Acta Crystallographica Section E: Crystallographic Communications最新文献

The crystal structure of LiLu[MoO₄]₂, which emerged as a by-product of the synthesis to obtain lithium derivatives of lutetium molybdate, adopts the scheelite type.

Coarse colorless single crystals of lithium lutetium bis­[orthomolybdate(VI)], LiLu[MoO₄]₂, were obtained as a by-product from a reaction aimed at lithium derivatives of lutetium molybdate. The title compound crystallizes in the scheelite structure type (tetra­gonal, space group I4₁/a) with two formula units per unit cell. The Wyckoff position 4b (site symmetry

This study presents two anhydrous polymorphic forms of psilocin, detailing their crystal structures and hydrogen-bonding differences, with Form II introducing a novel conformation and whole-mol­ecule disorder.

The title compound, C₁₂H₁₆N₂O, is a hy­droxy-substituted mono­amine alkaloid, and the primary metabolite of the naturally occurring psychedelic compound psilocybin. Crystalline forms of psilocin are known, but their characterization by single-crystal structure analysis is limited. Herein, two anhydrous polymorphic forms (I and II) of psilocin are described. The crystal structure of polymorphic Form I, in space group P2₁/c, was first reported in 1974. Along with the redeterm­ination to modern standards and unambiguous location of the acidic H atom and variable-temperature single-crystal unit-cell determinations for Form I, the Form II polymorph of the title compound, which crystallizes in the monoclinic space group P2₁/n, is described for the first time. The psilocin mol­ecules are present in both forms in their phenol–amine tautomeric forms (not resolved in the 1974 report). The mol­ecules in Forms I and II, however, feature different conformations of their N,N-dimethyl ethyl­ene substituent, with the N—C—C—C link in Form I being trans and in Form II being gauche, allowing the latter to bend back to the hydroxyl group of the same mol­ecule, leading to the formation of a strong intra­molecular O—H⋯N hydrogen bond between the hydroxyl moiety and ethyl­amino-nitro­gen group. In the extended structure of Form II, the mol­ecules form one-dimensional strands through N—H⋯O hydrogen bonds from the indole group to the oxygen atom of the hydroxyl moiety of an adjacent mol­ecule. Form II exhibits whole-mol­ecule disorder due to a pseudo-mirror operation, with an occupancy ratio of 0.689 (5):0.311 (5) for the two components. In contrast, Form I does not feature intra­molecular hydrogen bonds but forms a layered structure through inter­molecular N—H⋯O and O—H⋯N hydrogen bonds.

The competition between gauche and anti conformations in 2-chloro­ethyl- or 3-chloro­propyldi­methyl­ammonium cations is investigated for the title tetra­chloro­metallate salts in which the alkyl chain is found to disordered with the gauche conformation dominant.

The few examples of structures containing the 2-chloro-N,N-di­methyl­ethan-1-aminium or 3-chloro-N,N-di­methyl­propan-1-aminium cations show a compet­ition between gauche and anti conformations for the chloro­alkyl chain. To explore further the conformational landscape of these cations, and their possible use as mol­ecular switches, the title salts, (C₄H₁₁ClN)₂[CoCl₄] and (C₄H₁₁ClN)₂[ZnCl₄], were prepared and structurally characterized. Details of both structures are in close agreement. The inorganic complex exhibits a slightly flattened tetra­hedral geometry that likely arises from bifurcated N—H hydrogen bonds from the organic cations. The alkyl chain of the cation is disordered between gauche and anti conformations with the gauche conformation occupancy refined to 0.707 (2) for the cobaltate. The gauche conformation places the terminal Cl atom at a tetra­hedral face of the inorganic complex with a contact distance of 3.7576 (9) Å to the Co²⁺ center. The anti conformation places the terminal Cl atom at a contact distance to a neighboring anti conformation terminal Cl atom that is ∼1 Å less than the sum of the van der Waals radii. Thus, if the anti conformation is present at a site, then the nearest neighbor must be gauche. DFT geometry optimizations indicate the gauche conformation is more stable in vacuo by 0.226 eV, which reduces to 0.0584 eV when calculated in a uniform dielectric. DFT geometry optimizations for the unprotonated mol­ecule indicate the anti conformation is stabilized by 0.0428 eV in vacuo, with no strongly preferred conformation in uniform dielectric, to provide support to the notion that this cation could function as a mol­ecular switch via deprotonation.

