Crystal structure, spectroscopic characterization and Hirshfeld surface analysis of aquadichlorido{N- [(pyridin-2-yl)methylidene]aniline}copper(II) monohydrate

The reaction of N-phenyl-1-(pyridin-2-yl)methanimine with copper chloride dihydrate produced the title neutral complex, [CuCl2(C12H10N2)(H2O)]·H2O. The CuII ion is five-coordinated in a distorted square-pyramidal geometry, in which the two N atoms of the bidentate Schiff base, as well as one chloro and a water mol­ecule, form the irregular base of the pyramidal structure. Meanwhile, the apical chloride ligand inter­acts through a strong hydrogen bond with a water mol­ecule of crystallization. In the crystal, mol­ecules are arranged in pairs, forming a stacking of symmetrical cyclic dimers that inter­act in turn through strong hydrogen bonds between the chloride ligands and both the coordinated and the crystallization water mol­ecules. The mol­ecular and electronic structures of the complex were also studied in detail using EPR (continuous and pulsed), FT–IR and Raman spectroscopy, as well as magnetization measurements. Likewise, Hirshfeld surface analysis was used to investigate the inter­molecular inter­actions in the crystal packing.Centro de Química InorgánicaInstituto de Física La Plat

Twisted Imide Bond in Noncyclic Imides. Synthesis and Structural and Vibrational Properties of <i>N</i>,<i>N</i>-Bis(furan-2-carbonyl)-4-chloroaniline

A novel imide compound (C₁₆H₁₀ClNO₄) was synthesized in a single step by the reaction of 2-furoic acid with 4-chloroaniline in a 2:1 molar ratio using carbonyldiimidazole (CDI) in dry THF. The structure was supported by spectroscopic and elemental analyses and the single-crystal X-ray diffraction data. Crystallographic studies revealed that the compound crystallized in a monoclinic system with space group <i>P</i>2₁/<i>c</i> and unit cell dimensions <i>a</i> = 12.2575(5) Å, <i>b</i> = 7.7596(2) Å, <i>c</i> = 15.0234(7) Å, α = γ = 90°, β = 92.771(4)°, <i>V</i> = 1427.25(10) ų, <i>Z</i> = 4. The imide bond is twisted, and the OC–N–C­(O) units deviate significantly from planarity with dihedral angles around the imide group reaching ca. −150.3° (C1–N1–C2–O21 = −148.8° and C2–N1–C1–O11 = −151.9°). The nonplanarity of the imide moiety and the related conformational properties are discussed in a combined approach that includes the analysis of the vibrational spectra together with theoretical calculation methods, especially in terms of natural bond orbital (NBO) calculations

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX3CH2SNO, X = H and F)

Canneva A, Della Vedova CO, Mitzel NW, Erben MF. Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX3CH2SNO, X = H and F). The Journal of Physical Chemistry A. 2015;119(9):1524-1533.The simple 2,2,2-trifluoroethyl thionitrite molecule, CF3CH2SNO, has been prepared in good yield for the first time using CF3CH2SH and NOCl in slight excess. The vapor pressure of the red-brown compound CF3CH2SNO follows, in the temperature range between 226 and 268 K, the equation log p = 12.0-3881/T (p/bar, T/K), and its extrapolated boiling point reaches 51 degrees C. Its structural and conformational properties have been compared with the ethyl thionitrite analogue, CH3CH2SNO. The FTIR spectra of the vapor of both thionitrites show the presence of bands with well-defined contours, allowing for a detailed conformational analysis and vibrational assignment on the basis of a normal coordinate analysis. The conformational space of both thionitrite derivatives has also been studied by using the DFT and MP2(full) level of theory with extended basis sets [6-311+G(2df) and cc-pVTZ]. The overall evaluation of the experimental and theoretical results suggests the existence of a mixture of two conformers at room temperature. The relative abundance of the most stable syn form (N=O double bond syn with respect to the C-S single bond) has been estimated to be ca. 79 and 75% for CF3CH2SNO and CH3CH2SNO, respectively

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX₃CH₂SNO, X = H and F)

The simple 2,2,2-trifluoroethyl thionitrite molecule, CF₃CH₂SNO, has been prepared in good yield for the first time using CF₃CH₂SH and NOCl in slight excess. The vapor pressure of the red-brown compound CF₃CH₂SNO follows, in the temperature range between 226 and 268 K, the equation log <i>p</i> = 12.0–3881/<i>T</i> (<i>p</i>/bar, <i>T</i>/K), and its extrapolated boiling point reaches 51 °C. Its structural and conformational properties have been compared with the ethyl thionitrite analogue, CH₃CH₂SNO. The FTIR spectra of the vapor of both thionitrites show the presence of bands with well-defined contours, allowing for a detailed conformational analysis and vibrational assignment on the basis of a normal coordinate analysis. The conformational space of both thionitrite derivatives has also been studied by using the DFT and MP2­(full) level of theory with extended basis sets [6-311+G­(2df) and cc-pVTZ]. The overall evaluation of the experimental and theoretical results suggests the existence of a mixture of two conformers at room temperature. The relative abundance of the most stable syn form (NO double bond syn with respect to the C–S single bond) has been estimated to be ca. 79 and 75% for CF₃CH₂SNO and CH₃CH₂SNO, respectively