Journal of Chemical Crystallography最新文献

Two new optical spiro materials, C₁₇ H₁₆ F₃ N O₄ (F1) and C₁₄ H₁₂ F₃ N O₄ (F2), have been synthesized. Their structures were determined by X-ray diffraction and characterized using FT-IR, UV–vis, and (¹H and ¹³C) NMR spectroscopies. The crystal structure determinations show compound F1, belongs to the triclinic system, space group P (overline{1 }), with a = 6.1216(14) Å, b = 9.536(3) Å, c = 13.957(4) Å, α = 80.044(7)° Å, β = 86.260(8)°, γ = 81.694(7)°, Mr = 355.31, V = 793.4(3) ų, Z = 2, F(000) = 368. Compound J2, is monoclinic system, space group P2₁/c with a = 14.932(3) Å, b = 5.355(9) Å, c = 17.732(4) Å, β = 92.21(4)°, Mr = 315.25, V = 1417(2) ų, Z = 4, F(000) = 648. The both compounds form three-dimensional network structures via C–H···O and N–H···O intra- and intermolecular hydrogen bonds. The observed bond lengths, bond angles, vibrational frequencies, and UV–vis absorption peaks were in agreement with the data obtained from DFT calculations. Hirshfeld surface analyses of F1 and F2 highlighted that F···H/H···F and H···H intermolecular interactions were significant contributors. The TG/DTA demonstrated that both compounds possessed strong thermal stability. The energy gaps (ΔE_HOMO-LUMO) for F1 and F2 were calculated to be 4.369 eV and 4.316 eV, respectively. Potential electrophilic and nucleophilic sites were identified through MEP analysis. Additionally, NBO and Mulliken analyses were also studied.

Graphical Abstract

Two new nonlinear optical spiro materials containing CF3 group have been obtained, C17 H16 F3 N O4 (F1) and C14 H12 F3 N O4 (F2) and their structures were determined by FT-IR, UV–vis, TG analysis, (1H and 13C) NMR spectroscopies, and single crystal crystallography. The vibrational spectra, UV–vis spectra of F1 and F2 were compared to the predicted values using the level of B3LYP/6-31G(d,p). The HOMO–LUMO energies, NBO, MEP, NLO, Milliken charge distribution, TG/DTA and fluorescence behavior were also studied.

The structure of a 2-pyrenolato–coordinated gallium porphyrin complex incorporating an additional hydrogen-bonded 2-pyrenol molecule has been determined [monoclinic, a = 18.60720(10) Å, b = 15.74080(10) Å, c = 28.3753(2) Å, β = 106.9530(10)°, space group P2₁/c]. The additional 2-pyrenol molecule forms a hydrogen bond with the oxygen atom of the coordinated 2-pyrenol. The gallium ion (Ga³⁺) is five-coordinate, adopting a square-pyramidal geometry with four nitrogen atoms from the porphyrin ligand and one oxygen atom from the 2-pyrenolato ligand. The Ga–O bond distance is 1.8799(15) Å, which deviates from previously reported values for gallium porphyrins bearing oxygen-containing axial ligands. The introduction of 2-pyrenol imparts properties characteristic of pyrene, namely CH–π and π–π interactions.

Graphical Abstract

This paper describes a crystallographic study of a gallium porphyrin complex coordinated with 2-pyrenolato and incorporating an additional hydrogen-bonded 2-pyrenol molecule.

The reaction of the labile tri-osmium carbonyl cluster, [Os₃(CO)₁₀(NCMe)₂] 1, with 2-ethymercaptobenzothiazole 2 produced a novel hydrido­bridged tri­osmium complex, Os₃(CO)₁₀(μ-H){μ_N,C-NC(SC₂H₅)SC₆H₃} 3 in moderate yield. The complex was formed via the regioselective C–H bond activation at the ortho-position of the ligand. The crystal structure of 3 demonstrated an N,C-bridging NC(SC₂H₅)SC₆H₃ group coordinated to the two osmium atoms from the axial sites. The presence of the bridging hydride was confirmed by a distinctive resonance in the ¹H NMR spectroscopy at −13.12 ppm, X-ray crystallography, and computational study. Compound 3 crystallized in the monoclinic crystal system, space group P2₁/n, a = 17.642(11) Å, b = 7.720(4) Å, c = 18.102(11) Å, β = 100.773(6)°, Z = 4. The molecular geometry of 3 was very close to its DFT optimized geometry, demonstrating the N,C-bridged motif's stability.

