Acta Crystallographica Section C Structural Chemistry最新文献

{"title":"Two polymorph modifications of tris(hexafluoroacetylacetonato)iron(III) revealed: is that common for other trivalent metals?","authors":"Joyce Chang, Julianna N Defeo, Zheng Wei, Evgeny V Dikarev","doi":"10.1107/S2053229624007575","DOIUrl":"10.1107/S2053229624007575","url":null,"abstract":"<p><p>A long-standing issue about the correct identification of an important starting reagent, iron(III) hexafluoroacetylacetonate, Fe(hfac)₃ (1), has been resolved. The tris-chelated mononuclear complex was found to crystallize in two polymorph modifications which can be assigned as the low-temperature (1-L) monoclinic P2₁/n and the high-temperature (1-H) trigonal P-3. Low-temperature polymorph 1-L was found to transform to 1-H upon sublimation at 44 °C. Two modifications are clearly distinguished by powder X-ray diffraction (PXRD), single-crystal X-ray diffraction, differential scanning calorimetry (DSC), and melting-point measurements. On the other hand, the two forms share similar characteristics in direct analysis in real-time mass spectrometry (DART-MS), attenuated total reflection (ATR) spectroscopy, and some physical properties, such as color, volatility, sensitivity, and solubility. Analysis of the literature and some of our preliminary data strongly suggest that the appearance of two polymorph modifications for trivalent metal (both transition and main group) hexafluoroacetylacetonates is a common case for several largely used complexes not yet accounted for in the crystallographic databases.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"567-575"},"PeriodicalIF":0.7,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142003367","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 structures of two unexpected products of vicinal diamines left to crystallize in acetone.","authors":"Bruno Dival, Leonardo Pitinato, Letícia Develly, Willian X C Oliveira","doi":"10.1107/S2053229624007320","DOIUrl":"10.1107/S2053229624007320","url":null,"abstract":"<p><p>Herein we report the crystal structures of two benzodiazepines obtained by reacting N,N'-(4,5-diamino-1,2-phenylene)bis(4-methylbenzenesulfonamide) (1) or 4,5-(4-methylbenzenesulfonamido)benzene-1,2-diaminium dichloride (1·2HCl) with acetone, giving 2,2,4-trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepine, C₂₆H₃₀N₄O₄S₂ (2), and 2,2,4-trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepin-1-ium chloride 0.3-hydrate, C₂₆H₃₁N₄O₄S₂⁺·Cl^-·0.3H₂O (3). Compounds 2 and 3 were first obtained in attempts to recrystallize 1 and 1·2HCl using acetone as solvent. This solvent reacted with the vicinal diamines present in the molecular structures, forming a 5H-1,5-benzodiazepine ring. In the crystal structure of 2, the seven-membered ring of benzodiazepine adopts a boat-like conformation, while upon protonation, observed in the crystal structure of 3, it adopts an envelope-like conformation. In both crystalline compounds, the tosylamide N atoms are not in resonance with the arene ring, mainly due to hydrogen bonds and steric hindrance caused by the large vicinal groups in the aromatic ring. At a supramolecular level, the crystal structure is maintained by a combination of hydrogen bonds and hydrophobic interactions. In 2, amine-to-tosyl N-H...O and amide-to-imine N-H...N hydrogen bonds can be observed. In contrast, in 3, the chloride counter-ion and water molecule result in most of the hydrogen bonds being of the amide-to-chloride and ammonium-to-chloride N-H...Cl types, while the amine interacts with the tosyl group, as seen in 2. In conclusion, we report the synthesis of 1, 1·2HCl and 2, as well as their chemical characterization. For 2, two synthetic methods are described, i.e. solvent-mediated crystallization and synthesis via a more efficient and cleaner route as a polycrystalline material. Salt 3 was only obtained as presented, with only a few crystals being formed.