The crystal structure of the title compound has been determined. The compound crystallized in the triclinic space group P -1, Z = 2, V = 1839.42(18) Å3 and unit cell parameters a = 11.0460(6) Å, b = 13.3180(7) Å, c = 13.7321(8) Å, a = 80.659(3)°, ß = 69.800(3)° and ? = 77.007(2)° with one disordered dimethylsulfoxide solvent molecule with the sulfur and oxygen atoms are distributed over two sites; S101/S102 [site occupancy factors: 0.6035/0.3965] and O130/O131 [site occupancy factor 0.3965/0.6035]. The C22-S21 and C19-S20 bond distances of 1.779(7) Å and 1.788(8) Å indicate that both of the molecules are connected by the disulfide bond [S20-S21 2.055(2) Å] in its thiol form. The crystal structure reveals that both of the 5-bromoisatin moieties are trans with respect to the [S21-S20 and C19-N18] and [S20-S21 and C22-N23] bonds whereas the benzyl group from the dithiocarbazate are in the cis configuration with respect to [S21-S20 and C19-S44] and [S20-S21 and C22-S36] bonds. The crystal structure is further stabilized by intermolecular hydrogen bonds of N9-H35···O16 formed between the two molecules and N28-H281···O130, N28-H281···O131 and C41-H411···O131 with the solvent molecule.
The complete mol-ecule of the title hydrazine carbodi-thio-ate derivative, C32H30N4O2S4, is generated by a crystallographic twofold axis that bis-ects the di-sulfide bond. The mol-ecule is twisted about this bond with the C-S-S-C torsion angle of 90.70 (8)° indicating an orthogonal relationship between the symmetry-related halves of the mol-ecule. The conformation about the imine bond [1.282 (2) Å] is E and there is limited delocalization of π-electron density over the CN2C residue as there is a twist about the N-N bond [C-N-N-C torsion angle = -166.57 (15)°]. An intra-molecular hydroxyl-O-H⋯N(imine) hydrogen bond closes an S(6) loop. In the crystal, methyl-ene-C-H⋯π(tol-yl) contacts assemble mol-ecules into a supra-molecular layer propagating in the ab plane: the layers stack without directional inter-actions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of H⋯H contacts, which contribute 46.7% of all contacts followed by H⋯C/C⋯H contacts [25.5%] reflecting, in part, the C-H⋯π(tol-yl) contacts. The calculation of the inter-action energies confirm the importance of the dispersion term and the influence of the stabilizing H⋯H contacts in the inter-layer region.
Two bidentate Schiff base ligands having nitrogen sulphur donor sequence were derived from the condensation of S-benzyldithiocarbazate (SBDTC) with 2-chloroacetophenone and 4-chloroacetophenone to give S-benzyl- β -N-(2-chlorophenyl)methylenedithiocarbazate (NS2) and S-benzyl- β -N-(4-chlorophenyl)methylenedithiocarbazate (NS4) isomers. Each of the ligands was then chelated with Cd(2+), Zn(2+), Cu(2+), and Ni(2+). The compounds were characterized via IR spectroscopy and melting point while the structure of NS4 was revealed via X-ray crystallography. Finally, the compounds were screened for antimicrobial activity to investigate the effect that is brought by the introduction of the chlorine atom to the benzene ring. X-ray crystallographic analysis showed that the structure of NS4 is planar with a phenyl ring that is nearly perpendicular to the rest of the molecules. The qualitative antimicrobial assay results showed that NS4 and its complexes lacked antifungal activity while Gram-positive bacteria were generally inhibited more strongly than Gram-negative bacteria. Furthermore, NS4 metal complexes were inhibited more strongly than the ligand while the opposite was seen with NS2 ligand and its complexes due to the partial solubility in dimethyl sulfoxide (DMSO). It was concluded that generally NS2 derivatives have higher bioactivity than that of NS4 derivatives and that the Cd complexes of both ligands have pronounced activity specifically on K. rhizophila.
