Acta Crystallographica Section E: Crystallographic Communications最新文献

The coordination co-crystal (4-bromo-2-{[(2-hy-droxy-eth-yl)imino]-meth-yl}pheno-lolato-κ³ O,N,O')(thio-cyanato-κN)copper(II)-5-bromo-2-hy-droxy-benz-alde-hyde-water (2/1/1), [Cu(C₉H₉BrNO₂)(NCS)]·0.5C₇H₅BrO₂·0.5H₂O or [Cu(HL)(SCN)]₂·C₇H₅BrO₂·H₂O, crystallizes in the monoclinic space group P2₁/c. The asymmetric unit contains two mononuclear units of the complex, each consisting of one deprotonated ligand, one thio-cyanate anion (SCN^-) coordinated through its nitro-gen atom, one free water mol-ecule, and one free 5-bromo-salicyl-aldehyde mol-ecule, forming a co-crystal. The copper atom is four-coordinate, adopting a slightly distorted square-planar geometry defined by the tridentate ligand and the nitro-gen atom of the thio-cyanate anion. Bond length values show that the thio-cyanate ion has a linear S-C≡N arrangement, typical of a terminal, N-bound iso-thio-cyanate group. The water mol-ecule plays a key role in linking the two complex units through O-H⋯O hydrogen bonds. In the crystal, C-H⋯O and C-H⋯Br hydrogen bonds allow the free 5-bromo-salicyl-aldehyde mol-ecule to form a bridge between two adjacent layers. Additional O-H⋯O, C-H⋯S, O-H⋯S, and C-H⋯N inter-actions further consolidate the overall structure.

The title compound, {[CdCl₂(C₆H₈N₂)₂]·H₂O} _n (C₆H₈N₂ = 2,3-di-methyl-pyrazine) was prepared by the reaction of cadmium chloride with 2,3-di-methyl-pyrazine in water. The asymmetric unit consists of two crystallographically independent cadmium cations that are situated on a twofold rotation axis, two crystallographically independent chloride anions and 2,3-di-methyl-pyrazine ligands as well as one water mol-ecule that are all located in general positions. The cadmium cations are octa-hedrally coordinated by two terminally N-bonded 2,3-di-methyl-pyrazine ligands and four chloride anions and are linked by pairs of μ-1,1 bridging chloride anions into chains that propagate in the crystallographic b-axis direction. These chains are connected into layers via the water mol-ecule of crystallization by inter-chain O-H⋯N hydrogen bonding. Powder X-ray diffraction (PXRD) indicates that a pure phase has been obtained. Thermogravimetry (TG) coupled to differential thermal analysis (DTA) indicates that the water mol-ecules are removed in the first step and that the 2,3-di-methyl-pyrazine ligands are lost in the subsequent two steps, leading to a compound with the composition [CdCl₂(C₆H₈N₂)].

The BBr₃-promoted de-methyl-ation of 3-(meth-oxy-meth-yl)-6-phenyl-1,2,4,5-tetra-zine, C₁₀H₁₀N₄O, resulted in the alcohol (6-phenyl-1,2,4,5-tetrazin-3-yl)methanol, C₉H₈N₄O, and the bromide 3-(bromo-meth-yl)-6-phenyl-1,2,4,5-tetra-zine, C₉H₇BrN₄. All three compounds were analysed by nuclear magnetic resonance (NMR) spectroscopy in solution and by single-crystal X-ray diffraction using non-spherical scattering factors for structure refinement. The substrate as well as the corresponding bromide form π-π inter-actions between anti-parallel stacks of mol-ecules. In contrast, due to the inter-molecular hydrogen bonds present, which lead to the formation of a bent dimer, the alcohol forms only very weak parallel π-π stacks. Corresponding O-H⋯N hydrogen bonds are established between the hy-droxy group and an N atom of a neighbouring tetra-zine mol-ecule, an only rarely explored structural feature of 1,2,4,5-tetra-zines.

