Orthorhombic Space Group Research Articles

Crystal engineering with novel antipyrine derivatives: Insights from X-ray diffraction, Hirshfeld surface analysis, and DFT calculations on intermolecular interactions

In this study, we report the synthesis, structural characterization by X-ray diffraction, vibrational (Infrared and Raman) investigation, Hirshfeld surface analysis, and DFT calculations of three new antipyrine derivatives (1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl) bearing amide groups (1–3). The compounds were synthesized in good yields and characterized spectroscopically. X-ray diffraction revealed that compound 1 crystallizes as a monohydrate in the monoclinic space group P21/c, while compound 3 also crystallizes as a monohydrate in the orthorhombic space group Pccn, exhibiting quasi-isomorphism with 1. Compound 2 crystallizes in the P21/c space group, forming H-bonded centrosymmetric dimers. The crystal packing is stabilized by NH···O and CH···O hydrogen bonds, along with CH···π interactions. FTIR and Raman spectroscopic analysis, supported by DFT calculations, identified key vibrational modes in the amide and pyrazole moieties. Hirshfeld surface analysis indicated that the molecular sheets are primarily formed by hydrogen bonds, with stabilization dominated by electrostatic energy contributions. DFT calculations (PBE0-D3/def2-TZVP) and QTAIM/NCIplot analyses revealed that the H-bonding interactions are energetically significant.

Crystal structure and characterization of monascin from the extracts of Monascus purpureus-fermented rice.

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.

Structures and photochromic behavior of viologen-based compounds: Insights from Mn(II) and Cd(II) complexes

This study investigates the crystal structures and photochromic properties of two viologen-based compounds [Mn(CMbpy)(BTEC)0.5(H2O)4]·0.5(H2BTEC)·3H2O (1) and [Cd(CMbpy)(1,2,4-BTC)(H2O)]n (2) [CMbpyBr = 1-(1-cyclohexylmethane)-4,4′-bipyridinium bromide, H4BTEC=1,2,4,5-benzenetetracarboxylic acid, 1,2,4-H3BTC=1,2,4-benzenetricarboxylic acid]. X-ray diffraction analysis identified compound 1 as a triclinic ionic lattice featuring Mn(II) in an octahedral coordination with CMbpy cations, whereas compound 2 crystallizes in an orthorhombic space group forming a three-dimensional MOF stabilized by CMbpy cations. Compound 1 demonstrated no color change, while compound 2 exhibited a rapid transition to a blue state upon UV irradiation, with an accompanying emergence of new absorption peaks, indicative of viologen radical formation. This behavior was corroborated by electron paramagnetic resonance (EPR) spectroscopy. Our findings provide a profound understanding of the structure–function relationship in these viologen complexes, highlighting the synergy between metal coordination, hydrogen bonding, and the strategic positioning of donor–acceptor components.

Crystal structure of the cytotoxic macrocyclic trichothecene Isororidin A.

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.

A novel one-dimensional thiocyanate-bridged cobalt(III) complex: synthesis, crystal structure characterization and Hirshfeld surface analysis.

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(μ1,3-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 CoIII 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 CoIII 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.

Advancing Solid Oxide Fuel Cell Performance: Enhanced Electrochemical Properties of Pr1-xCaxBaFe2O5+δ Nanofiber Cathodes via Ca Doping.