The title ZnII complex, [Zn(C18H18N3S)2], (I), features two independent but chemically equivalent mol-ecules in the asymmetric unit. In each, the thio-semicarbazonate monoanion coordinates the ZnII atom via the thiol-ate-S and imine-N atoms, with the resulting N2S2 donor set defining a distorted tetra-hedral geometry. The five-membered ZnSCN2 chelate rings adopt distinct conformations in each independent mol-ecule, i.e. one ring is almost planar while the other is twisted about the Zn-S bond. In the crystal, the two mol-ecules comprising the asymmetric unit are linked by amine-N-H⋯N(imine) and amine-N-H⋯S(thiol-ate) hydrogen bonds via an eight-membered heterosynthon, {⋯HNCN⋯HNCS}. The dimeric aggregates are further consolidated by benzene-C-H⋯S(thiol-ate) inter-actions and are linked into a zigzag supra-molecular chain along the c axis via amine-N-H⋯S(thiol-ate) hydrogen bonds. The chains are connected into a three-dimensional architecture via phenyl-C-H⋯π(phen-yl) and π-π inter-actions, the latter occurring between chelate and phenyl rings [inter-centroid separation = 3.6873 (11) Å]. The analysis of the Hirshfeld surfaces calculated for (I) emphasizes the different inter-actions formed by the independent mol-ecules in the crystal and the impact of the π-π inter-actions between chelate and phenyl rings.
The title compound, C23H21N3O2, is constructed about an almost planar disubstituted amino-urea residue (r.m.s. deviation = 0.0201 Å), which features an intra-molecular amine-N-H⋯N(imine) hydrogen bond. In the 'all-trans' chain connecting this to the terminal meth-oxy-benzene residue, the conformation about each of the imine and ethyl-ene double bonds is E. In the crystal, amide-N-H⋯O(carbon-yl) hydrogen bonds connect centrosymmetrically related mol-ecules into dimeric aggregates, which also incorporate ethyl-ene-C-H⋯O(amide) inter-actions. The dimers are linked by amine-phenyl-C-H⋯π(imine-phen-yl) and meth-oxy-benzene-C-H⋯π(amine-phen-yl) inter-actions to generate a three-dimensional network. The importance of C-H⋯π inter-actions in the mol-ecular packing is reflected in the relatively high contributions made by C⋯H/H⋯C contacts to the Hirshfeld surface, i.e. 31.6%.
Two independent mol-ecules (A and B) comprise the asymmetric unit of the title compound, C18H21N3O3. The urea moiety is disubstituted with one amine being linked to a phenyl ring, which is twisted out of the plane of the CN2O urea core [dihedral angles = 25.57 (11) (A) and 29.13 (10)° (B)]. The second amine is connected to an imine (E conformation), which is linked in turn to an ethane bridge that links a disubstituted benzene ring. Intra-molecular amine-N-H⋯N(imine) and hydroxyl-O-H⋯O(meth-oxy) hydrogen bonds close S(5) loops in each case. The mol-ecules have twisted conformations with the dihedral angles between the outer rings being 38.64 (81) (A) and 48.55 (7)° (B). In the crystal, amide-N-H⋯O(amide) hydrogen bonds link the mol-ecules A and B via an eight-membered {⋯HNCO}2 synthon. Further associations between mol-ecules, leading to supra-molecular layers in the ac plane, are hydrogen bonds of the type hydroxyl-O-H⋯N(imine) and phenyl-amine-N-H⋯O(meth-oxy). Connections between layers, leading to a three-dimensional architecture, comprise benzene-C-H⋯O(hy-droxy) inter-actions. A detailed analysis of the calculated Hirshfeld surfaces shows mol-ecules A and B participate in very similar inter-molecular inter-actions and that any variations relate to conformational differences between the mol-ecules.