The synthesis and crystallization of a tri­fluoro­methane­sulfonate salt of 5,10,15,20-tetra­kis­(1-benzyl­pyridin-1-ium-4-yl)-21H,23H-porphyrin, C₆₈H₅₄N₈ ⁴⁺·4CF₃O₃S·4H₂O, 1·OTf, are reported. The asymmetric unit contains half a porphyrin mol­ecule, two tri­fluoro­methane­sulfonate anions and two water mol­ecules of crystallization. The macrocycle of tetra­pyrrole moieties is planar and unexpectedly it has coordinated Ca^II ions in occupational disorder. This Ca^II ion has only 10% occupancy (C₇₂H_61.80Ca_0.10F₁₂N₈O₁₆S₄).

The synthesis, crystallization and characterization of a tri­fluoro­methane­sulfonate salt of 5,10,15,20-tetra­kis­(1-benzyl­pyridin-1-ium-4-yl)-21H,23H-por­phy­rin, C₆₈H₅₄N₈ ⁴⁺·4CF₃SO₃ ⁻·4H₂O, 1·OTf, are reported in this work. The reaction between 5,10,15,20-tetra­kis­(pyridin-4-yl)-21H,23H-porphyrin and benzyl bromide in the presence of 0.1 equiv. of Ca(OH)₂ in CH₃CN under reflux with an N₂ atmosphere and subsequent treatment with silver tri­fluoro­methane­sulfonate (AgOTf) salt produced a red–brown solution. This reaction mixture was filtered and the solvent was allowed to evaporate at room temperature for 3 d to give 1·OTf. Crystal structure determination by single-crystal X-ray diffraction (SCXD) revealed that 1·OTf crystallizes in the space group P2₁/c. The asymmetric unit contains half a porphyrin mol­ecule, two tri­fluoro­methane­sulfonate anions and two water mol­ecules of crystallization. The macrocycle of tetra­pyrrole moieties is planar and unexpectedly it has coordinated Ca^II ions in occupational disorder. This Ca^II ion has only 10% occupancy (C₇₂H_61.80Ca_0.10F₁₂N₈O₁₆S₄). The pyridinium rings bonded to methyl­ene groups from porphyrin are located in two different arrangements in almost orthogonal positions between the plane formed by the porphyrin and the pyridinium rings. The crystal structure features cation⋯π inter­actions between the Ca^II atom and the π-system of the phenyl ring of neighboring mol­ecules. Both tri­fluoro­methane­sulfonate anions are found at the periphery of 1, forming hydrogen bonds with water mol­ecules.

The crystal structures of three new indole derivative are described. The supra­molecular relations in the system were assessed with a Hirshfeld surface analysis and calculation of the inter­action energies, which suggest a primary significance of π–π and C—H⋯π inter­actions involving the indole moieties.

Three new 1H-indole derivatives, namely, 2-(bromo­meth­yl)-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C₁₆H₁₄BrNO₂S, (I), 2-[(E)-2-(2-bromo-5-meth­oxy­phen­yl)ethen­yl]-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C₂₄H₂₀BrNO₃S, (II), and 2-[(E)-2-(2-bromo­phen­yl)ethen­yl]-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C₂₃H₁₈BrNO₂S, (III), exhibit nearly orthogonal orientations of their indole ring systems and sulfonyl-bound phenyl rings. Such conformations are favourable for inter­molecular bonding involving sets of slipped π–π inter­actions between the indole systems and mutual C—H⋯π hydrogen bonds, with the generation of two-dimensional monoperiodic patterns. The latter are found in all three structures, in the form of supra­molecular columns with every pair of successive mol­ecules related by inversion. The crystal packing of the compounds is additionally stabilized by weaker slipped π–π inter­actions between the outer phenyl rings (in II and III) and by weak C—H⋯O, C—H⋯Br and C—H⋯π hydrogen bonds. The structural significance of the different kinds of inter­actions agree with the results of a Hirshfeld surface analysis and the calculated inter­action energies. In particular, the largest inter­action energies (up to −60.8 kJ mol⁻¹) are associated with pairing of anti­parallel indole systems, while the energetics of weak hydrogen bonds and phenyl π–π inter­actions are comparable and account for 13–34 kJ mol⁻¹.