The title compound, [Ag(C₆F₅CN)₄][Al{OC(CF₃)₃}₄], was obtained by reaction of Ag[Al(OC(CF₃)₃)₄] with excess perfluoro-benzo-nitrile. The crystals belong to the chiral space group P2₁ with Z' = 2, containing two independent [Ag(C₆F₅CN)₄]⁺ cations and two [Al(OC(CF₃)₃)₄]^- anions in the asymmetric unit. Each Ag^I centre is four-coordinate and adopts a distorted tetra-hedral geometry. One of the nitrile ligands in both Ag^I centres has a noticeably longer Ag-N distance [2.383 (8) and 2.371 (9) Å] and the Ag-N-C angle [148.3 (7) and 148.8 (8)°] deviates significantly from linearity in both of these cases. The other Ag-N distances are between 2.207 (8) and 2.280 (8) Å with Ag-N-C angles between 165.4 (7) and 177.0 (7)°. N-Ag-N angles vary from 94.5 (3) to 120.3 (3)°. In the crystallographic overlay, the two Ag^I cations appear as approximate non-superimposable mirror images. The arrangement of the cations dominates the crystal packing with the anions occupying the spaces between the cations. There are no short Ag⋯anion contacts. The structure contains numerous short F⋯F contacts, which is unsurprising given the perfluorinated nature of the system, and there is an indication of C-F⋯π type inter-actions. ¹⁹F NMR spectra of the complex were consistent with the crystallographically determined structure with four perfluoro-benzo-nitrile ligands.

The 3-imino-3H-isoindol-1-amine tautomeric form of (Z)-N-allyl-3-(allyl-imino)-3H-isoindol-1-amine, C₁₄H₁₅N₃, was confirmed by a single-crystal X-ray diffraction study. The distribution of electron density within the -NH-C=N-C=N- conjugated fragment corresponds to that found in previously studied N,N'-disubstituted 3-imino-3H-isoindol-1-amines. The two mol-ecules in the asymmetric unit of the title compound differ in the conformation of the allyl substituents. In one of these mol-ecules, the two allyl fragments are disordered over two sets of sites in 0.628 (7):0.372 (7) and 0.755 (5):0.245 (5) ratios. In the crystal, the two unique mol-ecules are arranged alternately in infinite chains parallel to [001] due to the formation of inter-molecular N-H⋯N hydrogen bonds.

The asymmetric unit of the title compound, [Co(NCS)₂(C₆H₄N₂)₂] _n (C₆H₄N₂ = pyri-dine-4-car-bo-ni-trile), consists of two crystallographically independent cobalt cations that are located on centers of inversion as well as two independent thio-cyanate anions and two independent pyri-dine-4-car-bo-ni-trile coligands that occupy general positions. Each of the cobalt cations is sixfold coordinated by two N- and two S-bonding thio-cyanate anions and two pyri-dine-4-car-bo-ni-trile coligands in an slightly distorted CoN₄S₂ octa-hedral geometry with an all-trans coordination. The cobalt cations are linked by pairs of μ-1,3-bridging anionic ligands into linear chains. Powder X-ray diffraction (PXRD) experiments indicate that the title compound was obtained as a pure phase. Moreover, comparison of the experimental X-ray powder pattern of the residue obtained after water removal from [Co(NCS)₂(C₆H₄N₂)₂(H₂O)₂] reported recently [Näther (2026 ▸).Acta Cryst. E82, 441-445] with the calculated powder pattern of the title compound proves that the latter crystalline phase has formed and indicates that a second modification with the same composition as that of the title compound might exist.

Uran-yl(VI) complexes have been researched in many laboratories due to their relevance to actinide coordination chemistry and nuclear fuel reprocessing. The asymmetric unit of the title uranyl complex, [U(C₅H₇O₂)₂O₂(C₅H₄Cl₂N₂)]·0.5CH₃OH or [UO₂(acac)₂(4-amino-3,5-di-chloro-pyridine)]·0.5CH₃OH, contains two crystallographically independent uran-yl(VI) complex mol-ecules and one methanol solvent mol-ecule. Each U^VI atom adopts a UNO₆ penta-gonal-bipyramidal coordination geometry, in which two uranyl O atoms occupy the axial positions, whereas four O atoms from two chelating bidentate acac ligands and one N atom from a 4-amino-3,5-di-chloro-pyridine ligand define the equatorial plane. The U=O bond lengths are 1.757 (10) and 1.807 (11) Å for one independent mol-ecule and 1.752 (11) and 1.766 (11) Å for the other, while the U=O(acac) and U-N bond lengths lie in the ranges 2.302 (11)-2.384 (10) Å and 2.591 (13)-2.645 (13) Å, respectively. The bond lengths around the U atoms decrease in the order U-N > U-Oacac > U=O. The uranyl units are slightly bent, with O=U=O angles of 177.0 (5) and 176.5 (5)°. In the crystal, the methanol solvent mol-ecule is linked to the amino group in the coordinated ligand by an inter-molecular N-H⋯O hydrogen bond [N⋯O = 2.90 (2) Å], which is likely to contribute to the low-symmetry crystal arrangement.

