Carbonyl Reductase</i> enzyme involved in the developing of resistance to anticancer treatment, and the making of cardiotoxic derivatives of anthracyclines that are currently used in medicine. The oximino(2,6-dichlorophenyl)acetonitrile, H(2,6-diCl-PhCO) is a weak acid with pKa = 6.17 and does not dissociate in organic polar protic and aprotic solvents. The cyanoxime was obtained as a microcrystalline mixture of two diastereomers (<i>anti-</i> and <i>syn-</i>) and deprotonates in solutions with the formation of yellow anions which exhibit solvatochromic behavior. However, one specific diastereomer—<i>syn</i>—was isolated in crystalline form from a solvent system as colorless blocks overlayed with pentane ether solution in a monoclinic system in a P2/c (#13) space group with unit cell parameters: <i>a</i> = 8.1720(2), <i>b</i> = 8.8013(3), <i>c</i> = 13.0146(4) and β = 102.546(3); Z = 4. A single crystal was studied using filtered CuK_a radiation, providing R_int value of 0.0348 from a full-sphere of reflections. A crystal structure was solved using direct methods, and well refined to R1 = 0.0459, wR2 = 0.1268 and GOF = 1.107. The studied specimen of oximino(2,6-dichlorophenyl)acetonitrile, H(2,6-diCl-PhCO), represents a highly non-planar, rare syn-diastereomer in which the oxime fragment is positioned towards the chlorinated phenyl group. In the crystal, the compound forms a columnar structure extended along the c-direction by using slipped π–π stacking interactions. Columns are interconnected via H-bonding between the oxime OH-group and N atom of the nitrile group with the following parameters: N–H = 1.841 Å, and 169.20° N···H–O angle. No thermal interconversion of <i>syn</i>- into <i>anti-</i> diastereomer was observed upon heating of crystals of one isomer under flow of Ar.</p>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"194 - 204"},"PeriodicalIF":0.8,"publicationDate":"2021-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10870-021-00905-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5105540","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":"Cu(NH2SO3) π-Complexes with Allyl Derivatives of 1,3,4-Thiadizoles: Synthesis and Structural Formation Through Weak Interactions","authors":"Yurii I. Slyvka,&nbsp;Evgeny А. Goreshnik,&nbsp;Nazariy T. Pokhodylo,&nbsp;Marian G. Mys’kiv","doi":"10.1007/s10870-021-00906-0","DOIUrl":"10.1007/s10870-021-00906-0","url":null,"abstract":"<p>This work is directed toward the synthesis and structure characterization of the two novel copper(I) sulfamate π,σ-complexes [Cu₂(Thiaz2)₂(NH₂SO₃)₂] (<b>1</b>) and [Cu₂(Thiaz3)(NH₂SO₃)₂]·2H₂O (<b>2</b>) based on 2-amino-5-allylthio-1,3,4-thiadiazole (Thiaz2) and <i>N</i>²,<i>N</i>⁵-di(allyl)-1,3,4-thiadiazole-2,5-diamine (Thiaz3) ligands. Structural analysis of <b>1</b> was performed in comparison with the earlier-studied, similar complex [Cu₂(Thiaz1)₂(NH₂SO₃)₂] (<b>3</b>) (Thiaz1-2-allylamino-5-methyl-1,3,4-thiadiazole). In the structures of <b>1</b>–<b>3</b>, the respective organic molecule fully realizes its coordination ability being attached to the metal centres through two nitrogen atoms of 1,3,4-thiadiazole core as well as by one <i>η</i>²-allyl groups in <b>1</b> and <b>3</b> or by two <i>η</i>²-allyl groups in <b>2</b>. In crystal structures of <b>1</b> &amp; <b>2</b>, [Cu₂(Thiaz)₂(NH₂SO₃)₂] dimers are interconnected by N–H⋯O hydrogen bonds into layers, while water molecules in <b>2</b> connect NH₂SO₃⁻ anions into hydrogen-bonded ribbon which together with N–H⋯O bonds of Thiaz3 amino-groups stitch organometallic fragments into a framework. To depict H-bonded interaction in the structures <b>1</b>–<b>3</b> Hirshfeld surface analysis has been performed.</p><p>The synthesis and X-ray structures of Cu(NH₂SO₃) π,σ-complexes based on allyl-substituted 1,3,4-thiadiazole ligands are presented and weak interactions are specially discussed.\u0000</p>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"205 - 213"},"PeriodicalIF":0.8,"publicationDate":"2021-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10870-021-00906-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5098806","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":"N,N′-Di(pyridine-4-yl)-pyridine-3,5-dicarboxamide, a Pincer-Type Tricationic Compound; Synthesis, Crystal Structure, Hirshfeld Surface Analysis, and Computational Chemistry Studies","authors":"Bitrus Bikimi Ayiya,&nbsp;Obinna Chibueze Okpareke","doi":"10.1007/s10870-021-00902-4","DOIUrl":"10.1007/s10870-021-00902-4","url":null,"abstract":"<p>The synthesis, structure, and spectroscopic characterization of a pincer-type