The double perovskite oxide PrBaFe2O5+δ has great potential as a cathode material for solid oxide fuel cells (SOFCs). However, the electrochemical characteristics of Fe-based double perovskites are relatively inferior. To improve its electrochemical performance, Ca is investigated to partially replace Pr, forming Pr1-xCaxBaFe2O5+δ (PCBFx, x = 0.0-0.3) by an electrospinning technique. The PCBFx nanofibers exhibited a crystalline structure characterized by orthorhombic symmetry and space group P4/mmm. Furthermore, these PCBFx nanofibers displayed exceptional chemical compatibility with the Sm0.2Ce0.8O1.95 (SDC) electrolyte when sintered at a temperature of 900 °C for 5 h. The X-ray photoelectron spectroscopy (XPS) analysis reveals a progressive increase in the Fe4+ concentration as the Ca doping level rises. The polarization resistances (Rp) of the PCBF00, PCBF01, PCBF02, and PCBF03 nanofiber cathodes were 0.103, 0.079, 0.056, and 0.048 Ω cm2 at 750 °C. In the meantime, doping Ca increases the peak power density of the single cell by 46%, from 762.80 (PCBF00) to 1114.85 (PCBF03) mW cm-2 at 750 °C. The results demonstrate that PCBF03 double perovskite nanofibers exhibit great potential as cathode materials for SOFCs.

Synthesis and characterization of Eu3Ba5Cu8O18-δ superconductor doped with 0.1% Graphene oxide

This research presents the synthesis and evaluation of the structural and morphological properties of superconducting Eu3Ba5Cu8O18-δ doped with 0.1% graphene oxide, using the solid state reaction method. The structural analysis performed on the samples, both doped and undoped, allowed identifying the main phase as Eu3Ba5Cu8O18-δ (Eu358), with orthorhombic structure and space group Pmm2(25), maintaining superconducting properties in both cases. In addition, it was observed that doping with graphene oxide resulted in the formation of a minority phase of EuBa4Cu3O9 (Eu143), with cubic structure and space group P23(195). As for the morphological characterization, it was evidenced that the undoped sample presents aggregates formed by non-uniform size grains, with an average size of approximately 97 µm. In contrast, the sample doped with 0.1% graphene oxide exhibits significant improvements in uniformity and grain boundaries, with an average size of about 141 µm. These results confirm obtaining Eu3Ba5Cu8O18-δ with a 73% superconducting phase, exceeding the percentages previously reported using the solid-state reaction method.

A comprehensive study of crystal structure, UV–visible study, electric-dielectric properties of a recently developed Hybrid Material [(C6H5N2)2ZnCl4]

The advanced hybrid material, [(C6H5N2)2ZnCl4] was prepared using the gradual dehydration process by combining 4-cyanopyridine and ZnCl2 under standard ambient temperature conditions. The compound underwent various characterization techniques, including single crystal and Powder X-ray diffractions (SXRD, PXRD), Scanning Electron Microscopy (SEM) and EDX Energy-Dispersive X-ray, FT-IR spectroscopy, UV–Visible absorption analysis, Hirshfeld surface analysis (SHG), and thermal analysis. The molecular composition of the examined chemical substances was determined to belong to the orthorhombic P212121 space group through single crystal X-ray analysis. analysis. Its molecular arrangement was characterized by alternating layers of tetrahedral [ZnCl4]2- and 4-cyanopyridinium planes (C6H5N2)+. These layers are connected through NH···Cl and CH···Cl hydrogen bonds, which contribute to their cohesion and overall adherence. The UV–visible spectrum using Tauc plot relation, has unveiled the energy ratio of an optical band gap, which is measured at 4.80 eV. Additionally, thermal analysis has demonstrated that [(C6H5N2)2ZnCl4] exhibits thermal stability up to a temperature of 475 K. SHG study was employed to examine the interactions between molecules. Additionally, 2D finger plots were utilized to quantitatively assess the impact of these interactions on the crystal structure. This work discusses various electrical characteristics obtained through impedance measurements, including dielectric constants and electric modulus. To shed light on the electrical resistance and dielectric characteristics, we conducted complex impedance spectroscopy at different frequencies with temperature ranging between 313 and 423 K. The elaborate Nyquist curve revealed a solitary semicircle, indicating that the signal was generated by a single capacitive circuit associated with the grain. We also researched ac conduction to figure out how electricity is transmitted. The diagram unveils that the conduction mechanism is thermally activated. The activation energy value obtained from the dc conductivity is approximately 0.768 eV. The analysed material allows for the movement of space charge through a hopping mechanism. Finally, the dielectric constant estimate demonstrates that this title compound is a suitable candidate for the fabrication of opto-electronic materials. Modulus analysis demonstrated that the mobile charge carriers exhibited mobility both at low and high frequencies, covering short and long distances.