The title ZnII complex, [Zn(C19H20N3OS)2] {systematic name: bis-[(N-ethyl-N'-{(Z)-[(2E)-3-(4-meth-oxy-phen-yl)-1-phenyl-prop-2-en-1-yl-idene]amino}-carb-am-im-id-o-yl)sulfanido]zinc(II)}, features a tetra-hedrally coordinated ZnII ion within an N2S2 donor set provided by two N,S-chelating thio-semicarbazone anions. The resulting five-membered Zn,C,N2,S chelate rings adopt different conformations, i.e. almost planar and an envelope with the Zn atom being the flap atom. The configuration about the imine bond within the chelate ring is Z but those about the exocyclic imine and ethyl-ene bonds are E. In the crystal, supra-molecular [100] chains mediated by thio-amide-N-H⋯S(thione) hydrogen bonds and eight-membered thio-amide {⋯HNCS}2 synthons are observed. A range of inter-actions, including C-H⋯O, C-H⋯π, C-H⋯π(chelate ring) and π(meth-oxy-benzene)-π(chelate ring) consolidate the packing. The Hirshfeld surface analysis performed on the title complex also indicates the influence of the inter-actions involving the chelate rings upon the packing along with the more conventional contacts.
The title hydrazine carbodi-thio-ate, C13H18N2OS2, is constructed about a central and almost planar C2N2S2 chromophore (r.m.s. deviation = 0.0263 Å); the terminal meth-oxy-benzene group is close to coplanar with this plane [dihedral angle = 3.92 (11)°]. The n-butyl group has an extended all-trans conformation [torsion angles S-Cm-Cm-Cm = -173.2 (3)° and Cm-Cm-Cm-Cme = 180.0 (4)°; m = methyl-ene and me = meth-yl]. The most prominent feature of the mol-ecular packing is the formation of centrosymmetric eight-membered {⋯HNCS}2 synthons, as a result of thio-amide-N-H⋯S(thio-amide) hydrogen bonds; these are linked via meth-oxy-C-H⋯π(meth-oxy-benzene) inter-actions to form a linear supra-molecular chain propagating along the a-axis direction. An analysis of the calculated Hirshfeld surfaces and two-dimensional fingerprint plots point to the significance of H⋯H (58.4%), S⋯H/H⋯S (17.1%), C⋯H/H⋯C (8.2%) and O⋯H/H⋯O (4.9%) contacts in the packing. The energies of the most significant inter-actions, i.e. the N-H⋯S and C-H⋯π inter-actions have their most significant contributions from electrostatic and dispersive components, respectively. The energies of two other identified close contacts at close to van der Waals distances, i.e. a thione-sulfur and meth-oxy-benzene-hydrogen contact (occurring within the chains along the a axis) and between methyl-ene-H atoms (occurring between chains to consolidate the three-dimensional architecture), are largely dispersive in nature.
The title hydrazine carbodi-thio-ate chloro-form hemisolvate, 2C15H14N2O2S2·CHCl3, comprises two independent hydrazine carbodi-thio-ate mol-ecules, A and B, and a chloro-form mol-ecule; the latter is statistically disordered about its mol-ecular threefold axis. The common features of the organic mol-ecules include an almost planar, central CN2S2 chromophore [r.m.s. deviation = 0.0203 Å (A) and 0.0080 Å (B)], an E configuration about the imine bond and an intra-molecular hydroxyl-O-H⋯N(imine) hydrogen bond. The major conformational difference between the mol-ecules is seen in the relative dispositions of the phenyl rings as indicated by the values of the dihedral angles between the central plane and phenyl ring of 71.21 (6)° (A) and 54.73 (7)° (B). Finally, a difference is seen in the disposition of the outer hydroxyl-H atoms, having opposite relative orientations. In the calculated gas-phase structure, the entire mol-ecule is planar with the exception of the perpendicular phenyl ring. In the mol-ecular packing, the A and B mol-ecules assemble into a two-mol-ecule aggregate via N-H⋯S hydrogen bonds and eight-membered {⋯HNCS}2 synthons. The dimeric assemblies are connected into supra-molecular chains via hydroxyl-O-H⋯O(hydrox-yl) hydrogen bonds and these are linked into a double-chain through hy-droxy-O-H⋯π(phen-yl) inter-actions. The double-chains are connected into a three-dimensional architecture through phenyl-C-H⋯O(hydrox-yl) and phenyl-C-H⋯π(phen-yl) inter-actions. The overall assembly defines columns along the a-axis direction in which reside the chloro-form mol-ecules, which are stabilized by chloro-form-methine-C-H⋯S(thione) and phenyl-C-H⋯Cl contacts. The analysis of the calculated Hirshfeld surfaces, non-covalent inter-action plots and inter-action energies confirm the importance of the above-mentioned inter-actions, but also of cooperative, non-standard inter-actions such as π(benzene)⋯π(hydrogen-bond-mediated-ring) contacts.
