Journal of Chemical Crystallography最新文献

Reaction of N-benzyl-1-chloromethanesulfonamide with phenyl isothiocyanate formed N-benzyl-3-phenylimino-1,4,2-dithiazolidine 1,1-dioxide. Crystals of this compound occurred in the monoclinic system, space group P 2(1), a = 26.7099(16) Å, b = 13.2518(5) Å, c = 8.2769(4) Å, β = 97.099(5)^o, Z = 8, with four molecules in the asymmetric unit. The structure confirms a prior assignment that the C = S bond of the isothiocyanate was the reactive moiety. Using the same reaction conditions, 3,5-dimethylphenyl isocyanate was reacted N-benzyl-1-chloromethanesulfonamide to produce a product in 81% yield, which was determined to be 2-benzyl-4-(3’,5’-dimethylphenyl)-1,2,4-thiadiazolidin-3-one 1,1-dioxide. Crystals of this compound are monoclinic, space group P 2(1)/n, a = 5.2243(11) Å, b = 15.844(5) Å, c = 18.628(3) Å, β = 96.72(2)^o, and Z = 4. This product demonstrated that the C = N bond of the aryl isocyanate reacted to form the 1,2,4-thiadiazolidin-3-one 1,1-dioxide ring system.

Graphical Abstract

Heterocyclic rings formed from N-benzyl-1-chloromethanesulfonamide and phenyl isothiocyanate via the C = S bond (structure on the left) or 3,5-dimethylphenyl isocyanate via the C = N bond (structure on the right)

8-Nitrobenzo-1,3-thiazin-4-ones (BTZs) are a promising class of antitubercular agents with a novel mechanism of action, viz. suicide inhibition of decaprenylphosphoryl-β-D-ribose 2’-epimerase 1 (DprE1), an enzyme crucial for cell wall synthesis in the pathogen Mycobacterium tuberculosis. 8-Nitro-2-(piperidin-1-yl)-6-(trifluoromethyl)-4H-benzo-1,3-thiazin-4-one (1) is a chemically simplified analogue of the anti-tuberculosis phase 2 clinical drug candidate BTZ-043. Structural elucidation of 1 in the solid-state has been carried out by X-ray crystallography and two polymorphic forms of 1 have been revealed. 1-I crystallizes in the triclinic system (space group P-1, Z = 6) with one molecule exhibiting whole-molecule disorder with a preferred orientation. The crystal structure of 1-II belongs to the tetragonal system (space group P4₃, Z = 4) and exhibits positional disorder in several parts of the molecule.

Graphical Abstract

X-ray crystallography revealed a triclinic (space group P-1, Z = 6) and a tetragonal (space group P4₃, Z = 4) polymorph of the antimycobacterial agent 8-nitro-2-(piperidin-1-yl)-6-(trifluoromethyl)-4H-benzo-1,3-thiazin-4-one

The study about the supramolecular interactions in the organic–inorganic hybrids will be significant for the design of new photo/electrical functional materials. In this work, 1,ω-bis(isoquinoline)alkane cations with different spacer lengths (n = 3, 5, 6) have been incorporated with iodobismuthates to construct three new hybrids, which have been formula as [BIQPP]₂[Bi₄I₁₆] (1), [BIQPT]₂[Bi₄I₁₆] (2) and [BIQHX]₂[Bi₄I₁₆] (3) through X-ray single crystal diffraction method (BIQPP²⁺ = 1,3-bis(isoquinoline)propane, BIQPT²⁺ = 1,5-bis(isoquinoline) pentane, BIQHX²⁺ = 1,6-bis(isoquinoline)hexane). The centrosymmetric [Bi₄I₁₆]⁴⁻ anions are constructed from four edge-sharing BiI₆ octahedra. Interestingly, with the elongation of spacer length on isoquinoline from 3, 5 to 6, the iodobismuthate anions exhibit 0-D [Bi₄I₁₆]⁴⁻ tetramers (n = 3, 6 for 1 and 3) and pseudo 3-D [Bi₄I₁₆]_n⁴ⁿ⁻ network (n = 5, for 2) based on I···I interactions. Supramolecular interactions including π–π stacking interactions and C–H···I hydrogen bonds contribute to their structural extensions. Consequently, the enhanced red emission intensity and the lower thermochromic temperature can be observed in 2. The clarification on the spacer effect on the supramolecular interactions and functional properties of this work will be beneficial for the design of new functional materials.