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"497-504"},"PeriodicalIF":0.7,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142034940","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, structure and red-light emission of a manganese halide directed by a methyldiphenylphosphine oxide complex.","authors":"Jia Wei Li, Mengyuan Niu, Wei Feng, Wenke Dong, Yanjie Liu, Jingjing Yang, Chunjie Wang, Hui Zhang, Wei Wu Song","doi":"10.1107/S2053229624006405","DOIUrl":"10.1107/S2053229624006405","url":null,"abstract":"<p><p>Controlling the optical activity of halide perovskite materials through modulation of the coordination configurations of the metal ions is important. Herein, a novel manganese-based halide, specifically diaquatetrakis(methyldiphenylphosphine oxide)manganese(II) tetrachloridomanganate(II), [Mn(C₁₃H₁₃OP)₄(H₂O)₂][MnCl₄] or [Mn(MDPPO)₄(H₂O)₂][MnCl₄] (MDPPO is methyldiphenylphosphine oxide), was synthesized through the solvothermal reaction of MnCl₂ with the neutral molecule MDPPO. In this compound, [Mn(MDPPO)₄(H₂O)₂]²⁺ acts as the cation, while [MnCl₄]^2- serves as the anion, enabling the co-existence of tetrahedral and octahedral structures within the same system. Remarkably, the compound exhibits efficient red-light emission at 662 nm, distinct from the green-light emission typically observed in MnX₄-based halides. Theoretical calculations show that the red emission comes from the charge transfer from the MDPPO to the Mn²⁺ of [MnCl₄]^2-. This work provides a new perspective for the design and synthesis of red-light-emitting manganese-based halides with unique structures.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"412-418"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141589413","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, spectroscopic and crystallographic characterization of various cymantrenyl thioethers [Mn{C₅H_xBr_y(SMe)_z}(PPh₃)(CO)₂].","authors":"Christian Klein-Hessling, Tobias Blockhaus, Karlheinz Sünkel","doi":"10.1107/S205322962400603X","DOIUrl":"10.1107/S205322962400603X","url":null,"abstract":"<p><p>Starting from [Mn(C₅H₄Br)(PPh₃)(CO)₂] (1a), the cymantrenyl thioethers [Mn(C₅H₄SMe)(PPh₃)(CO)₂] (1b) and [Mn{C₅H_4-nBr(SMe)_n}(PPh₃)(CO)₂] (n = 1 for compound 2, n = 2 for 3 and n = 3 for 4) were obtained, using either n-butyllithium (n-BuLi), lithium diisopropylamide (LDA) or lithium tetramethylpiperidide (LiTMP) as base, followed by electrophilic quenching with MeSSMe. Stepwise consecutive reaction of [Mn(C₅Br₅)(PPh₃)(CO)₂] with n-BuLi and MeSSMe led finally to [Mn{C₅(SMe)₅}(PPh₃)(CO)₂] (11), only the fifth complex to be reported containing a perthiolated cyclopentadienyl ring. The molecular and crystal structures of 1b, 3, 4 and 11 were determined and were studied for the occurrence of S...S and S...Br interactions. It turned out that although some interactions of this type occurred, they were of minor importance for the arrangement of the molecules in the crystal.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"383-393"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11299206/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141533364","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 and cryomagnetic study of a mononuclear erbium(III) oxamate inclusion complex.","authors":"Cleber R Araujo Junior, Willian X C Oliveira, Carlos B Pinheiro, Emerson F Pedroso, Wallace C Nunes, Adriele A de Almeida, Marcelo Knobel, Miguel Julve, Cynthia L M Pereira","doi":"10.1107/S2053229624005977","DOIUrl":"10.1107/S2053229624005977","url":null,"abstract":"<p><p>The synthesis, crystal structure and magnetic properties of an oxamate-containing erbium(III) complex, namely, tetrabutylammonium aqua[N-(2,4,6-trimethylphenyl)oxamato]erbium(III)-dimethyl sulfoxide-water (1/3/1.5), (C₁₆H₃₆N)[Er(C₁₁H₁₂NO₃)₄(H₂O)]·3C₂H₆OS·1.5H₂O or n-Bu₄N[Er(Htmpa)₄(H₂O)]·3DMSO·1.5H₂O (1), are reported. The crystal structure of 1 reveals the occurrence of an erbium(III) ion, which is surrounded by four N-phenyl-substituted oxamate ligands and one water molecule in a nine-coordinated environment, together with one tetrabutylammonium cation acting as a counter-ion, and one water and three dimethyl sulfoxide (DMSO) molecules of crystallization. Variable-temperature static (dc) and dynamic (ac) magnetic measurements were carried out for this mononuclear complex, revealing that it behaves as a field-induced single-ion magnet (SIM) below 5.0 K.