Journal of Chemical Crystallography最新文献

4-(2-amino-2-oxoethyl) phenyl 4-methylbenzenesulfonate (APMBS), a novel compound, has been synthesized and characterized by spectro-analytical techniques. X-ray diffraction data reveals it crystallizes in the triclinic crystal system with space group (Poverline{1}). The structure is stabilized through strong N–H⋯O, weak C–H⋯O and C–H⋯π hydrogen bond interactions yielding a supramolecular structure. The N1A–H1AA⋯O4A, C4–H4⋯O3, and C14–H14⋯Cg1 (Ring: C8–C13) interactions link the molecules into dimers, while the interaction C9-H9–O2 results in the formation of a molecular chain along the a-axis. The optimized structural geometry, by and large, as calculated using DFT and HF techniques is in conformity with the corresponding X-ray data. The DFT computation further aid in the follow up investigations including frontier molecular orbitals (FMOs), density of states (DOS), atomic charges, and molecular electrostatic potential surface (MEP). For a comprehensive description of various molecular intersections, Hirsheld surface and fingerprint plots analysis has been reported, besides the combined atoms-in-molecules (QTAIM) and reduced density gradient (RDG) analysis. Docking studies have been performed against the target protein Tubulin-Colchicine: Stathmin-Like Domain Complex.

Graphical Abstract

A new coordination polymer, namely, {[Zn(DTPP)(H₂O)₂]·H₂O}_n (H₂DTPP = 3-(3,5-di(2H-tetrazol-5-yl)phenoxy)pyridine, compound 1), was successfully assembled by using a new semirigid tripodal nitrogen-containing heterotopic ligand and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, TG, and luminescence. X-ray single-crystal diffraction analysis revealed that compound 1 crystallizes in an orthorhombic crystal system with space groups of Ibca. It is a 2D coordination network with (4·8²) topology, and the 2D networks are further connected by hydrogen bonds between coordinated water molecules and tetrazole N atoms to form a 3D supramolecular framework. Moreover, compound 1 exhibits intense blue emission centered at 345 nm upon excitation at 276 nm and has the ability to sense Fe³⁺ via photoluminescence quenching.

Graphical Abstract

A new coordination polymer synthesized from a new semirigid tripodal nitrogen-containing heterotopic ligand, {[Zn(DTPP)(H₂O)₂]·H₂O}_n, was characterized.

New polymorphs of (2-(chloro(pyrrol-2-ylidene)methyl)pyrrole)-difluoro-borane (1) and (2-(chloro(4-ethyl-3,5-dimethyl-2H-pyrrol-2-ylidene)methyl)pyrrole)-4-ethyl-3,5-dimethyl-1H-pyrrolato)-difluoro-borane (2) were identified using single crystal X-ray diffraction. The new polymorph of 1 crystallises in the triclinic, P-1 space group with an asymmetric unit comprising two crystallographically-independent molecules (Z′ = 2). The differences between this structure and that of the known polymorph of 1 are attributed to the formation of two distinct dimer motifs in each polymorph and the packing between these dimer units. The new polymorph structure of 2, exhibits a similar asymmetric unit to the known form, comprising 3 molecules (Zʹ = 3). The two structures differ in the orientation of the molecules within the trimeric asymmetric unit and the manner in which these trimers pack along the crystallographic [010] direction.

Graphical Abstract

The triclinic polymorph of 8-chloro BODIPY exhibits an asymmetric unit with two crystallographically-independent molecules.

In this study, we have synthesized a novel organic–inorganic hybrid crystal 4-nitrobenzyl-4-aminopyridinium tetrachlorocuprate(II) [4NO₂Bz-4NH₂Py]₂[CuCl₄](1). The single-crystal X-ray diffraction analysis revealed that the crystal belongs to the triclinic space group P–1, and consists of four [4NO₂Bz-4NH₂Py]⁺ cations and two [CuCl₄]²⁻ anions. O⋯π, C–H⋯π, π⋯π, N–H⋯Cl, C–H⋯Cl, C–H⋯O, and C–H⋯N weak interactions in the crystals play an important role in facilitating the stacking and stabilization of the crystals. The different types of contribution have been quantified by the calculation of Hirshfeld surface percentage and depicted by fingerprint plots. The bulk phase purity, homogeneity, and morphology of the desired compound were checked using powder XRD, and SEM–EDX analysis. Vibrational, optical, and thermal properties were investigated by FT-IR, UV–Vis spectrum, and TG–DTA measurements of [4NO₂Bz-4NH₂Py]₂[CuCl₄](1), respectively. The low energy gap (2.41 eV) suggested that the crystal was a suitable semiconductor material for optical applications. In addition, the compound presented good bactericidal activity against E. coli and S. aureus.