Graphical Abstract

A new tri-osmium cluster, Os₃(CO)₁₀(µ-H){µ_N,C-NC(SC₂H₅)SC₆H₃} 3, was synthesized from the reaction of the labile tri-osmium cluster, [Os₃(CO)₁₀(NCMe)₂] 1 and 2-ethylmercaptobenzothiazole 2, which was structurally characterized.

The guest encapsulation behavior and solid-state supramolecular assembly of four bromoethoxy-substituted pillar[5]arenes were investigated. These macrocycles selectively encapsulate 1,4-dibromobutane from equimolar mixtures of four α,ω-dibromoalkanes, forming 1:1 crystalline inclusion complexes. Single-crystal X-ray diffraction revealed that encapsulation is stabilized by C–H···π and C–H···O interactions within the macrocyclic cavity. The number and position of bromoethoxy groups significantly influence the supramolecular packing. While mono- and di-bromoethoxy-functionalized pillar[5]arenes exhibit only C–H···π and C–H···O interactions, the tetra- and hexa-bromoethoxy derivatives additionally display C–H···Br contacts, with the guest contributing to the assembly. Notably, the hexabromoethoxy-functionalized pillar[5]arene also exhibits Br···Br contacts, resulting in a distinct packing arrangement compared to the other systems.

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The structures of [Fe(CO)₃(η⁴-6-exo-(OH)cyclohepta-2,4-dien-1-one] [monoclinic, a = 6.6080(2), b = 11.9177(3), c = 13.1157(4), β = 102.590(3) space group P2₁/c] and [Fe(CO)₃(η⁴-6-exo-(OD)cyclohepta-2,4-dien-1-one] [monoclinic, a = 6.5999(3), b = 11.8947(4), c = 13.1040(5), β = 102.497(4) space group P2₁/c] have been determined. There is moderate intermolecular hydrogen bonding observed between the alcohol and the ketone. The iron centers adopt a slightly distorted square pyramidal geometry.

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Addition of H₂O or D₂O to [Fe(CO)₃(η⁵-cyclohepta-2,4-dien-5-yl-1-one)][BF₄] results in a product that is formally attack at the coordinated ring in a position exo- to the iron atom forming the corresponding [Fe(CO)₃(η⁴-6-exo-(OH/OD)cyclohepta-2,4-dien-1-one] compounds, which were structurally characterized

Treatment of [Re₂(CO)₈(NCMe)₂] with caffeine in boiling toluene produces the dirhenium hydrido-carbonyl complex [Re₂(CO)₈(µ,η¹,κ¹-C₅N₄(CH₃)₃O₂}(µ-H)] (1) in low yield. Complex 1 is formed during this reaction through a C–H bond activation of caffeine at the imidazole ring. Crystal structure of 1, determined by XRD analysis, reveals that both the metalated caffeine and hydride act in bridging capacity by spanning across the rhenium-rhenium vector. The bonding in 1 has been confirmed by DFT calculations.

Graphical abstract

A new dirhenium complex containing a metalated caffeine ligand has been isolated and structurally characterized from the reaction of [Re₂(CO)₈(NCMe)₂] with caffeine.

The synthesis, X-ray crystallographic, and spectroscopic studies of N-(4-chlorophenyl)-6-[(4-chlorophenyl)carbamothioyl]pyridine-2-carboxamide (Cl-pcta) grown from EtOAc/ hexane (1:8) is reported. The compound crystallized in a monoclinic space group P 2₁/c with a = 9.8905(4) Å, b = 21.5491(9) Å, c = 8.9818(4) Å, β = 111.1277(13)° and V = 1785.62(13) ų with Z = 4. The structure of Cl-pcta is pseudo-planar with the Cl-aryl rings twisted in opposite directions out of the plane of the pyridyl ring. The packing of the molecules were stabilized by classical hydrogen bonding between NH and C = O/C = S groups. In the ¹H NMR the NH(C = O) and the NH(C = S) where observed at 9.44 and 11.19 ppm, respectively. In the IR spectrum, the NH(C = O) and the NH(C = S) were also resolved and observed at 3216 and 3302 cm^–1, respectively; coherent with the asymmetrical nature of the molecule.