In the Pd^II complex, two substituted 3-(pyridin-2-yl)-1,2,4-triazole ligands in the neutral form coordinate to the metal atom through the pyridine-N and triazole-N atoms in a trans-configuration.

The new palladium(II) complex, [Pd(C₁₆H₁₆N₄O₃)₂](CF₃COO)₂·2CF₃COOH, crystallizes in the triclinic space group P

In the crystal, mol­ecules are connected by C—H⋯O hydrogen bonds, forming C(8) chains running along the a-axis direction. Cohesion of the packing is provided by weak van der Waals inter­actions between the chains.

In the title compound, C₁₅H₁₃NO₃S, the mol­ecular conformation is stable with the intra­molecular O—H⋯O hydrogen bond forming a S(7) ring motif. In the crystal, mol­ecules are connected by C—H⋯O hydrogen bonds, forming C(8) chains running along the a-axis direction. Cohesion of the packing is provided by weak van der Waals inter­actions between the chains. A Hirshfeld surface analysis was undertaken to investigate and qu­antify the inter­molecular inter­actions. The thio­phene ring is disordered in a 0.9466 (17):0.0534 (17) ratio over two positions rotated by 180°.

A thio­urea derivative with two dissimilar functional groups was prepared and characterized. In the crystal, pairs of adjacent mol­ecules inter­act via inter­molecular hydrogen bonds of type C—H⋯N, C—H⋯S and N—H⋯S, resulting in mol­ecular layers parallel to the ac plane.

The chemical reaction of 4-bromo­benzoyl­chloride and 2-amino­thia­zole in the presence of potassium thio­cyanate yielded a white solid formulated as C₁₅H₁₀BrN₃OS₂, which consists of 4-bromo­benzamido and 2-benzo­thia­zolyl moieties connected by a thio­urea group. The 4-bromo­benzamido and 2-benzo­thia­zolyl moieties are in a trans conformtion (sometimes also called s-trans due to the single bond) with respect to the N—C bond. The dihedral angle between the mean planes of the 4-bromo­phenyl and the 2-benzo­thia­zolyl units is 10.45 (11)°. The thio­urea moiety, —C—NH—C(=S) —NH— fragment forms a dihedral angle of 8.64 (12)° with the 4-bromo­phenyl ring and is almost coplanar with the 2-benzo­thia­zolyl moiety, with a dihedral angle of 1.94 (11)°. The mol­ecular structure is stabilized by intra­molecular N—H⋯O hydrogen bonds, resulting in the formation of an S(6) ring. In the crystal, pairs of adjacent mol­ecules inter­act via inter­molecular hydrogen bonds of type C—H⋯N, C—H⋯S and N—H⋯S, resulting in mol­ecular layers parallel to the ac plane.

Ethyl 2-[(2-oxo-2H-chromen-6-yl)­oxy]acetate, a coumarin derivative, crystallizes in sheets, within which mol­ecules are held by weak C—H⋯O hydrogen-bonding inter­actions and between which mol­ecules inter­act by π–π stacking and additional C—H⋯O weak hydrogen bonds between ethyl acet­oxy groups.

Ethyl 2-[(2-oxo-2H-chromen-6-yl)­oxy]acetate, C₁₃H₁₂O₅, a member of the pharmacologically important class of coumarins, crystallizes in the monoclinic C2/c space group in the form of sheets, within which mol­ecules are related by inversion centers and 2₁ axes. Multiple C—H⋯O weak hydrogen-bonding inter­actions reinforce this pattern. The planes of these sheets are oriented in the approximate direction of the ac face diagonal. Inter­sheet inter­actions are a combination of coumarin system π–π stacking and additional C—H⋯O weak hydrogen bonds between ethyl acet­oxy groups.

Very large high-quality crystals of a new member of the family of double nitrates, namely, [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O, were crystallized in large amounts. The structure was determined via single-crystal X-ray diffraction to high resolution. Extensive structural information, including hydrogen-bonding details, was obtained at the same time.

This study introduces bis­[hexa­kis­(nitrato-κ² O,O′)lanthanum(III)] tris­[hexa­aqua­nickel(II)] hexa­hydrate, [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O, with a structure refined in the hexa­gonal space group R