Preliminary X-ray diffraction and ligand-binding analyses of the N-terminal domain of hypothetical protein Rv1421 from Mycobacterium tuberculosis H37Rv.

Mycobacterium tuberculosis can reside and persist in deep tissues; latent tuberculosis can evade immune detection and has a unique mechanism to convert it into active disease through reactivation. M. tuberculosis Rv1421 (MtRv1421) is a hypothetical protein that has been proposed to be involved innucleotide binding-related metabolism in cell-growth and cell-division processes. However, due to a lack of structural information, the detailed function of MtRv1421 remains unclear. In this study, a truncated N-terminal domain (NTD) of MtRv1421, which contains a Walker A/B-like motif, was purified and crystallized using PEG 400 as a precipitant. The crystal of MtRv1421-NTD diffracted to a resolution of 1.7 Å and was considered to belong to either the C-centered monoclinic space group C2 or the I-centered orthorhombic space group I222, with unit-cell parameters a = 124.01, b = 58.55, c = 84.87 Å, β=133.12° or a = 58.53, b = 84.86, c = 90.52 Å, respectively. The asymmetric units of the C2 or I222 crystals contained two or one monomers, respectively. Interms of the binding ability of MtRv1421-NTD to various ligands, uridine diphosphate (UDP) and UDP-N-acetylglucosamine significantly increased the melting temperature of MtRv1421-NTD, which indicates structural stabilization through the binding of these ligands. Altogether, the results reveal that a UDP moiety may be required for the interaction of MtRv1421-NTD as a nucleotide-binding protein with its ligand.

The Synthesis and Crystallographic Characterization of Emissive Pt(II) and Au(I) Compounds Exploiting the 2-Ethynylpyrimidine Ligand

The luminescent properties of Au(I) and Pt(II) compounds are commonly tuned by exploiting the alkynyl ligand with varying electron density. Herein, we describe the synthesis of three new emissive transition metal compounds, tbpyPt(C2pym)2, Ph3PAuC2pym, and Cy3PAuC2pym (where HC2pym = 2-ethynylpyrimidine), verified by 1H-NMR, EA, and a single-crystal X-ray diffraction analysis. The tbpyPt(C2pym)2 complex crystallized as an Et2O solvate in the orthorhombic space group Pbca with Z = 24 with three unique Pt(II) species within the unit cell. The Cy3PAuC2pym species crystallizes in a monoclinic space group with one unique complex in the asymmetric unit. Changing the identity of the phosphine from Cy3P to Ph3P influences interactions within the unit cell. Ph3PAuC2pym, which also crystalizes in a monoclinic space group, has an aurophilic bonding interaction Au–Au distance of 3.0722(2) Å, which is not present in crystalline Cy3PAuC2pym. Regarding optical properties, the use of an electron-deficient heterocycle provides an alternate approach to blue-shifting the emission of Pt(II) transition metals’ compounds, where the aryl moiety is made more electron-deficient by exploiting nitrogen within this moiety instead of the typical strategy of decorating the aryl ring with electron withdrawing substituents (e.g., fluorines). This is indicated by the blue-shift in emission that occurs in tbpyPt(C2pym)2 (λmax, emission = 512 nm) compared to the previously reported tbpyPt(C22-py)2 (where HC22-py = 2-ethynylpyridine) complex (λmax, emission = 520 nm).

Advancing Heteroanionicity in Zintl Phases: Crystal Structures, Thermoelectric and Magnetic Properties of Two Quaternary Semiconducting Arsenide Oxides, Eu8Zn2As6O and Eu14Zn5As12O.

