RESUMEN
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).
RESUMEN
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].
RESUMEN
[This corrects the article DOI: 10.1107/S2414314623009719.].
RESUMEN
The reaction of (2E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-yl-idene]hydra-zine-carbo-thio-amide (common name: cinnamaldehyde-4-phenyl-thio-semi-carbazone) deprotonated with NaOH in ethanol with an ethano-lic suspension of PdII chloride in a 2:1 molar ratio yielded the title compound, [Pd(C16H14N3S)2]. The anionic ligands act as metal chelators, κ2 N 1 S-donors, forming five-membered rings with a trans-configuration. The PdII ion is fourfold coordinated in a slightly distorted square-planar geometry. For each ligand, one Hâ¯S and one Hâ¯N intra-molecular inter-actions are observed, with S(5) and S(6) graph-set motifs. Concerning the Hâ¯S inter-actions, the coordination sphere resembles a hydrogen-bonded macrocyclic environment-type. In the crystal, the complexes are linked via pairs of Hâ¯S inter-actions, with graph-set motif R 2 2(8), and building a mono-periodic hydrogen-bonded ribbon along [001]. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are: Hâ¯H (45.3%), Hâ¯C/Câ¯H (28.0%), Hâ¯S/Sâ¯H (8.0%) and Hâ¯N/Nâ¯H (7.4%).
RESUMEN
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.
RESUMEN
The reaction between a racemic mixture of (R,S)-fixolide and 4-methyl-thio-semicarbazide in ethanol with a 1:1 stoichiometric ratio and catalysed with HCl, yielded the title compound, C20H31N3S [common name: (R,S)-fixolide 4-methyl-thio-semicarbazone]. There is one crystallographically independent mol-ecule in the asymmetric unit, which is disordered over the aliphatic ring [site-occupancy ratio = 0.667â (13):0.333â (13)]. The disorder includes the chiral C atom, the neighbouring methyl-ene group and the methyl H atoms of the methyl group bonded to the chiral C atom. The maximum deviations from the mean plane through the disordered aliphatic ring amount to 0.328â (6) and -0.334â (6)â Å [r.m.s.d. = 0.2061â Å], and -0.3677â (12) and 0.3380â (12)â Å [r.m.s.d. = 0.2198â Å] for the two different sites. Both fragments show a half-chair conformation. Additionally, the N-N-C(=S)-N entity is approximately planar, with the maximum deviation from the mean plane through the selected atoms being 0.0135â (18)â Å [r.m.s.d. = 0.0100â Å]. The mol-ecule is not planar due to the dihedral angle between the thio-semicarbazone entity and the aromatic ring, which amounts to 51.8â (1)°, and due to the sp 3-hybridized carbon atoms of the fixolide fragment. In the crystal, the mol-ecules are connected by Hâ¯S inter-actions with graph-set motif C(4), forming a mono-periodic hydrogen-bonded ribbon along [100]. The Hirshfeld surface analysis suggests that the major contributions for the crystal cohesion are [(R,S)-isomers considered separately] Hâ¯H (75.7%), Hâ¯S/Sâ¯H (11.6%), Hâ¯C/Câ¯H (8.3% and Hâ¯N/Nâ¯H (4.4% for both of them).
RESUMEN
The reaction between the (R,S)-fixolide 4-methyl-thio-semicarbazone and PdII chloride yielded the title compound, [Pd(C20H30N3S)2]·C2H6O {common name: trans-bis-[(R,S)-fixolide 4-methyl-thio-semicarbazonato-κ2 N 2 S]palladium(II) ethanol monosolvate}. The asymmetric unit of the title compound consists of one bis-thio-semicarbazonato PdII complex and one ethanol solvent mol-ecule. The thio-semicarbazononato ligands act as metal chelators with a trans configuration in a distorted square-planar geometry. A C-Hâ¯S intra-molecular inter-action, with graph-set motif S(6), is observed and the coordination sphere resembles a hydrogen-bonded macrocyclic environment. Additionally, one C-Hâ¯Pd anagostic inter-action can be suggested. Each ligand is disordered over the aliphatic ring, which adopts a half-chair conformation, and two methyl groups [s.o.f. = 0.624â (2):0.376â (2)]. The disorder includes the chiral carbon atoms and, remarkably, one ligand has the (R)-isomer with the highest s.o.f. value atoms, while the other one shows the opposite, the atoms with the highest s.o.f. value are associated with the (S)-isomer. The N-N-C(=S)-N fragments of the ligands are approximately planar, with the maximum deviations from the mean plane through the selected atoms being 0.0567â (1) and -0.0307â (8)â Å (r.m.s.d. = 0.0403 and 0.0269â Å) and the dihedral angle with the respective aromatic rings amount to 46.68â (5) and 50.66â (4)°. In the crystal, the complexes are linked via pairs of N-Hâ¯S inter-actions, with graph-set motif R 2 2(8), into centrosymmetric dimers. The dimers are further connected by centrosymmetric pairs of ethanol mol-ecules, building mono-periodic hydrogen-bonded ribbons along [011]. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are [atoms with highest/lowest s.o.f.s considered separately]: Hâ¯H (81.6/82.0%), Hâ¯C/Câ¯H (6.5/6.4%), Hâ¯N/Nâ¯H (5.2/5.0%) and Hâ¯S/Sâ¯H (5.0/4.9%).
