{"id":"SEDICI_cae896a17a3302f8ca821fe187c03681","dc:title":"Crystal data for O=DZP","dc:creator":"Ulic, Sonia Elizabeth","dc:date":"2024","dc:description":["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 (d<sub>norm<\/sub>, shape index, or curvedness) allowing for intuitive recognition and visual analysis of interactions between molecules. All distances to the Hirshfeld surface (d<sub>i<\/sub> and d\u2091) 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 d<sub>norm<\/sub> (normalized contact distance) surfaces were mapped over a fixed color scale of \u22120.135 au (red) to 0.460 au (blue). The 2D fingerprint plots were displayed by using the translated 0.6\u22122.6 \u00c5 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 \u2192 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 (\u03c1), the Laplacian electron density (\u2207\u00b2\u03c1), 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 F\u00edsica La Plata","Planta Piloto Multiprop\u00f3sito - Laboratorio de Servicios a la Industria y al Sistema Cient\u00edfico","Centro de Qu\u00edmica Inorg\u00e1nica"],"dc:format":["application\/octet-stream","All starting materials were purchased from standard commercial sources and used without further purification. Solvents were reagent grade and were used as received. The \u00b9H (600.1 MHz) and \u00b9\u00b3C (150.9 MHz) NMR spectra were recorded on a Bruker Advance III spectrometer in CDCl\u2083 using TMS as internal standard. The IR absorption spectra of the solid were measured on a FTIR PerkinElmer GX1 in the 4000\u2212400 cm\u207b\u00b9 frequency range with spectral resolution of 4 cm\u207b\u00b9. The Raman spectrum of the solid was performed in the 3500\u2212100 cm\u207b\u00b9 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\u207b\u00b9. 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\u2212800 nm, using a quartz cell of 10 mm optical path length. Diffuse reflectance UV\u2212vis (DR) spectra were performed with a Shimadzu UV-2600 spectrophotometer using BaSO\u2084 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 \u223c1.03 g (98%); mp 206\u2212209 \u00b0C. The measurements were performed on an Oxford Xcalibur Gemini, Eos CCD diffractometer with graphite-monochromated MoK\u03b1 (\u03bb = 0.71073 \u00c5) radiation. X-ray diffraction intensities were collected (\u03c9 scans with \u03d1 and \u03ba-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 \u2212CF\u2083 group showed severe rotational disorder around the C\u2212CF\u2083 bond, which could be modeled in terms of three split angular conformations with approximate equal occupancies. The three C\u2212CF\u2083 replicas were refined (with anisotropic displacement parameters) by restraining all of the C\u2212F bond lengths and F\u00b7\u00b7\u00b7F 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."],"dc:language":["spa"],"dc:type":"dataset","dc:subject":["Ciencias Exactas","F\u00edsica","Qu\u00edmica","diazepine derivative","tautomerism","NMR spectroscopy","molecular interactions"],"dc:rights":["info:eu-repo\/semantics\/openAccess","http:\/\/creativecommons.org\/licenses\/by\/4.0\/","Creative Commons Attribution 4.0 International (CC BY 4.0)"],"dc:relation":["info:eu-repo\/semantics\/altIdentifier\/doi\/10.5517\/ccdc.csd.cc2011jn","info:eu-repo\/semantics\/reference\/hdl\/10915\/124102"],"dc:identifier":"https:\/\/repositoriosdigitales.mincyt.gob.ar\/vufind\/Record\/SEDICI_cae896a17a3302f8ca821fe187c03681"}