Two novel quaternary oxyarsenides, Eu8Zn2As6O and Eu14Zn5As12O, were synthesized through metal flux reactions, and their crystal structures were established by single-crystal X-ray diffraction methods. Eu8Zn2As6O crystallizes in the orthorhombic space group Pbca, featuring polyanionic ribbons composed of corner-shared triangular [ZnAs3] units, running along the [100] direction. The structure of Eu14Zn5As12O crystallizes in the monoclinic space group P2/m and its anionic substructure can be described as an infinite "ribbonlike" chain comprised of [ZnAs3] trigonal-planar units, although the structural complexity here is greater and also amplified by disorder on multiple crystallographic positions. In both structures, the O2- anion occupies an octahedral void with six neighboring Eu2+ cations. Formal electron counting, electronic structure calculations, and transport properties reveal the charge-balanced semiconducting nature of these heteroanionic Zintl phases. High-temperature thermoelectric transport properties measurements on Eu14Zn5As12O reveal relatively high resistivity (ρ500K = 8 Ω·cm) and Seebeck coefficient values (S500K = 220 μV K-1), along with a low concentration and mobility of holes as the dominant charge-carriers (n500K = 8.0 × 1017 cm-3, μ500K = 6.4 cm2/V s). Magnetic studies indicate the presence of divalent Eu2+ species in Eu14Zn5As12O and complex magnetic ordering, with two transitions observed at T1 = 21.6 K and T2 = 9 K.

Synthesis, crystal structure, spectroscopic characterization, in vitro, molecular docking and DFT studies of 1- (Tert-Butyl) 2-methyl (2S, 4R)-4-hydroxy pyrrolidine-1,2-dicarboxylate

A chiral pyrrolidine-based compound, namely 1-(Tert-Butyl) 2-Methyl (2S, 4R)-4-Hydroxy Pyrrolidine-1,2-Dicarboxylate (NHP), was synthesized and crystallized by the slow evaporation technique. NMR, FT-IR, ESI-MS, UV–visible spectroscopy, and elemental analysis designate the molecule. The molecule crystallized in the orthorhombic space group P212121, identified by X-ray diffraction (XRD). Quantum chemical calculations were performed using DFT at the B3LYP/6–311++G (d,p) level. The DFT-calculated optimal structural parameters and the XRD-derived parameters showed a good correlation. The frequency of NHP is calculated using the DFT method and compared with observed results. The synthesized compound's molecular reactivity was further investigated using Mulliken atomic charges, HOMO-LUMO, and molecular electrostatic potential (MEP). The molecule was tested for molecular docking with bio-enzymes such as α-amylase (1HNY) and cyclooxygenases (1PGG & 4COX). The compound showed 7 hydrogen bonding interactions with 1HNY and 8 hydrogen bonding interactions with 4COX. The DFT investigations strongly support the molecular docking results. The molecule's in-vitro anti-inflammatory and anti-diabetic activity was compared with conventional medication. The NHP showed superior anti-inflammatory activity with protein denaturation technique than the standard diclofenac sodium. The results showed that the molecule outperformed the conventional medication in tests for inflammation.

Comment on “Ferroelectric composite-based piezoelectric energy harvester for self-powered detection of obstructive sleep”

SrTi2O5 particles were claimed by Panda et al. in J. Materiomics 2023; 9:609 as a new lead-free ferroelectric material with orthorhombic symmetry and space group of Cmm2, being, therefore, employed as a base of piezoelectric energy harvesters. However, in this comment we express concerns regarding the presence of the piezoelectricity in the studied material and the interpretation of the structural, microstructural, and ferroelectric results in that publication as those associated with SrTi2O5. We also note that the presented dielectric results are contradictory and that many important details are missing.

Molecular Insights of an Avian Species with Low Oxygen Affinity, the Crystal Structure of Duck T-State Methemoglobin.