RESUMEN
The reaction in methanol of CuII acetate monohydrate with 5-fluoro-isatin 3-oxime deprotonated with KOH in a 1:2 molar ratio and recrystallization from pyridine yielded the title compound, [Cu(C8H4FN2O2)2(C5H5N)2]. In the centrosymmetric complex, the anionic form of the isatin oxime acts as a κ2N,O donor, building five-membered metallarings. The CuII cation is sixfold coordinated in a slightly distorted octa-hedral environment by two trans, equatorial, anionic isatin derivatives and two trans pyridine ligands in axial positions. The complexes are linked by hydrogen bonding into a three-dimensional network, which is also stabilized by π-π stacking inter-actions [centroid-to-centroid distance = 3.7352â (9)â Å] and C-Hâ¯π contacts. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are Hâ¯H (31.80%), Hâ¯C (24.30%), Hâ¯O (15.20%) and Hâ¯F (10.80%). This work is the second report in the literature of a crystal structure of a coordination compound with isatin 3-oxime ligands (coordination chemistry).
RESUMEN
The reaction between 5-fluoro-isatin and hydroxyl-amine hydro-chloride in acidic ethanol yields the title compound, C8H5FN2O2, whose mol-ecular structure matches the asymmetric unit and is nearly planar with an r.m.s. deviation for the mean plane through all non-H atoms of 0.0363â Å. In the crystal, the mol-ecules are linked by N-Hâ¯N, N-Hâ¯O and O-Hâ¯O hydrogen-bonding inter-actions into a two-dimensional network along the (100) plane, forming rings with R22 (8) and R12 (5) graph-set motifs. The crystal packing also features weak π-π inter-actions along the [100] direction [centroid-to-centroid distance 3.9860â (5)â Å]. Additionally, the Hirshfeld surface analysis indicates that the major contributions for the crystal structure are the Oâ¯H (28.50%) and Hâ¯F (16.40%) inter-actions. An in silico evaluation of the title compound with the vascular endothelial growth factor receptor-2 (VEGFR-2) was carried out. The title compound and the selected biological target VEGFR-2 show the N-Hâ¯O(GLU94), (CYS96)N-Hâ¯O(isatine) and (PHE95)N-Hâ¯O(isatine) inter-molecular inter-actions, which suggests a solid theoretical structure-activity relationship.
RESUMEN
The reaction of NiII acetate tetra-hydrate with 4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amide in a 2:1 molar ratio and recrystallization from di-methyl-formamide yielded the title compound, [Ni(C12H14N3S)2]·C3H7NO. The ligands act as monoanionic κ2N1,S-donors, forming five-membered metallarings. The NiII ion is fourfold coordinated in a distorted square-planar cis-configuration, which is rather uncommon for mono-thio-semicarbazone complexes. Intra-molecular Hâ¯Ni trans-inter-actions are observed [Hâ¯Ni distances are 2.50 and 2.57â Å] and thus anagostic inter-actions can be suggested. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are Hâ¯H (66.6%), Hâ¯S (12.3%) and Hâ¯C (10.9%) inter-actions. In the crystal, the complex mol-ecules are linked by di-methyl-formamide solvent mol-ecules through N-Hâ¯O inter-actions into one-dimensional hydrogen-bonded polymers along [010].
