RESUMO
The title compound (C14H23N3S, common name: cis-jasmone 4-ethyl-thio-semicarbazone) was synthesized by the equimolar reaction of cis-jasmone and 4-ethyl-thio-semicarbazide in ethanol facilitated by acid catalysis. There is one crystallographically independent mol-ecule in the asymmetric unit, which shows disorder of the terminal ethyl group of the jasmone carbon chain [site-occupancy ratio = 0.911â (5):0.089â (5)]. The thio-semicarbazone entity [N-N-C(=S)-N] is approximately planar, with the maximum deviation of the mean plane through the N/N/C/S/N atoms being 0.0331â (8)â Å, while the maximum deviation of the mean plane through the five-membered ring of the jasmone fragment amounts to -0.0337â (8)â Å. The dihedral angle between the two planes is 4.98â (7)°. The mol-ecule is not planar due to this structural feature and the sp 3-hybridized atoms of the jasmone carbon chain. Additionally, one Hâ¯N intra-molecular inter-action is observed, with graph-set motif S(5). In the crystal, the mol-ecules are connected through pairs of Hâ¯S inter-actions with R 2 2(8) and R 2 1(7) graph-set motifs into centrosymmetric dimers. The dimers are further connected by Hâ¯N inter-actions with graph-set motif R 2 2(12), which are related by an inversion centre, forming a mono-periodic hydrogen-bonded ribbon parallel to the b-axis. The crystal structure and the supra-molecular assembly of the title compound are compared with four known cis-jasmone thio-semicarbazone derivatives (two crystalline modifications of the non-substituted form, the 4-methyl and the 4-phenyl derivatives). A Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are from Hâ¯H (70.7%), Hâ¯S/Sâ¯H (13.5%), Hâ¯C/Câ¯H (8.8%), and Hâ¯N/Nâ¯H (6.6%) inter-faces (only the disordered atoms with the highest s.o.f. were considered for the evaluation).
RESUMO
The equimolar and hydro-chloric acid-catalysed reaction between cis-jasmone and 4-methyl-thio-semicarbazide in ethano-lic solution yields the title compound, C13H21N3S (common name: cis-jasmone 4-methyl-thio-semicarbazone). Two mol-ecules with all atoms in general positions are present in the asymmetric unit. In one of them, the carbon chain is disordered [site occupancy ratio = 0.821â (3):0.179â (3)]. The thio-semicarbazone entities [N-N-C(=S)-N] are approximately planar, with the maximum deviation from the mean plane through the selected atoms being -0.0115â (16)â Å (r.m.s.d. = 0.0078â Å) for the non-disordered mol-ecule and 0.0052â (14)â Å (r.m.s.d. = 0.0031â Å) for the disordered one. The mol-ecules are not planar, since the jasmone groups have a chain with sp 3-hybridized carbon atoms and, in addition, the thio-semicarbazone fragments are attached to the respective carbon five-membered rings and the dihedral angles between them for each mol-ecule amount to 8.9â (1) and 6.3â (1)°. In the crystal, the mol-ecules are connected through pairs of N-Hâ¯S and C-Hâ¯S inter-actions into crystallographically independent centrosymmetric dimers, in which rings of graph-set motifs R 2 2(8) and R 2 1(7) are observed. A Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are from Hâ¯H (70.6%), Hâ¯S/Sâ¯H (16.7%), Hâ¯C/Câ¯H (7.5%) and Hâ¯N/Nâ¯H (4.9%) inter-actions [considering the two crystallographically independent mol-ecules and only the disordered atoms with the highest s.o.f. for the evaluation].