Graphical Abstract

Different iodobismuthate anions and photo-physical properties including red emission intensity and thermochromism can be achieved by elongating the spacer lengths in 1,ω-Bis(isoquinoline)alkane cations

The structures of [Fe(CO)₃(η⁴-6-exo-(tri-m-tolylphosphine)cyclohepta-2,4-dien-1-one][BF₄] [tetragonal, a = 35.6005(7), b = 35.6005(7), c = 10.5456(3), space group I4₁/a] and [Fe(CO)₃(η⁴-6-exo-(tri-p-fluorophenylphosphine)cyclohepta-2,4-dien-1-one][BF₄] [triclinic, a = 9.8852(3), b = 10.0996(4), c = 16.0526(4), α = 99.813(3), β = 94.164(2), g = 102.911(3) space group P-1] have been determined. Both structures contain a disordered CH₂Cl₂ molecule. The tetrafluoroborate ion in [Fe(CO)₃(η⁴-6-exo-(tri-m-tolylphosphine)cyclohepta-2,4-dien-1-one][BF₄] is also disordered. There are no close contacts indicative of hydrogen bonding within either structure, but there is π-π stacking observed for [Fe(CO)₃(η⁴-6-exo-(tri-m-tolylphosphine)cyclohepta-2,4-dien-1-one][BF₄].

Graphical Abstract

Addition of PAr₃ (Ar = m-C₆H₄CH₃ or p-C₆H₄F) to [Fe(CO)₃(η⁵-cyclohepta-2,4-dien-5-yl-1-one)][BF₄] results in attack at the coordinated ring in a position exo- to the iron atom forming the corresponding [Fe(CO)₃(η⁴-6-exo-(PAr₃)cyclohepta-2,4-dien-1-one][BF₄] compounds, which were structurally characterized

The structures of [Fe(CO)₃(η⁴-6-exo-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF₄] [orthorhombic, a = 12.3269(4), b = 13.5243(5), c = 13.7127(4), space group Pna2₁] and [Fe(CO)₃(η⁴-6-exo-(tert-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF₄] [monoclinic, a = 9.7947(3), b = 12.8766(3), c = 20.2168(5), β = 91.089(3), space group P2₁/c] have been determined. The disordered tetrafluoroborate ion in [Fe(CO)₃(η⁴-6-exo-(methyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF₄] sits between two of the cations and displays interactions with hydrogen atoms in the ortho- position of the phenyl rings, the methyl group and the 6-position of the seven-membered ring. There is also close contact between the ketone oxygen atom and two protons in another cation, a proton of the methyl group and the proton in the 5-position of the seven-membered ring. The tetrafluoroborate anion in [Fe(CO)₃(η⁴-6-exo-(tert-butyldiphenylphosphine)cyclohepta-2,4-dien-1-one][BF₄] is not disordered and shows close contacts with protons in three cation units. In one cation the interaction is with two protons from separate methyl groups of the tert-butyl substituent. The remaining interactions are with a proton in the ortho- position of a phenyl ring in one cation and the proton in the 2-position of the seven-membered ring. There is also an interaction between the ketone oxygen and a proton from the tert-butyl group in another cationic unit.

Graphical abstract

Addition of PPh₂R (R = Me or ^tBu) to [Fe(CO)₃(η⁵-cyclohepta-2,4-dien-5-yl-1-one)][BF₄] results in exo- attack at the coordinated ring forming the [Fe(CO)₃(η⁴-6-exo-(PPh₂R)cyclohepta-2,4-dien-1-one][BF₄] compounds, both of which were structurally characterized.

Crystal structures of two 2-nitropropene derivatives, namely 1,4-bis((E)-2-nitroprop-1-enyl)benzene and 4,4′-bis((E)-2-nitroprop-1-enyl)biphenyl, support relevance of lone pair-π-hole interactions of nitro groups to the crystal packing of extended polyaromatic molecules. For the former structure, these bonds complement slipped π–π interactions of the benzene rings within a basic supramolecular motif representing infinite stacks. In the biphenyl derivative, only one out of two nitro groups afford NO₂⋯NO₂ bonds (N⋯O = 3.191(2) Å) as a local pattern. The decreased significance of lone pair-π-hole interactions is in line with growing contribution of weak dispersion forces, which favor close alignment of the molecules and larger interaction areas to generate multiple C–H⋯π bonds. Different types of C–H⋯O, C–H⋯π, π–π, NO₂–π, NO₂⋯NO₂, tetrel CH₃⋯O and CH₃⋯π bonds, which actualize in the present structures were further assessed by Hirshfeld surface analysis and intermolecular interaction energies were calculated using the CE B3LYP/6 31G(d,p) energy model. In addition, the facile and high-yielding preparations by condensation of dialdehydes and nitroethane, provide a straightforward access to the present 2-nitropropenes, as valuable synthetic intermediates.

Graphical Abstract

The X-ray structures of 1,4-bis((E)-2-nitroprop-1-enyl)benzene and 4,4′-bis((E)-2-nitroprop-1-enyl)biphenyl reveal coexistence and interplay of lone pair-π-hole NO₂⋯NO₂ bonds, weak hydrogen and tetrel bonds and aromatic interactions.