RESUMEN
The acetic acid-catalyzed reaction between 5-chloro-isatin and 4-methyl-thio-semicarbazide yields the title compound, C10H9ClN4OS (I) (common name: 5-chloro-isatin-4-methyl-thio-semicarbazone). The mol-ecule is nearly planar (r.m.s. deviation = 0.047â Å for all non-H atoms), with a maximum deviation of 0.089â (1)â Å for the O atom. An S(6) ring motif formed by an intra-molecular N-Hâ¯O hydrogen bond is observed. In the crystal, mol-ecules are linked by N-Hâ¯O hydrogen bonds, forming chains propagating along the a-axis direction. The chains are linked by N-Hâ¯S hydrogen bonds, forming a three-dimensional supra-molecular structure. The three-dimensional framework is reinforced by C-Hâ¯π inter-actions. The absolute structure of the mol-ecule in the crystal was determined by resonant scattering [Flack parameter = 0.006â (9)]. The crystal structure of the same compound, measured at 100â K, has been reported on previously [Qasem Ali et al. (2012 â¸). Acta Cryst. E68, o964-o965]. The Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are the Hâ¯H (23.1%), Hâ¯C (18.4%), Hâ¯Cl (13.7%), Hâ¯S (12.0%) and Hâ¯O (11.3%) inter-actions. A mol-ecular docking evaluation of the title compound with the ribonucleoside diphosphate reductase (RDR) enzyme was carried out. The title compound (I) and the active site of the selected enzyme show Clâ¯H-C(LYS140), Cg(aromatic ring)â¯H-C(SER71), Hâ¯O-C(GLU200) and FeIIIâ¯Oâ¯FeIII inter-molecular inter-actions, which suggests a solid theoretical structure-activity relationship.
RESUMEN
The equimolar reaction between 4-(di-methyl-amino)-benzaldehyde and 2-acetyl-thio-phene in basic ethano-lic solution yields the title compound, C15H15NOS, whose mol-ecular structure matches the asymmetric unit. The mol-ecule is not planar, the dihedral angle between the aromatic and the thio-phene rings being 11.4â (2)°. In the crystal, mol-ecules are linked by C-Hâ¯O and weak C-Hâ¯S inter-actions along [100], forming R22 (8) rings, and by weak C-Hâ¯O inter-actions along [010], forming chains with a C(6) graph-set motif. In addition, mol-ecules are connected into centrosymmetric dimers by weak C-Hâ¯π inter-actions, as indicated by the Hirshfeld surface analysis. The most important contributions for the crystal structure are the Hâ¯H (46.50%) and Hâ¯C (23.40%) inter-actions. The crystal packing resembles a herringbone arrangement when viewed along [100]. A mol-ecular docking calculation of the title compound with the neuraminidase enzyme was carried out. The enzyme shows (ASN263)N-Hâ¯O, (PRO245)C-Hâ¯Cg(thio-phene ring) and (AGR287)C-Hâ¯N inter-molecular inter-actions with the title compound. The crystal structure was refined as a two-component twin with a fractional contribution to the minor domain of 0.0181â (8).
RESUMEN
The reaction between 5-nitro-isatin and phenyl-hydrazine in acidic ethanol yields the title compound, C14H10N4O3, whose mol-ecular structure deviates slightly from a planar geometry (r.m.s. deviation = 0.065â Å for the mean plane through all non-H atoms). An intra-molecular N-Hâ¯O hydrogen bond is present, forming a ring of graph-set motif S(6). In the crystal, mol-ecules are linked by N-Hâ¯O and C-Hâ¯O hydrogen-bonding inter-actions into a two-dimensional network along (120), and rings of graph-set motif R22(8), R22(26) and R44(32) are observed. Additionally, a Hirshfeld surface analysis suggests that the mol-ecules are stacked along [100] through C=Oâ¯Cg inter-actions and indicates that the most important contributions for the crystal structure are Oâ¯H (28.5%) and Hâ¯H (26.7%) inter-actions. An in silico evaluation of the title compound with the DHFR enzyme (di-hydro-folate reductase) was performed. The isatin-hydrazone derivative and the active site of the selected enzyme show N-Hâ¯O(ASP29), N-Hâ¯O(ILE96) and Cgâ¯Cg(PHE33) inter-actions.
RESUMEN
There are two crystallographically independent mol-ecules in the asymmetric unit of the title compound, C13H17N3S, one of them being disordered over the methyl group [site-occupancy ratio = 0.705â (5):0.295â (5)]. The maximum r.m.s. deviations from the mean plane of the non-H atoms for the tetra-lone fragments amount to 0.4572â (17) and 0.4558â (15)â Å. The N-N-C-N fragments are not planar and torsion angles are -9.4â (2) and 8.3â (2)°. In the crystal, the mol-ecules are linked by weak N-Hâ¯S inter-actions into chains along [100] with graph-set motif C(4) and connected by weak N-Hâ¯S and C-Hâ¯S inter-actions, forming R21(10) rings. The Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are the Hâ¯H (64.20%), Hâ¯S (12.60%) and Hâ¯C (12.00%) inter-actions. The crystal packing resembles a herringbone arrangement when viewed along [001].
RESUMEN
In the title compound, C9H7FN4OS, the mol-ecules are almost planar, with an r.m.s. deviation of 0.047â (3)â Å from the mean plane defined by the non-H atoms and a maximum deviation of 0.123â (2)â Å for the amine N atom. The torsion angle for the N-N-C-S unit is 176.57â (19)°. In the crystal, mol-ecules are linked into inversion dimers via pairs of N-Hâ¯F hydrogen bonds and, additionally, through N-Hâ¯O and N-Hâ¯S hydrogen bonds, building a two-dimensional hydrogen-bond network parallel to the (103) plane. An intra-molecular N-Hâ¯O inter-action is also observed.
