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Crystal data for O=DZP

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Crystal data for O=DZP
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The Hirshfeld surface analysis is a well-known method to investigate in detail the characteristics of the crystal packing, such as polymorphism and other aspects of supramolecular assembly. Different functions describe specific properties of the Hirshfeld surface (dnorm, shape index, or curvedness) allowing for intuitive recognition and visual analysis of interactions between molecules. All distances to the Hirshfeld surface (di and dₑ) can be summarized in the form of two-dimensional diagrams (2D fingerprint plots), whose shapes are typical for certain close contacts environment. 2D fingerprint plots were used for decoding and quantifying the intermolecular interactions in the crystal lattice. Hirshfeld surfaces and their associated 2D fingerprint plots were performed using the CrystalExplorer17 program. The O=DZP structural parameters were taken from the CIF file. The 3D dnorm (normalized contact distance) surfaces were mapped over a fixed color scale of −0.135 au (red) to 0.460 au (blue). The 2D fingerprint plots were displayed by using the translated 0.6−2.6 Å range and including reciprocal contacts. Quantum chemical calculations were performed using the Gaussian 03 program. The X-ray structure coordinates were used as starting parameters for geometry optimization at the B3LYP/6-311++G(d,p) level of theory. Vibrational frequencies were calculated to confirm the proper convergence to energy minima on the potential energy surface. The potential energy distribution was calculated with the VEDA4 program. For the electronic spectra, time-dependent density functional theory (TDDFT) method at B3LYP/6-311++G(d,p) approximation was used to compute energies and intensity of 20 lowest energy singlet to singlet electronic excitations in solution (ethanol and toluene) using PCM. NBO analysis, as implemented in the Gaussian 03 package, was performed at the B3LYP/6-311++G(d,p) level for the monomeric and for dimeric structures of the O=DZP molecule, in order to obtain second-order donor → acceptor interaction energies. The AIM2000 program was applied for the topological analysis of selected dimers identified from the crystal structure of O=DZP. To evaluate the nature of different intra- and intermolecular interactions, some topological parameters such as electron density (ρ), the Laplacian electron density (∇²ρ), local potential energy density (V), and kinetic energy density (G) at the bond critical points (BCPs) were calculated adopting the geometry of the crystal structure with normalized hydrogen positions at B3LYP/6-311++G(d,p) approximation. The energies of the intra- and intermolecular interactions were estimated using the formula proposed by Espinosa and coworkers. The molecular electrostatic potential (MEP) of the ketoenamine tautomeric form has also been calculated at the same level of theory.
Facultad de Ciencias Exactas
Instituto de Física La Plata
Planta Piloto Multipropósito - Laboratorio de Servicios a la Industria y al Sistema Científico
Centro de Química Inorgánica
Año de publicación
Formato (Tipo MIME)
All starting materials were purchased from standard commercial sources and used without further purification. Solvents were reagent grade and were used as received. The ¹H (600.1 MHz) and ¹³C (150.9 MHz) NMR spectra were recorded on a Bruker Advance III spectrometer in CDCl₃ using TMS as internal standard. The IR absorption spectra of the solid were measured on a FTIR PerkinElmer GX1 in the 4000−400 cm⁻¹ frequency range with spectral resolution of 4 cm⁻¹. The Raman spectrum of the solid was performed in the 3500−100 cm⁻¹ range at room temperature on a Thermoscientific DXR Raman microscope using a diode pump and solid-state laser of 780 nm, with spectral resolution of 5 cm⁻¹. The electronic spectra of DZP in ethanol, dimethylformamide, chloroform, and toluene were recorded on a Beckman/DU 7500 spectrophotometer in the spectral region of 200−800 nm, using a quartz cell of 10 mm optical path length. Diffuse reflectance UV−vis (DR) spectra were performed with a Shimadzu UV-2600 spectrophotometer using BaSO₄ as reference. The compound was synthesized by mixing 10 mL of an ethanolic solution of 2-(trifluoromethyl)chromone (4 mmol, 0.856 g) and ethylendiamine (4 mmol, 0.240 g) with continuous stirring at room temperature. After a few minutes, an orange solid became visible, and the mixture was stirred for about 30 min. The precipitate was separated by filtration and recrystallized from hot ethanol to provide the purified compound (1.03 g) in excellent yield. Single crystals, adequate for XRD measurements were obtained from slow evaporation of an ethanolic solution. The orange crystalline solid was identified as the keto-enamine tautomer: (5Z)-5- (6-oxo-cyclohexa-2,4-dien-1-ylidene)-7-trifluoromethyl-2,3,4,5-tetrahydro-1H-1,4-diazepine, O=DZP. Yield ∼1.03 g (98%); mp 206−209 °C. The measurements were performed on an Oxford Xcalibur Gemini, Eos CCD diffractometer with graphite-monochromated MoKα (λ = 0.71073 Å) radiation. X-ray diffraction intensities were collected (ω scans with ϑ and κ-offsets), integrated, and scaled with the CrysAlisPro suite of programs. The unit cell parameters were obtained by least-squares refinement (based on the angular setting for all collected reflections with intensities larger than seven times the standard deviation of measurement errors) using CrysAlisPro. Data were corrected empirically for absorption employing the multiscan method implemented in CrysAlisPro. The structure was solved by intrinsic phasing with SHELXT and the molecular model was refined by full-matrix least-squares procedure with SHELXL. The −CF₃ group showed severe rotational disorder around the C−CF₃ bond, which could be modeled in terms of three split angular conformations with approximate equal occupancies. The three C−CF₃ replicas were refined (with anisotropic displacement parameters) by restraining all of the C−F bond lengths and F···F distances to be respectively equal to one another while restraining the occupancies such as to add up to one. At this stage, a difference Fourier map phased on the heavier atoms showed all of the H atoms. These were refined at their found positions with isotropic displacement parameters.
Clasificación temática de acuerdo a la FORD
Ciencias físicas
Ciencias Exactas; Física; Química; diazepine derivative; tautomerism; NMR spectroscopy; molecular interactions;
Condiciones de uso
Disponible en acceso abierto bajo licencia Creative Commons http://creativecommons.org/licenses/by/4.0/ Creative Commons Attribution 4.0 International (CC BY 4.0)
Repositorio digital
SEDICI (UNLP) - Universidad Nacional de La Plata
Identificador alternativo
Publicación referenciada


Rocha, Mariana Gil, Diego Mauricio Echeverría, Gustavo Alberto Piro, Oscar Enrique Jios, Jorge Luis Ulic, Sonia Elizabeth (): Crystal data for O=DZP. Universidad Nacional de La Plata, http://sedici.unlp.edu.ar/handle/10915/124104.

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