Graphical Abstract

A novel organic–inorganic hybrid material, 4-nitrobenzyl-4-aminopyridinium tetrachlorocuprate(II), has been synthesised and characterized with a study of its crystal structure, vibrational spectra, weak interaction, Hirshfield surface, thermal stability and antibacterial activity.

A new polymorph of tert-butyl (2-aminophenyl)carbamate was identified using single crystal X-ray diffraction. The compound crystallised in the centrosymmetric, monoclinic space group P2₁/n with an asymmetric unit comprising two crystallographically-independent molecules (Zʹ = 2). This new structure was compared to that of the known polymorph with the differences between the two being attributed to a combination of space group symmetry, conformational variation, hydrogen bonding network dimensionality and crystal packing.

The crystal and molecular structure of 7-dimethylamino-4-hydroxycoumarin as its hydrate (1, C₁₁H₁₁NO₃ • H₂O) has been determined. Crystals are monoclinic, space group P2(1)/n with a = 7.1435(4) Å, b = 20.1763(6) Å, c = 7.8590(3) Å, β = 110.018(5)^o and V = 1064.28(8)ų for 4 formula units per cell. Both coumarin enol ester hydroxy and carboxy groups engage in hydrogen-bonding with the water of crystallization. Several 3-substituted derivatives were prepared from this material including 7-dimethylamino-3-benzyl-4-hydroxycoumarin (2) and 7-dimethylaminowarfarin (4). Compound 2 (C₁₈H₁₆NO₃) crystallizes in the triclinic system, space group P-1, with a = 7.0180(7) Å, b = 7.8143(7) Å, c = 14.3158(10) Å, α = 90.586(6)^o, β = 94.738(5)^o, γ = 104.639(7)^o, and V = 756.57(9) ų for 2 molecules in the cell. For compound 2, the crystal structure shows infinite hydrogen-bonded translational β-chains linking well aligned hydroxy and ester carboxy groups with a repeat distance of 7.018 Å. The dipolar nature of the substituted 4-hydroxycoumarin strengthens the β-chains compared to unsubstituted systems in which the repeat is longer and weaker at 7.17 Å. Computations (DFT) support the bond length changes due to a dipolar influence of the 7-dimethylamino group (compared to the unsubstituted compounds), and a more negative carboxy oxygen hydrogen-bond acceptor. For compound 4 (C₂₁H₂₁NO₄), a stereoselective synthesis allowed preparation of the (S)-isomer which crystallized in the orthorhombic system, space group P2(1)2(1)2(1), with a = 6.7857(3) Å, b = 14.7140(5) Å, c = 17.4652(7) Å and V = 1743.81(12) ų for 4 molecules in the cell. Compound 4 forms the trans cyclic hemiketal from methanol in the crystal. In CDCl₃ solution (298 K), 4 exists as an equilibrium mixture of three tautomers: 12.8% open form, 45.5% cis hemiketal and 41.7% trans hemiketal (coumarin forms).

Graphical Abstract

Elisei Cosovan, Victor Cosovan, Daniel A. Osborne, David H. Magers, Edward J. Valente-3-Benzyl-4-hydroxy-7-dimethylaminocoumarin forms enhanced translational β-chain hydrogen-bonded arrays in the crystal

Synthesis, characterization and structural relevance of four new copper carboxylate complexes (1–4) has been presented here. The complexes have been synthesized by direct treatment of the substituted phenyl acetate and pyridine ligands in aqueous medium. The complexes were stable indefinitely with excellent yields and were characterized using spectroscopic and single crystal XRD techniques. FTIR spectroscopy revealed the bridging bidentate coordination mode for the carboxylate moiety in accordance to the actual structure revealed by XRD. Moreover, UV-Visible spectroscopic and cyclic voltammetric studies helped in their characterization and yielded signals which were typical of the copper(II) complexes. Successfully solved single crystal XRD data showed binuclear paddlewheel structures for all the complexes with both copper ions linked through four OCO bridges of ortho-methoxy phenyl acetate (1–3) and ortho-methyl-meta-nitrophenyl acetate (4). The geometry around each copper was distorted square pyramidal where the apical positions are occupied by meta-bromopyridine (1), meta-methylpyridine (2) and DMSO (3 and 4) molecules. The complexes exhibited excellent DNA-binding activity majorly via intercalation as revealed by four experimental techniques. This preliminary study showed that the synthesized complexes add to the existing treasury on the paddlewheel complexes.