RESUMO
A second crystalline modification of the title compound, C12H19N3S [common name: cis-jasmone thio-semicarbazone] was crystallized from tetra-hydro-furane at room temperature. There is one crystallographic independent mol-ecule in the asymmetric unit, showing disorder in the cis-jasmone chain [site-occupancy ratio = 0.590â (14):0.410â (14)]. The thio-semicarbazone entity is approximately planar, with the maximum deviation from the mean plane through the N/N/C/S/N atoms being 0.0463â (14)â Å [r.m.s.d. = 0.0324â Å], while for the five-membered ring of the jasmone fragment, the maximum deviation from the mean plane through the carbon atoms amounts to 0.0465â (15)â Å [r.m.s.d. = 0.0338â Å]. The mol-ecule is not planar due to the dihedral angle between these two fragments, which is 8.93â (1)°, and due to the sp 3-hybridized carbon atoms in the jasmone fragment chain. In the crystal, the mol-ecules are connected by N-Hâ¯S and C-Hâ¯S inter-actions, with graph-set motifs R 2 2(8) and R 2 1(7), building mono-periodic hydrogen-bonded ribbons along [010]. A Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are Hâ¯H (67.8%), Hâ¯S/Sâ¯H (15.0%), Hâ¯C/Câ¯H (8.5%) and Hâ¯N/Nâ¯H (5.6%) [only non-disordered atoms and those with the highest s.o.f. were considered]. This work reports the second crystalline modification of the cis-jasmone thio-semicarbazone structure, the first one being published recently [Orsoni et al. (2020 â¸). Int. J. Mol. Sci. 21, 8681-8697] with the crystals obtained in ethanol at 273â K.
RESUMO
The hydro-chloric acid-catalyzed equimolar reaction between cis-jasmone and 4-phenyl-thio-semicarbazide yielded the title compound, C18H23N3S (common name: cis-jasmone 4-phenyl-thio-semicarbazone). Concerning the hydrogen bonding, an N-Hâ¯N intra-molecular inter-action is observed, forming a ring with graph-set motif S(5). In the crystal, the mol-ecules are connected into centrosymmetric dimers by pairs of N-Hâ¯S and C-Hâ¯S inter-actions, forming rings of graph-set motifs R 2 2(8) and R 2 1(7), with the sulfur atoms acting as double acceptors. The thio-semicarbazone entity is approximately planar, with the maximum deviation from the mean plane through the N/N/C/S/N atoms being 0.0376â (9)â Å (the r.m.s.d. amounts to 0.0234â Å). The mol-ecule is substantially twisted as indicated by the dihedral angle between the thio-semicarbazone fragment and the phenyl ring, which amounts to 56.1â (5)°, and because of the jasmone fragment, which bears a chain with sp 3-hybridized carbon atoms in the structure. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are: Hâ¯H (65.3%), Hâ¯C/Câ¯H (16.2%), Hâ¯S/Sâ¯H (10.9%) and Hâ¯N/Nâ¯H (5.5%).
RESUMO
A series of related acetylacetonate-carbonyl-rhodium compounds substituted by functionalized phosphines has been prepared in good to excellent yields by the reaction of [Rh(acac)(CO)2] (acac is acetylacetonate) with the corresponding allyl-, cyanomethyl- or cyanoethyl-substituted phosphines. All compounds were fully characterized by 31P, 1H, 13C NMR and IR spectroscopy. The X-ray structures of (acetylacetonato-κ2O,O')(tert-butylphosphanedicarbonitrile-κP)carbonylrhodium(I), [Rh(C5H7O2)(CO)(C8H13N2)] or [Rh(acac)(CO)(tBuP(CH2CN)2}] (2b), (acetylacetonato-κ2O,O')carbonyl[3-(diphenylphosphanyl)propanenitrile-κP]rhodium(I), [Rh(C5H7O2)(C15H14N)(CO)] or [Rh(acac)(CO){Ph2P(CH2CH2CN)}] (2h), and (acetylacetonato-κ2O,O')carbonyl[3-(di-tert-butylphosphanyl)propanenitrile-κP]rhodium(I), [Rh(C5H7O2)(C11H22N)(CO)] or [Rh(acac)(CO){tBu2P(CH2CH2CN)}] (2i), showed a square-planar geometry around the Rh atom with a significant trans influence over the acetylacetonate moiety, evidenced by long Rh-O bond lengths as expected for poor π-acceptor phosphines. The Rh-P distances displayed an inverse linear dependence with the coupling constants JP-Rh and the IR ν(C[triple-bond]O) bands, which accounts for the Rh-P electronic bonding feature (poor π-acceptors) of these complexes. A combined study from density functional theory (DFT) calculations and an evaluation of the intramolecular H...Rh contacts from X-ray diffraction data allowed a comparison of the conformational preferences of these complexes in the solid state versus the isolated compounds in the gas phase. For 2b, 2h and 2i, an energy-framework study evidenced that the crystal structures are mainly governed by dispersive energy. In fact, strong pairwise molecular dispersive interactions are responsible for the columnar arrangement observed in these complexes. A Hirshfeld surface analysis employing three-dimensional molecular surface contours and two-dimensional fingerprint plots indicated that the structures are stabilized by H...H, C...H, H...O, H...N and H...Rh intermolecular interactions.