Hemoglobin (Hb) is the key metalloprotein within red blood cells involved in oxygen transportation from lungs to body cells. The heme-iron atom inherent within Hb effectuates the mechanism of oxygen transportation and carbon dioxide removal. Structural investigations on avian Hb are limited when compared with the enormous work has been carried out on mammalian Hb. Here, the crystal structure of T-state methemoglobin (T-metHb) from domestic duck (Anas platyrhynchos), a low oxygen affinity avian species, determined to 2.1Å resolution is presented. Duck T-metHb crystallized in the orthorhombic space group C2221 with unit cell parameters a = 59.89, b = 109.42 and c = 92.07Å. The final refined model with R-factor: 19.5% and Rfree: 25.2% was obtained. The structural analysis reveals that duck T-metHb adopts a unique quaternary structure that is distinct from any of the avian liganded Hb structures. Moreover, it closely resembles the deoxy Hb of bar-headed goose, a high oxygen-affinity species. Besides the amino acid αPro119 located in the α1β1 interface, a unique quaternary structure with a constrained heme environment is attributed for the intrinsic low oxygen-affinity of duck Hb. This study reports the first protein crystal structure of low oxygen-affinity avian T-metHb from Anas platyrhynchos.

Uranium Oxide Hydrate Frameworks with Dy(III) or Lu(III) Ions: Insights Into the Framework Structures With Lanthanide Ions.

Two uranium oxide hydrate frameworks (UOHFs) with either Dy3+ or Lu3+ ions, Dy1.36(H2O)6[(UO2)10UO13(OH)4] (UOHF-Dy) or Lu2(H2O)8[(UO2)10UO14(OH)3] (UOHF-Lu), were synthesized hydrothermally and characterized with a range of structural and spectroscopic techniques. Although SEM-EDS analysis confirmed the same atomic ratio of ~5.5 for U : Dy and U : Lu, they displayed different crystal morphologies, needles for UOHF-Dy in the orthorhombic C2221 space group and plates for UOHF-Lu in the triclinic P-1 space group. Both frameworks are composed of β-U3O8 type layers linked by pentagonal bipyramidal uranium polyhedra, with the Dy3+/Lu3+ ions inside the channels. However, the arrangements of Dy3+/Lu3+ ions are different, with disordered Dy3+ ions well aligned at the centers of the channels and single Lu3+ ions well-separated in a zigzag pattern in the channels. While the characteristic vibrational modes were revealed by Raman spectroscopy, the presence of a pentavalent uranium center in UOHF-Lu was confirmed with diffuse reflectance spectroscopy. The formation of two types of UOHFs with lanthanide ions, high or low symmetry, and the structure trend were discussed regards to synthesis conditions and lanthanide ionic radius. This work highlights the complex chemistry driving the formation of UOHFs with lanthanide ions and has implications to the spent nuclear fuel under geological disposal.

Investigation of structural, morphological, dielectric, optical, and ferroelectric-energy storage properties of [(1-x) BCT-(x) BZT] electroceramics

Extensive research and advancements have been progressed by the vast potential of eco-friendly dielectric capacitors in high-level electronic elements and high-performance pulsed power systems thus far. Ferroelectric ceramic materials exhibiting relaxor properties and significant dielectric constants are prime candidates for attaining exceptional energy storage capabilities. Herein, a lead-free (1-x) Ba0.9Ca0.1TiO3–xBaZr0.15Ti0.85O3 (abbreviated as (1-x) BCT-xBZT) solid solution system has been synthesized via the conventional solid-state reaction technique, with varying levels of BZT doping. The X-ray diffraction study confirmed pure perovskite structure formation in the prepared ceramics, and the coexistence of orthorhombic (O) (space group- Amm2) and tetragonal (T) (space group-P4mm) phases has been detected through the Rietveld refinement technique at room temperature. Rietveld refinement data and associated analysis highlight the gradual shift of crystal symmetry from Amm2 to P4mm as the x content increases. Replacing BZT in Ca-modified BaTiO3 has led to significant enhancements in microstructural properties and an increase in the width of the optical band gap. This, in turn, enhances energy storage capabilities compared to pure BCT. Incorporating BZT into BCT has led to the evolution of relaxor ceramics, a crucial development for achieving elevated levels of recoverable energy storage density. In this study, the solid solution comprising 0.6BCT-0.4BZT exhibits distinct traits, including a diffuse phase transition, high breakdown strength, shallow dielectric loss (tanδ <0.007), and significantly high dielectric constant. Due to enhanced electrical characteristics, the 0.6BCT-0.4BZT possesses very high saturation polarization of ∼48 μCcm−2, a total energy density of 1.71 J/cm3, and a recoverable energy density of 1.1 J/cm3. In addition, the optimized ceramics demonstrate concurrent achievement of high-frequency stability (10–250 Hz), fatigue resistance (up to 104 cycles), and favorable temperature stability (20–160°C). This study showcased a potential material candidate suitable for energy storage devices functioning within low to medium-electric fields.

