Acta Crystallographica Section C Structural Chemistry最新文献

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.

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.

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.

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.

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.

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.

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.

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.

Ruxolitinib {RUX; systematic name: (3R)-3-cyclopentyl-3-[4-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]propanenitrile, C₁₇H₁₈N₆} is an orally bioavailable JAK1/2 inhibitor approved for treating intermediate- or high-risk myelofibrosis (MF) and high-risk polycythemia vera (PV). Recent patents claim that RUX can exist in many different forms, information for which is important for the clinical utilization of RUX, especially for the formulation and bioavailability of the drug. But there has been no detailed study on its forms so far. Herein crystals of RUX and its dihydrate (RUX-2H; C₁₇H₁₈N₆·2H₂O) and phosphate (RUX-P; systematic name: 4-{1-[(1R)-2-cyano-1-cyclopentylethyl]-1H-pyrazol-4-yl}-7H-pyrrolo[2,3-d]pyrimidin-3-ium dihydrogen phosphate, C₁₇H₁₉N₆⁺·H₂PO₄^-) were prepared successfully and their structures studied in detail for the first time. Our study shows that the three crystals of RUX differ in the orientation of the pyrimidine ring relative to the pyrazole ring of the RUX molecule, and in their hydrogen-bond interactions. The water molecules in RUX-2H and the dihydrogen phosphate anion in RUX-P enrich the hydrogen-bond networks in these forms. The expected proton transfer occurs in RUX phosphate and the protonated N atom is engaged in a charge-assisted hydrogen bond with the counter-anion. Hydrogen-bonding interactions dominate in the crystal packing of the three forms. The detailed conformations and packing of the three forms were compared through the calculation of both Hirshfeld surfaces and fingerprint plots.

The title compound, 3-[(benzo-1,3-dioxol-5-yl)amino]-4-methoxycyclobut-3-ene-1,2-dione, C₁₂H₉NO₅ (3), is a precursor to an antimycobacterial squaramide. Block-shaped crystals of a monoclinic form (3-I, space group P2₁/c, Z = 8, Z' = 2) and needle-shaped crystals of a triclinic form (3-II, space group P-1, Z = 4, Z' = 2) were found to crystallize concomitantly. In both crystal forms, R₂²(10) dimers assemble through N-H...O=C hydrogen bonds. These dimers are formed from crystallographically unique molecules in 3-I, but exhibit crystallographic C_i symmetry in 3-II. Twinning by pseudomerohedry was encountered in the crystals of 3-II. The conformations of 3 in the solid forms 3-I and 3-II are different from one another but are similar for the unique molecules in each polymorph. Density functional theory (DFT) calculations on the free molecule of 3 indicate that a nearly planar conformation is preferred.