compound; <i>N,N</i>′-di(pyridine-4-yl)-pyridine-3,5-dicarboxamide is described_. The tricationic pro-ligand (C₂₀H₂₂N₅O₂)³⁺ bearing two pendant alkylated 4-pyridyl arms at the 3,5-positions of the central pyridyl group features three triflate anions (CF₃SO₃⁻) in the asymmetric unit. Two of the triflate ligands in the structure are connected to the pincer cation by strong N–H⋯O hydrogen bonds. The central <i>N</i>-methyl moiety is planar to a r.m.s deviation of 0.01, and the two adjacent <i>N</i>-methylpyridine moieties are out of the plane with dihedral angles of 33.62° (3) and 86.08° (3). The molecular packing structure of the compound shows an 18-molecule aggregate in a 3-dimensional supramolecular synthon stabilized by intermolecular N–H⋯O and C–H⋯O contacts. The Hirshfeld surface analysis and fingerprint plots show that the OH/HO contacts resulting from C–H⋯O intermolecular interactions contributed significantly to the overall surface interaction with a total percentage contribution of 35.4%. The pairwise interaction energy calculations were implemented with a Gaussian plugin in Crystal Explorer 17 at the B3LYP/6-31G(d,p) level of theory. Energy profile diagrams and interaction energy values indicate that the crystal structure was stabilized by a combination of electrostatic and dispersion forces in the crystal lattice.</p><p>The crystal structure of a tricationic pro-ligand <i>N,N</i>′-di(pyridine-4-yl)-pyridine-3,5-dicarboxamide is described. The structures features three triflate anions in the asymmetric unit with two of the triflate ligands in the structure connected to the pincer pro-ligand by strong N–H⋯O hydrogen bonds. Hirshfeld surface interaction and pairwise interaction energies are explored.</p>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"174 - 184"},"PeriodicalIF":0.8,"publicationDate":"2021-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4558762","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":"Alkylpyridinium lodobismuthates(III)","authors":"Robert D. Pike,&nbsp;Neal E. Marshall,&nbsp;Abigail L. Martucci","doi":"10.1007/s10870-021-00901-5","DOIUrl":"10.1007/s10870-021-00901-5","url":null,"abstract":"<div><p>The reaction of N-alkyl pyridinium iodide salts (RPy⁺I⁻, R = Me, Et, ^<i>n</i>Pr, ^<i>n</i>Bu) with BiI₃ produced various alkyl pyridinium iodobismuthate(III) compounds, (RPy)_y−3x[Bi_xI_y]. A wide nuclearity range was observed in the iodobismuthate(III) clusters when crystallized from acetone/acetonitrile: For R = Me, the dominant phase, {(MePy)[BiI₄]}_n, is a chain of edge-sharing BiI₆ octahedra. Another phase, (MePy)₃[Bi₂I₉]‧MeCN, has a face-sharing dimer of BiI₆ octahedra. Five phases are reported for R = Et: (EtPy)₃[Bi₂I₉]·<span>({raise0.5exhbox{$scriptstyle 2$} kern-0.1em/kern-0.15em lower0.25exhbox{$scriptstyle 3$}})</span> MeCN, (EtPy)₃[Bi₃I₁₂], (EtPy)₃[Bi₃I₁₂]·MeCN (a new V-shaped trimeric anion structural type), (EtPy)₄[Bi₄I₁₆], and (EtPy)₄[Bi₆I₂₂]·2MeCN. Two R = ^<i>n</i>Pr phases were found: (PrPy)₃[Bi₂I₉] and (PrPy)₄[Bi₄I₁₆]·MeCN. Two phases were also found for R = ^<i>n</i>Bu: (BuPy)₃[Bi₂I₉] and (BuPy)₄[Bi₄I₁₆]. Bulk synthesized products shown diffraction matches to {(MePy)[BiI₄]}_n, (EtPy)₃[Bi₃I₁₂], (PrPy)₄[Bi₄I₁₆], and (BuPy)₄[Bi₄I₁₆], respectively. Thermal analysis of all four bulk compounds showed near complete mass loss above 300 °C.</p><h3>Graphic Abstract</h3><p>The structures, phases, and thermal behavior of N-alkyl pyridinium iodobismuthate(III)\u0000compounds (RPy)_y−3x[Bi_xI_y] (R = Me, Et, ^<i>n</i>Pr, ^<i>n</i>Bu) are presented and discussed.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"161 - 173"},"PeriodicalIF":0.8,"publicationDate":"2021-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10870-021-00901-5","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4960304","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":"Identification of Seven-coordinate LnIII Ions in a LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl Species Crystallized from Methanol and Pyridine","authors":"Elizabeth S. Biros,&nbsp;Cassandra L. Ward,&nbsp;Matthew J. Allen,&nbsp;Jacob C. Lutter","doi":"10.1007/s10870-021-00900-6","DOIUrl":"10.1007/s10870-021-00900-6","url":null,"abstract":"<div><p>The title metallacrown (MC) complexes Ln^III[15-MC_Fe^III_N(shi)-5](OAc)₂Cl(C₅H₅N)₆ (<b>Ln1</b>), where OAc^– is acetate, shi³⁻ is salicylhydroximate, and Ln = Gd and Dy, were synthesized via a self-assembly reaction in methanol and pyridine. Single crystals were grown using slow evaporation and characterized using X-ray diffraction. Seven-coordinate capped octahedron geometries were observed for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species. The 15-MC-5 is a ruffled metallacrown archetype similar to previously reported mixed-valent manganese metallacrowns.