Stereoisomers of oxime ethers of 1,4-naphthoquinone: Synthesis, characterization, X-ray crystal structures, and DFT studies

In the present work, we use the C-3 substituted 2-hydroxy-1,4-naphthoquinones viz. 2-hydroxynaphthalene-1,4-dione (1), 2-hydroxy-3-methylnaphthalene-1,4-dione (2), and 2-chloro-3-hydroxynaphthalene-1,4-dione (3) as starting materials and obtained naphthoquinoneoxime ethers viz. 3-hydroxy-4-(methoxyimino)naphthalen-1(4H)-one (4), 3-hydroxy-4-(methoxyimino)-2-methylnaphthalen-1(4H)-one (5) and 2-chloro-3-hydroxy-4-(methoxyimino)naphthalen-1(4H)-one (6) via a facile and efficient synthesis involving condensation with methoxyamine hydrochloride. X-ray structure showed that 4 belongs to the orthorhombic (P212121) space group, whereas 5 and 6 (P21/c) crystalize in the monoclinic crystal system. The isomer ratios derived from NMR experiments elucidating stereoisomerism in compounds comprised of carbon-nitrogen double bonds have been analyzed; the naphthoquinone oxime ethers 4, 5, and 6 were also characterized employing the ωB97x-D/6–311++G (d, p) level of density functional theory. Theoretical studies reveal different conformational isomers with the ‘amphi’ and ‘syn’ isomers as low-lying structures along their energy hierarchy in accordance with the X-ray crystallography data. The spectral characterization of vibrational frequencies and 1H /13C NMR chemical shifts in unison with experiments and theory has been presented.

Synthesis, structure and photocatalytic performance of {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n and its derivatives

A polynuclear metal-organic framework, {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n (Htza=1H-tetrazole-1-acetic acid), was successfully synthesized and characterized, and its photocatalytic properties, along with those of its derivatives, were investigated. The crystal structure of the compound was determined to belong to the orthorhombic space group Pn ma, featuring a 3D framework comprising cage-like [Bi6(µ3-O)3(µ3-OH)5]7+ clusters. {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n demonstrated significant photocatalytic activity with UV light response within the pH range of 6.0–8.0 and a band gap energy of 3.32 eV. Under optimal conditions, a reduction in chemical oxygen demand (COD) and total organic carbon (TOC) (from 126.90 mg/L to 4.57 mg/L) clearly validated the efficient methyl orange degradation. The main active groups in the degradation process were h+, ·O2− and ·OH, and the catalyst demonstrated reusability for up to six cycles. Moreover, it was hydrolyzed to Bi2O2CO3 and BiOCl under alkaline (pH=9.0–11.0) and acidic (pH=1.0–5.0) conditions, respectively, thus serving as a valuable precursor. Notably, the Bi2O2CO3 and BiOCl derivatives exhibited higher catalytic activities than catalysts synthesized using alternative methods under the same experimental conditions. Therefore, within the pH range of 1.0–11.0, {[Bi6(tza)5(NO3)2(OH)5O3]·H2O}n, along with its in situ derivatives BiOCl and Bi2O2CO3, were highly efficient UV light-driven photocatalysts.

Synthesis, structure and photoluminescence properties of heterometallic-based coordination polymers of trimesic acid.