RESUMO
The crystal structure is reported of sodium 2-[2-(2,6-di-chloro-anilino)phen-yl]acetate 3.5-hydrate or tetra-µ-aqua-κ8 O:O-deca-aqua-bis-{µ3-2-[2-(2,6-di-chloro-anilino)phen-yl]acetato-κ3 O:O:O}tetra-sodium(I) bis-{2-[2-(2,6-di-chloro-anil-ino)phen-yl]acetate}, {[Na4(C14H10Cl2NO2)2(H2O)14](C14H10Cl2NO2)2} n , which re-presents a new hydrate form of the NSAID sodium diclofenac (SD). The triclinic unit cell contains one ionic compound with formula Na4(C14H10Cl2NO2)4(H2O)14, in which two symmetry-related carboxyl-ate anions C14H10Cl2NO2 - are bonded to a centrosymmetric [Na4]4+ core cationic cluster, while the others are only hydrogen bonded to the cationic cluster. The conformation for the anions is similar to that found in other diclofenac compounds, and the [Na4(Ocarbox)2(H2O)14]4+ cluster displays an unprecedented geometry, which can be described as an incomplete dicubane cluster formed by face-sharing incomplete cubes. A complex framework of O-Hâ¯O hydrogen bonds stabilizes the crystal structure. The herein reported crystal structure for SD·3.5H2O in space group P is different from those previously reported for other hydrates, namely SD·4.75H2O (P21) and SD·5H2O (P21/m).
RESUMO
Lapachol acetate [systematic name: 3-(3-methyl-but-2-en-yl)-1,4-dioxonaph-thalen-2-yl acetate], C17H16O4, was prepared using a modified high-yield procedure and its crystal structure is reported for the first time 80 years after its first synthesis. The full spectroscopic characterization of the mol-ecule is reported. The mol-ecular conformation shows little difference with other lapachol derivatives and lapachol itself. The packing is directed by inter-molecular π-π and C-Hâ¯O inter-actions, as described by Hirshfeld surface analysis. The former inter-actions make the largest contributions to the total packing energy in a ratio of 2:1 with respect to the latter.
RESUMO
Despite the large number of reported crystalline structures of coordination complexes bearing pyridines as ligands, the relevance of π-π interactions among these hereroaromatic systems in the stabilization of their supramolecular structures and properties is not very well documented in the recent literature. The title compound, [CoCl2(C5H6N2)2], was obtained as bright-blue crystals suitable for single-crystal X-ray diffraction analysis from the reaction of 4-aminopyridine with cobalt(II) chloride in ethanol. The new complex was fully characterized by a variety of spectroscopic techniques and single-crystal X-ray diffraction. The crystal structure showed a tetrahedral complex stabilized mainly by bidimensional motifs constructed by π-π interactions with large horizontal displacements between the 4-aminopyridine units, and N-H...Cl hydrogen bonds. Other short contacts, such as C-H...Cl interactions, complete the three-dimensional arrangement. The supramolecular investigation was extended by statistical studies using the Cambridge Structural Database and a Hirshfeld surface analysis.