In the title compound, C₁₅H₁₂FNO₄, the dihedral angle between the aromatic rings is 77.78 (8)°. In the crystal, the mol-ecules are linked into zigzag ribbons propagating along the [210] direction by pairwise O-H⋯O hydrogen bonds through their two carb-oxy-lic acid groups to generate centrosymmetric R ² ₂(8) dimers in each case. In addition, mol-ecules are connected via pairwise N-H⋯π inter-actions between the NH groups and the fluoro-benzene rings. Aromatic π-π stacking inter-actions and weak C-H⋯F and C-H⋯O inter-actions also contribute to the packing. A Hirshfeld surface analysis shows that the most important contributions to the crystal packing are from H⋯H (30.7%), O⋯H/H⋯O (26.1%) and C⋯H/H⋯C (20.3%) contacts.

The title compounds μ-oxido-bis-[(2-{[2-(3-meth-oxy-2-oxido-benzyl-idene-amino)-phenyl-imino]-meth-yl}-6-meth-oxy-phenolato)iron(III)] penta-hydrate, [Fe₂(C₂₂H₁₈N₂O₄]·5H₂O or {[(Fe^III(L)](μ₂-O)[Fe^III(L)]}·5H₂O (2), and di-chlorido-bis-(μ-2-{[2-(3-meth-oxy-2-oxido-benzyl-idene-amino)-phenyl-imino]-meth-yl}-6-meth-oxy-phenolato)diiron(III)potassium(I) nitrate, [KFe₂(C₂₂H₁₈N₂O₄)₂Cl₂]NO₃ or {[(Fe^III(L)(Cl)](K)[Fe^III(L)(Cl)]}·NO₃ (3), were formed from the reaction of the metallo-ligand [Fe^II(L)]·(H₂O) (H₂ L is 2-{[2-(2-hy-droxy-3-meth-oxy-benzyl-idene-amino)-phenyl-imino]-meth-yl}-6-meth-oxy-phenol, C₂₂H₂₀N₂O₄) with yttrium acetate and potassium nitrate, respectively. In complex 2, the Fe^III ions, which presumably arise through aerial oxidation from Fe^II, have a distorted square-pyramidal environment and are bridged by a μ₂ oxo oxygen atom with an Fe-O-Fe angle of 137.97 (5)°. In complex (3) the environment around the Fe^III ions is a distorted square pyramid. All four phenoxo oxygen atoms link the Fe^III ions to a potassium atom (site symmetry 2), yielding two four-membered Fe/O/K/O rings. The K⁺ ion is linked also to four meth-oxy oxygen atoms.

The crystal structure of the title compound, [Zn(C₁₀H₈NO₃S)₂(C₁₂H₈N₂)(H₂O)]·H₂O, is reported together with an analysis of its inter-molecular inter-actions. The Zn^II ion is five-coordinate, being bonded to two monodentate carboxyl-ate O atoms from two crystallographically independent 3-(2-sulfanylidene-2,3-di-hydro-1,3-benzoxazol-3-yl)propano-ate ligands, two N atoms of a chelating 1,10-phenanthroline ligand and one water O atom. The coordination geometry is distorted square-pyramidal (τ₅ ≃ 0.30). Although the two carboxyl-ate ligands adopt the same κO coordination mode, they differ in their Zn-O bond lengths and in the conformations of their propano-ate chains. In the crystal, O-H⋯O hydrogen bonds involving the coordinated and solvent water mol-ecules link the complexes into one-dimensional ribbons parallel to [100], reinforced by C-H⋯O and C-H⋯S contacts. Additional consolidation is provided by π-π stacking inter-actions involving the phenanthroline and benzoxazoline-derived aromatic rings. Hirshfeld surface analysis shows that H⋯H (42.0%), H⋯O/O⋯H (19.1%), H⋯S/S⋯H (13.7%) and H⋯C/C⋯H (11.9%) contacts dominate the inter-molecular surface, while C⋯C contacts (5.8%) are consistent with the observed π-π stacking.