Reacting trimesic acid (H3TMA, C9H6O6) with CaCl2 and MCl2 at 110 °C under hydrothermal conditions gave the isostructural heterobimetallic coordination polymers (CPs) catena-poly[[tetraaquazinc(II)]-μ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-μ-5-carboxybenzene-1,3-dicarboxylato], [CaZn(HTMA)2(H2O)8]n, 1, and catena-poly[[tetraaquacobalt(II)]-μ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-μ-5-carboxybenzene-1,3-dicarboxylato], [CaCo(HTMA)2(H2O)8]n, 2. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. The solid-state structures consist of eight-coordinate CaII ions and six-coordinate MII ions. These ions are connected by a doubly deprotonated HTMA2- ligand to create a one-dimensional (1D) zigzag chain. Poly[[decaaquabis(μ3-benzene-1,3,5-tricarboxylato)calcium(II)dizinc(II)] dihydrate], {[CaZn2(TMA)2(H2O)10]·2H2O}n, 3, was found incidentally as a minor by-product during the synthesis of 1 at a temperature of 140 °C. It forms crystals in the orthorhombic space group Ccce. The structure of 3 consists of a two-dimensional (2D) layer composed of [Zn(TMA)] chains that are interconnected by CaII ions. The presence of aromatic carboxylic acid ligands and water molecules, which can form numerous hydrogen bonds and π-π interactions, increases the stability of the three-dimensional (3D) supramolecular architecture of these CPs. Compounds 1 and 2 exhibit thermal stability up to 420 °C, as indicated by the thermogravimetric analysis (TGA) curves. The powder X-ray diffraction (PXRD) data reveal the formation of unidentified phases in methanol and dimethyl sulfoxide, while 1 exhibits chemical stability in a wide range of solvents. The luminescence properties of 1 dispersed in various low molecular weight organic solvents was also examined. The results demonstrate excellent selectivity, sensitivity and recyclability for detecting acetone molecules in aqueous media. Additionally, a possible sensing mechanism is also outlined.

Anionic and Magnetic Ordering in Rare Earth Tantalum Oxynitrides with an n = 1 Ruddlesden-Popper Structure.

The new compounds R2TaO4-xNx with R = La, Ce, Nd, and Eu and 1.20 ≤ x ≤ 2.81 have been obtained by a solid-state reaction between metal nitrides and oxides or oxynitrides under N2 gas at temperatures between 1200 and 1700 °C. They are the first examples of rare earth transition metal oxynitrides with an n = 1 Ruddlesden-Popper structure and show different anion stoichiometries, crystal structures, and magnetic properties. Synchrotron X-ray powder diffraction and electron diffraction indicate that the lanthanum, cerium, and neodymium compounds crystallize in the orthorhombic space group Pccn, with cell parameters a = 5.72949(2), b = 5.73055(5), and c = 12.77917(6) Å for La2TaO1.31N2.69, a = 5.70500(5), b = 5.71182(4), and c = 12.61280(7) Å for Ce2TaO1.19N2.81, and a = 5.70466(3), b = 5.70476(5), and c = 12.32365(5) Å for Nd2TaO1.46N2.54. In contrast, Eu2TaO2.80N1.20 shows a tetragonal I41/acd superstructure doubling the c axis, with parameters a = 5.71867(2) and c = 25.00092(19) Å. Refinement of neutron powder diffraction data of Ce2TaO1.19N2.81 indicated the nitrogen order in the two equatorial positions of the tantalum octahedron, with refined N/O occupancies of 0.930(7)/0.070 and 0.876(13)/0.124, and the axial position is occupied by 50% of each anion. This anion ordering agrees with the distribution predicted by Pauling's second crystal rule. Magnetization measurements show that the cerium and europium compounds are ordered magnetically at low temperatures, while the neodymium compound remains paramagnetic down to 2 K, as a consequence of suppression of the effective magnetic moment of the latter when reducing the temperature.