The synthesis and structural details of a mixed-ligand Cu(II) coordination compound, specifically catena-poly[bis(dicyanamido)(1,10-phenanthroline-5,6-dione)copper(II)] 1, are reported. The title compound was synthesized utilizing a solvothermal method by employing dicyanamide, 1,10-phenanthroline-5,6-dione (phendione) and copper(II) sulfate pentahydrate (CuSO₄•5H₂O) as the starting materials. The title compound was characterized by standard analytical and spectroscopic methods. The 3D structure was determined by single-crystal X-ray diffraction. Examination of the supramolecular interaction patterns indicates that the stability of the ladder structure is achieved by the bridging dca anions and the presence of weak hydrogen-bonding contacts, specifically C-H···O and C-H···N bonds, as well as C-O/N···π interactions. These interactions together contribute to the formation of a ladder-type infinite chain structure. The generated structure has been theoretically investigated with Hirshfeld surface analysis, QTAIM and NCI analysis to reveal the interaction energies and bonds present inside and between molecules. The non-covalent interactions present in the crystal structure were further investigated theoretically, with particular attention to the cooperative C ≡ N···π(py) and N···π(hole) interactions involving the dicyanamide ligand and nitrile moieties in the compound. The solid-state stability of compound 1 appears to be strongly influenced by the cooperative effect of H-bonding interactions as well as the C ≡ N···π(py) and N···π(hole) contacts, as confirmed by theoretical calculations.

Graphical Abstract

Synthesis, Structure and Theoretical Calculations of a Unique Ladder Chain Containing the Dicyanamido Ligand (dca), Consisting of 2 µ_1,5-dca Bridged Dinuclear Cu₂(dca)₂Units and Having µ_1,3-dca Bridges along the Chain.

One sentence essence:

catena-poly[bis(dicyanamido)(1,10-phenanthroline-5,6-dione)copper(II)] is a unique ribbon ladder, infinite chain structure with two differently bridged dicyanamide anions

A novel Cadmium(II) coordination polymer, namely {[Cd(L)(bpmh)_0.5(DMA)(H₂O)]}_n (CP 1), has been successfully synthesized under solvothermal conditions using H₂L (5-(1-oxoisoindion-2-yl)isophthalic acid) and bpmh ((1E,2E)-1,2-bis(pyridine-4-ylmethylene)hydrazine) ligand. The CP 1 is well described by single-crystal X-ray diffraction, PXRD, FT-IR, TGA and solid-state fluorescence properties. X-ray single crystal diffraction analysis shows that CP 1 crystallizes in the P-1 space group, and possesses 1D ladder chains, which were further connected by hydrogen bonding interactions to form 3D supramolecular architecture. Results of the property studies showed that we successfully synthesized a pure phase fluorescent material with good thermal stability and has potential applications for the development of future fluorescent materials.(II)

Graphical Abstract

Single-crystal X-ray analysis shows that a novel Cd (II) fluorescence coordination polymer based on nitrogen-containing aromatic ligands was described in this work.

Two chiral ferrocenylamine alcohols of (R)-[Fe(η⁵-C₅H₅){η⁵-C₅H₄CH₂NHCH(ⁱPr)(CH₂OH)}] (1) and (R)-[Fe(η⁵-C₅H₅){η⁵-C₅H₄CH₂NHCH(C₆H₅)(CH₂OH)}] (2) were synthesized by condensation reaction of ferrocenylformaldehyde and chiral aminoalcohols followed by the reduction with sodium borohydride. The crystal structures of the two compounds were determined by single crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic space group P2₁2₁2 with a = 16.600(8) Å, b = 28.990(14) Å, c = 6.531(3) Å, and Z = 8. Compound 21.13H₂O crystallizes in the monoclinic space group I2 with a = 22.671(4) Å, b = 6.2481(10) Å, c = 22.112(4) Å, β = 96.763(12)°, and Z = 8.

Graphical Abstract

The ionic compound N-(2-hydroxyethyl)piperazinium chloride (HEPH)Cl, containing a piperazinium cation with a + 1 charge, was crystallized in the orthorhombic space group P2₁2₁2₁. The unit cell parameters were determined to be a = 8.6083(3) Å, b = 8.8523(3) Å, and c = 10.7405(4) Å. The volume of the unit cell was found to be 818.46(5) ų, with a Z value of 4. Refinement yielded R[F² > 2σ(F²)] = 0.018, wR(F²) = 0.028, and a goodness-of-fit parameter of S = 1.77. The crystal structure reveals the presence of three hydrogen bonds: O1–H1o1···Cl1, N1–H1n1···N2, and N1–H2n1···Cl1, which contribute to the specific molecular arrangements within the crystal lattice.Electrochemical properties of (HEPH)Cl were examined by cyclic voltammetry (CV). Molecular docking experiments were conducted to assess the interactions of (HEPH)Cl with Mycobacterium tuberculosis DNA gyrase, coronavirus main protease, Plasmodium falciparum protein, and human serum albumin.

Graphical Abstract

N-(2-hydroxyethyl)piperazinium chloride cation uniquely adopts a chair conformation carrying a +1 charge, stabilized by crucial hydrogen bonding interactions that enhance molecular recognition and binding affinity observed in docking study.