RESUMEN
The reaction of the N-phenyl-2-(1,2,3,4-tetrahydronaphthalen-1-yl-idene)hy-dra-zine-car-bo-thio-amide ligand with zinc acetate dihydrate in a 2:1 molar ratio yielded a yellow solid, which was crystallized from DMSO to obtain the title compound, [Zn(C17H16N3S)2]·C2H6OS. The Zn(II) ion is four-coordinated in a distorted tetra-hedral environment by two deprotonated ligands. Each ligand acts as an N,S-donor, forming a five-membered metallacycle. The maximum deviation from the mean plane of the N-N-C-S chelate group is 0.0029â (14)â Å for the N-donor atom of one ligand and 0.0044â (14)â Å for the non-coordinating N atom of the second. The dihedral angle between the planes of the two chelate groups is 72.80â (07)°. Bond lengths in the ligands are compared with those in the crystal structure of the free ligand. In the crystal, complex mol-ecules are connected by dimethyl sulfoxide solvate mol-ecules via N-Hâ¯O hydrogen-bonding inter-actions, building a one-dimensional hydrogen-bonded polymer along the a-axis direction. The S atom and one C atom of the dimethyl sulfoxide solvate mol-ecules are disordered over two sets of sites with an occupancy ratio of 0.6:0.4.
RESUMEN
In the title solvate, C15H15N3O2S·CH3OH, the thio-semicarbazone mol-ecule is approximately planar; the maximum deviation from the mean plane is 0.4659â (14)â Å and the dihedral angle between the aromatic rings is 9.83â (8)°. This conformation is supported by an intra-molecular N-Hâ¯N hydrogen bond. In the crystal, the thio-semicarbazone mol-ecules are linked into dimers by pairs of N-Hâ¯S hydrogen bonds, thereby generating R 2 (2)(8) loops. The methanol solvent mol-ecule bonds to the thio-semicarbazone mol-ecule through a bifurcated O-Hâ¯(O,O) hydrogen bond and also accepts an O-Hâ¯O link from the thio-semicarbazone mol-ecule. Together, these links generate a three-dimensional network.
RESUMEN
In the title compound, C12H15N3O2S, the 1,3-benzdioxole fragment is nearly planar [the maximum deviation being 0.0515â (14)â Å], the N-N-C(=S)-N fragment is also nearly planar [the maximum deviation being 0.0480â (10)â Å], and the dihedral angle between their mean planes is 23.49â (10)°. In the crystal, mol-ecules are linked by pairs of N-Hâ¯S hydrogen bonds, forming inversion dimers. The dimers are stacked along the a axis with neighbouring columns having the same direction; however, the mol-ecules show different orientations leading to a centrosymmetric arrangement. In the crystal, the methyl-ene group of the ethyl substituent and the terminal methyl H atoms are disordered over two sets of sites and were refined using a split model with an occupancy ratio of 0.5:0.5.
RESUMEN
The title compound, C11H15N3OS, is a thio-semicarbazone derivative of the raspberry ketone rheosmin [systematic name: 4-(4-hy-droxy-phen-yl)butane-2-one]. The mol-ecule deviates from planarity, with the bridging C-C-C=N torsion angle equal to -101.3â (2)°. The maximum deviation from the mean plane of the non-H atoms of the thio-semicarbazone fragment [C=N-N-C(= S)-N] is 0.085â (5)â Å for the Schiff base N atom, and the dihedral angle between this mean plane and the aromatic ring is 50.31â (8)°. In the crystal, mol-ecules are linked by N-Hâ¯O, N-Hâ¯S and O-Hâ¯S hydrogen bonds, forming a three-dimensional structure, with the mol-ecules stacked along [011].
RESUMEN
In the title compound, C11H13N3O2S, there is a short intra-molecular N-Hâ¯N contact. The benzo[d][1,3]dioxole ring system is approximately planar (r.m.s. deviation = 0.025â Å) and makes a dihedral angle of 56.83â (6)° with the mean plane of the methyl-thio-semicarbazone fragment [-N-N-C(=S)-N-C; maximum deviation = 0.1111â (14)â Å for the imino N atom]. In the crystal, mol-ecules are linked via pairs of N-Hâ¯S hydrogen bonds, forming inversion dimers. The dimers are connected by N-Hâ¯S hydrogen bonds into layers parallel to (100). The H atoms of both methyl groups are disordered over two sets of sites and were refined with occupancy ratios of 0.5:0.5 and 0.75:0.25.