Graphical abstract

Synthesis, X-ray crystallographic and spectroscopic studies of N-(4-chlorophenyl)-6-[(4-chlorophenyl)carbamothioyl]pyridine-2-carboxamide. The synthesis, X-ray crystallographic, and spectroscopic studies of N-(4-chlorophenyl)-6-[(4-chlorophenyl)carbamothioyl]pyridine-2-carboxamide (Cl-pcta) is reported.

A methanol solvate of the tetranuclear Cu(II) complex with 4-methoxypyridine (4-MOP) as co-ligand have been synthesized, [Cu₄OCl₆.(4-MOP)₄].CH₂OH, (4-MOP = 4-methoxypyridine) and characterized by IR, UV–Vis spectroscopy and single crystal X-ray diffraction. The complex exhibits a tetrahedral {Cu₄O} core, where four Cu(II) ions are bridged by six chloride ligands and further stabilized through coordination with 4-methoxypyridine ligands. Each copper center displays a distorted trigonal bipyramidal geometry. Intermolecular C–H···Cl and C–H···O hydrogen bonds interconnect the molecules, forming a three-dimensional supramolecular framework. Spectroscopic data, including UV-Vis and FT-IR, substantiate the formation of the Cu₄O cluster and align with the structural observations. These findings offer valuable insights into the coordination behavior and supramolecular organization of µ₄-oxo copper complexes, presenting a useful model for biomimetic systems and a potential foundation for applications in catalysis and material science.

Graphical Abstract

A rare example of a µ₄-oxo-bridged tetranuclear Cu(II) complex stabilized by 4-methoxypyridine ligands has been selectively synthesized and structurally characterized. This is among the few known Cu₄OCl₆ type architectures incorporating 4-MOP, revealing a well-defined {Cu₄O} core and a 3D supramolecular network through weak hydrogen bonding.

The title compound (1) was synthesized through reaction between Pd(CH₃CN)₄(BF₄)₂ and m-xylylenebis(pyridyltriazole) (m-xpt) in a mixture of CH₂Cl₂ and CH₃CN. The solid product was crystallized by vapor diffusion of ethyl ether into a DMSO solution. In the crystal structure of 1, square-planar trans-[Pd(pyridyltriazole)₂]²⁺ groups are joined by m-xylylene bridges to make centrosymmetric [Pd₂(m-xpt)₂]⁴⁺ cations with Pd⋯Pd = 5.1337(4) Å. As in previously published structures with the isomeric o-xpt ligand, ([Ag₂(o-xpt)₂]²⁺ and [Pd₂(o-xpt)₂]⁴⁺), the Pd(pyridyltriazole)₂ planes in 1 make close π contact (3.302 Å); this is accomplished by twisting of the m-xpt bridging groups, so that the longer Pd⋯Pd vector makes a 40° angle with the Pd(pyridyltriazole)₂ planes.

Graphical Abstract

The crystal structure of the title compound shows a Pd⋯Pd distance approximately as expected (5.1337(4) Å), but with its m-xylylene groups twisted in order to permit close π–π interactions (3.302 Å) between its Pd(pyridyltriazole)₂ planes.

A new tetrameric complex of Ba(II), [Ba₄(PA)₄(H₂O)₂₀]·4H₂O (PA = pamoate) has been prepared by gel diffusion technique at ambient condition. The grown crystals were characterized by elemental analysis, single crystal X-ray diffraction studies, thermogravimetry, FT-IR and UV–visible spectral studies. The single crystal X-ray diffraction studies show that the crystal structure consists of two different types of nine coordinated Ba centers (Ba1 and Ba2). In addition to the carboxylate groups of pamoate, two coordinated water also interconnect the Ba(II) centers. The carboxylate groups of pamoate exhibit monodentate, bismonodentate and bidentate, coordination modes with Ba(II) ions. Hydrogen bonding further stabilizes the crystal structure. Photoluminescence studies were also carried out.

Graphical Abstract

A new tetrameric complex of Ba(II) with pamoic acid (H₂PA) of formula [Ba₄(PA)₄(H₂O)₂₀]·4H₂O (BaPA) has been prepared by gel diffusion technique at ambient condition and is characterized by various analytical techniques.