The Index Abstract

Air stable newly synthesized and purified crystalline complexes with their preliminary structural relevance.

The presented study describe the crystal structure of 2-(Ethoxymethylene)malononitrile (1), C₆H₆N₂O, in the monoclinic space group P2₁/m with Z = 2, a = 6.798(3), b = 6.172(3), c = 8.844(5) Å. The unit cell of a single crystal of 1 contains two antiparallel oriented molecules. Ethyl fragment demonstrates a disorder with equal occupancy values of 0.5 and a total site-occupation factor (s.o.f.) of 1.0. The molecules of 1 are linked into infinite chains of co-oriented molecules parallel to the a axis via N-H···N ≡ C close contacts with the distance of 2.494(3) Å. There are also weak hydrogen bonds > O···H- between the oxygen atom and the ethyl moiety. The estimation of the energy of non-covalent interactions was conducted by DFT method with different functionals. The best reproducibility of the geometric parameters of those interactions was obtained by using M06-2X functional. The estimated energy value was found to be − 1.20 kcal/mol.

Graphical Abstract

The interplay between conformation and hydrogen bond pattern was studied in 211 (C(O)NH)(N)₂P(O)-based phosphoric triamides retrieved from the Cambridge Structural Database (CSD) and one new molecular structure, (CHCl₂C(O)NH)(CH₃CH₂CH₂NH)₂P(O). The O═C–N–P and C–N–P═O torsion angles were extracted for the conformational study of the C(O)NP(O) segment, and the conformations of ±sp±ap, ±sp±sc and ±ap±sp were found (sp = synperiplanar, ap = antiperiplanar, sc = synclinal). The conformations of hydrogen bond donor group(s) with respect to the acceptor group(s) were also considered. The investigated structures belong to three classes of (RC(O)NH)(R¹R²N)₂P(O) (R¹ and R² ≠ H), (RC(O)NH)(R¹NH)₂P(O) (R¹ ≠ H) and heterocyclic (RC(O)NH)P(O)[NR¹]₂R² phosphoric triamides (R¹ = H or ≠ H, R² = a hydrocarbon fragment), and the hydrogen bond patterns include dimer, tetramer, chain, tape, ladder, two-dimensional assembly and three-dimensional architecture. In the new structure, the conformation of the C(O)NP(O) fragment is –sp+ap, and molecules are assembled in a tape arrangement (parallel to the [110] axis) through N_CP–H···O═P and N_P–H···O═C hydrogen bonds (N_CP is the nitrogen atom of the C(O)NHP(O) fragment and N_P is the other N atom bonded to phosphorus).

Graphical Abstract

The interplay between conformation and hydrogen bond pattern was studied in 211 (C(O)NH)(N)₂P(O)-based phosphoric triamides retrieved from the Cambridge Structural Database (CSD) and one new structure, (CHCl₂C(O)NH)(CH₃CH₂CH₂NH)₂P(O).

A homochiral metal-organic framework, [Ni(D-L)(py)₂(H₂O)₂]_n (1) [D-H₂L = 4,4′-[[(1R,3S)-1,2,2-trimethylcyclopentane-1,3-dicarbonyl]bis-(azanediyl)]dibenzoic acid], has been successfully synthesized based on D-camphorate-derived enantiopure ligand. 1 was characterized by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), Fourier transform infrared spectral analysis (FTIR), thermogravimetric analysis (TGA) and the circular dichroism (CD) spectrum. The experimental results show that 1 features a homochiral triple helix and is formed a 3D supramolecular framework by supramolecular interactions. In addition, the circular dichroism (CD) spectrum verifies the chirality introduction from the ligand to crystal. The successful preparation of the homochiral Ni-MOF provides more possibilities of employing the chiral ligand to produce various chiral MOFs.

Graphical Abstract

A homochiral Ni(II)-MOF 1 was prepared by using D-camphorate-derived enantiopure ligand under solvothermal condition, in which the chirality of 1 was confirmed by the circular dichroism (CD) spectrum