</p><h3>Graphic Abstract</h3><p>The title metallacrown (MC) complexes Ln^III[15-MC_Fe^III_N(shi)-5](OAc)₂Cl(C₅H₅N)₆ (<b>Ln1</b>), where OAc^– is acetate, shi³⁻ is salicylhydroximate, and Ln = Gd and Dy, contains seven-coordinate capped octahedron geometries for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species.</p>\u0000 <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\u0000 </div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"152 - 160"},"PeriodicalIF":0.8,"publicationDate":"2021-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10870-021-00900-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4814433","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":"Structural and Conformational Analysis of 1-Butyl-3-methylimidazolium Nitrate","authors":"Dean H. Johnston,&nbsp;Mallory Gasbarre,&nbsp;Carolanne E. Norris","doi":"10.1007/s10870-021-00899-w","DOIUrl":"10.1007/s10870-021-00899-w","url":null,"abstract":"<div><p>The crystal structures of two polymorphic forms of 1-butyl-3-methylimidazolium nitrate are reported. The form observed at 100 K and 200 K (<b>Ia</b> and <b>Ib</b>) crystallizes in the <span>(P{bar{1}})</span> space group and contains two independent imidazolium cations and nitrate anions. At 100 K the butyl chain of one cation adopts a TT (<i>trans</i>–<i>trans</i>) conformation and the other cation adopts a G′G′ (<i>gauche</i>–<i>gauche</i>) conformation. At 200 K, the G′G′ chain is disordered with about twelve percent of the GT conformation present. A different polymorph (Form <b>II</b>, also crystallizing in the <span>(P{bar{1}})</span> space group with two independent ion pairs) is present at 273 K displaying significant disorder in the butyl chains with a mixture of G′T, G′G′, and GT conformers. Raman spectra were collected on samples between 100 and 350 K and show changes in band frequencies and intensities consistent with conversion between different butyl chain conformations. Hydrogen bond interactions are present between cation C–H’s and oxygen atoms of the nitrate ions, with significant lengthening observed for three of the six close contacts (and formation of one new contact) upon conversion to the higher-temperature form. The structural details revealed in this study shed light on the intermolecular forces and the conformational changes that accompany phase changes in 1-butyl-3-methylimidazolium nitrate.</p><h3>Graphic Abstract</h3><p>X-ray diffraction and Raman spectroscopy of the ionic liquid 1-butyl-\u00003-methylimidazolium nitrate at temperatures from 100 to 300 K show\u0000evidence of two different polymorphs and significant temperature-dependent\u0000conformational changes.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"140 - 151"},"PeriodicalIF":0.8,"publicationDate":"2021-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10870-021-00899-w","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4928062","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":"Molecular and Crystal Structures of Some Fluorocymantrenes","authors":"Karlheinz Sünkel,&nbsp;Christian Klein-Heßling","doi":"10.1007/s10870-021-00898-x","DOIUrl":"10.1007/s10870-021-00898-x","url":null,"abstract":"<div><p>The crystal and molecular structures of the fluorocymantrenes [(C₅H₄F)Mn(CO)₃] and [(C₅H_5−nF_n)Mn (CO)₂(PPh₃)] (n = 1–3) have been studied. The influence of the phosphine for carbonyl substitution on the bond parameters is larger than the influence of the increasing fluorine content. In most cases the Mn → P vector is in a transoid position relative to the fluorine substituents, and therefore the conformational parameters of the PPh₃ propeller are in these cases very similar. The crystal structures show many intermolecular C–H⋯O hydrogen bonds and only very few C–H⋯F hydrogen bonds.</p><h3>Graphic Abstract</h3><p>The influence of the phosphine for carbonyl substitution on the bond parameters of the fluorocymantrenes [(C₅H₄F)Mn(CO)₃] and [(C₅H_5−nF_n)Mn (CO)₂(PPh₃)] (n = 1–3) is larger than the influence of the increasing fluorine content.</p>\u0000 <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\u0000 </div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"52 2","pages":"131 - 139"},"PeriodicalIF":0.8,"publicationDate":"2021-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10870-021-00898-x","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4865335","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}