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"349-356"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141562395","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 and characterization of monascin from the extracts of Monascus purpureus-fermented rice.","authors":"Jia Yin Xu, Han Qing Li, Jian Ming Chen, Feng Zheng Chen","doi":"10.1107/S2053229624006788","DOIUrl":"10.1107/S2053229624006788","url":null,"abstract":"<p><p>We present a novel solid form of monascin, an azaphilonoid derivative extracted from Monascus purpureus-fermented rice. The crystal structure, C₂₁H₂₆O₅, was characterized by single-crystal X-ray diffraction and belongs to the orthorhombic space group P2₁2₁2₁. To gain insight into the electronic properties of the short contacts in the crystalline state of monascin, we utilized the Experimental Library of Multipolar Atom Model 2 (ELMAM2) database to transfer the electron density of monascin in its crystalline state. Hirshfeld surface analysis, fingerprint analysis, electronic properties and energetic characterization reveal that intermolecular C-H...O hydrogen bonds play a crucial role in the noncovalent bonding interactions by connecting molecules into two- and three-dimensional networks. The molecular electrostatic potential (MEP) map of the monascin molecule demonstrates that negatively charged regions located at four O atoms are favoured binding sites for more positively charged amino acid residues during molecular recognition. In addition, powder X-ray diffraction confirms that no transformation occurs during the crystallization of monascin.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"425-433"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141722847","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 and Hirshfeld surface analysis of two iHOFs based on CH...NC hydrogen bonding.","authors":"Qiaoqi Qin, Jiamin Liu, Xinyu Luan, Jianqiao Xu, Long Jiang","doi":"10.1107/S2053229624005850","DOIUrl":"10.1107/S2053229624005850","url":null,"abstract":"<p><p>Two ionic hydrogen-bonded organic frameworks (iHOFs) assembled from 4-cyano-N-(4-cyanobenzyl)pyridinium, have been crystallized with Br^- and antimony(III) pentabromide, [SbBr₅]^2-, as counter-ions and characterized. These are 4-cyano-N-(4-cyanobenzyl)pyridinium bromide, C₁₄H₁₀N₃⁺·Br^-, and bis[4-cyano-N-(4-cyanobenzyl)pyridinium] antimony(III) pentabromide, (C₁₄H₁₀N₃)₂[SbBr₅]. The CH...NC interactions induced by templating anions construct disparate frameworks. Hirshfeld surface analysis indicated that these crystals exhibit two types of hydrogen-bonding interactions, specifically CH...NC and CH...Br. Consecutive reverse-parallel CH...NC hydrogen-bonding interactions in these crystals induced the formation of a large number of CH...NC bonds which exhibit both cis and trans configurations.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"419-424"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141589412","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":"A novel one-dimensional thiocyanate-bridged cobalt(III) complex: synthesis, crystal structure characterization and Hirshfeld surface analysis.","authors":"Uttam Mandal, Corrado Rizzoli, Bikash Chakraborty, Debasis Bandyopadhyay, Santanu Mandal","doi":"10.1107/S2053229624006375","DOIUrl":"10.1107/S2053229624006375","url":null,"abstract":"<p><p>A new one-dimensional thiocyanate-bridged cobalt(III) Schiff base complex, namely, catena-poly[[[4-bromo-2-((Z)-{[2-(thiophen-2-yl)ethyl]imino}methyl)phenolato-κ²N,O]cobalt(III)]-μ-thiocyanato-κ²N:S], [Co(SCN)(C₁₃H₁₁BrNOS)₂]_n or [Co(μ_1,3-SCN)L₂]_n (1), where HL is 4-bromo-2-((Z)-{[2-(thiophene-2-yl)ethyl]imino}methyl)phenol, a bidentate Schiff base prepared from the condensation reaction of 5-bromosalicylaldehyde and 2-(thiophen-2-yl)ethylamine, has been synthesized by stirring Co(ClO₄)₂·6H₂O, the Schiff base HL and ammonium thiocyanate (in a 1:2:1 molar ratio) in ethanol medium. The complex was characterized by FT-IR, electronic spectra and single-crystal X-ray diffraction (SC-XRD) studies. The SC-XRD data suggest that the compound crystallizes in the orthorhombic space group Pca2₁. The Co^III ion in 1 adopts a distorted octahedral geometry, the metal sites being six-coordinated by one thiocyanate N atom and one thiocyanate S atom in apical positions, and by two imine N atoms and two phenolate O atoms from two anionic L^- ligands which form the basal plane. The thiocyanate ligand acts as a μ-1,3 bridge, joining neighbouring Co^III atoms and forming a uniform zigzag one-dimensional polymeric chain. The crystallographic data were also used in the Hirshfeld surface (HS) analysis, which aimed to investigate the nature and quantitative significance of any noncovalent intermolecular interactions inside the crystal lattice. The crystal void parameters have also been computed and show the molecules to be tightly packed.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"394-400"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141562394","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":"Na[GeF₅]·2HF: the first quarternary phase in the H-Na-Ge-F system.","authors":"Valentin Bockmair, Constantin Hoch, Irina Schusterbauer, Andreas J Kornath","doi":"10.1107/S2053229624006338","DOIUrl":"10.1107/S2053229624006338","url":null,"abstract":"<p><p>The structure of cis- or trans-bridged [GeF₅]^- anionic chains have been investigated [Mallouk et al. (1984). Inorg. Chem. 23, 3160-3166] showing the first crystal structures of μ-F-bridged pentafluorogermanates. Herein, we report the second crystal structure of trans-pentafluorogermanate anions present in the crystal structure of sodium trans-pentafluorogermanate(IV) bis(hydrogen fluoride), Na[GeF₅]·2HF. The crystal structure [orthorhombic Pca2₁, a = 12.3786 (3), b = 7.2189 (2), c = 11.4969 (3) Å and Z = 8] is built up from infinite chains of trans-linked [GeF₆]^2- octahedra, extending along the b axis and spanning a network of pentagonal bipyramidal distorted Na-centred polyhedra. These [NaF₇] polyhedra are linked in a trans-edge fashion via hydrogen fluoride molecules, in analogy to already known sodium hydrogen fluorides and potassium hydrogen fluorides.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"401-406"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11299209/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141562409","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 the cytotoxic macrocyclic trichothecene Isororidin A.","authors":"Mostafa A Asmaey, Dimitris A Kalofolias, Maria Despoina Charavgi, Ismail R Abdel-Rahim, Evangelia D Chrysina, Dennis Abatis","doi":"10.1107/S2053229624006144","DOIUrl":"10.1107/S2053229624006144","url":null,"abstract":"<p><p>The highly cytotoxic macrocyclic trichothecene Isororidin A (C₂₉H₄₀O₉) was isolated from the fungus Myrothesium verrucaria endophytic on the wild medicinal plant `Datura' (Datura stramonium L.) and was characterized by one- (1D) and two-dimensional (2D) NMR spectroscopy. The three-dimensional structure of Isororidin A has been confirmed by X-ray crystallography at 0.81 Å resolution from crystals grown in the orthorhombic space group P2₁2₁2₁, with one molecule per asymmetric unit. Isororidin A is the epimer of previously described (by X-ray crystallography) Roridin A at position C-13' of the macrocyclic ring.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"407-411"},"PeriodicalIF":0.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11299208/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141562408","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}