Eight selective nitrogen-sulfur donor ligands have been synthesized from the condensation of S-methyldithiocarbazate (SMDTC) with aldehydes and ketones with a view to evaluating their antimicrobial and cytotoxic activities, and also to correlate the biological properties with the structure of the ligands. The compounds were all characterized by elemental analyses and other physicochemical techniques. SMDTC and the Schiff bases were screened for antimicrobial and cytotoxic activities. SMDTC showed very large inhibition zones (24-44 mm) against bacteria and fungi with a minimum inhibitory concentration (MIC) of 390-25,000 and 1562-6250 microg ml(-1), against different bacteria and fungi, respectively. Streptomycin and nystatin were used as the internal standards against bacteria and fungi, respectively. SMDTC along with its Schiff bases with pyridine-2-carboxaldehyde, acetylacetone and 2,3-butanedione were strongly antifungal and the MIC values were comparable to nystatin. Most of the Schiff bases were strongly cytotoxic. In particular, those with pyridine-2-carboxaldehyde and 2,3-butanedione have CD(50) values of 5.5, 1.9-2.0 microg ml(-1), respectively, against leukemic cells, while against colon cancer cells, the values were 3.7 and 2.0 microg ml(-1), respectively. The glyoxal Schiff base was strongly active only against leukemic cell with CD(50) value of 4.0 microg ml(-1). The present findings have been compared with standard drugs.
The title zinc bis-(thio-semicarbazone) complex, [Zn(C22H17N4O2S)2], comprises two N,S-donor anions, leading to a distorted tetra-hedral N2S2 donor set. The resultant five-membered chelate rings are nearly planar and form a dihedral angle of 73.28 (3)°. The configurations about the endocyclic- and exocyclic-imine bonds are Z and E, respectively, and that about the ethyl-ene bond is E. The major differences in the conformations of the ligands are seen in the dihedral angles between the chelate ring and nitro-benzene rings [40.48 (6) cf. 13.18 (4)°] and the N-bound phenyl and nitro-benzene ring [43.23 (8) and 22.64 (4)°]. In the crystal, a linear supra-molecular chain along the b-axis direction features amine-N-H⋯O(nitro) hydrogen bonding. The chains assemble along the 21-screw axis through a combination of phenyl-C-H⋯O(nitro) and π(chelate ring)-π(phen-yl) contacts. The double chains are linked into a three-dimensional architecture through phenyl-C-H⋯O(nitro) and nitro-O⋯π(phen-yl) inter-actions.
The title thio-urea derivative, C17H19N3OS, adopts a U-shaped conformation with the dihedral angle between the terminal aromatic rings being 73.64 (5)°. The major twist in the mol-ecule occurs about the ethane bond with the Ci-Ce-Ce-Cb torsion angle being -78.12 (18)°; i = imine, e = ethane and b = benzene. The configuration about the imine bond is E, the N-bound H atoms lie on opposite sides of the mol-ecule and an intra-molecular amine-N-H⋯N(imine) hydrogen bond is evident. In the mol-ecular packing, hydroxyl-O-H⋯S(thione) and amine-N-H⋯O hydrogen bonding feature within a linear, supra-molecular chain. The chains are connected into a layer in the ab plane by a combination of methyl-ene-C-H⋯S(thione), methyl-ene-C-H⋯O(hydrox-yl), methyl-C-H⋯π(phen-yl) and phenyl-C-H⋯π(hy-droxy-benzene) inter-actions. The layers stack without directional inter-actions between them. The analysis of the calculated Hirshfeld surface highlights the presence of weak methyl-C-H⋯O(hydrox-yl) and H⋯H inter-actions in the inter-layer region. Computational chemistry indicates that dispersion energy is the major contributor to the overall stabilization of the mol-ecular packing.
The asymmetric unit of the title compound, [Ni(C(15)H(14)N(3)S(2))(2)], consists of two independent mol-ecules with similar configurations. Each Ni(2+) cation is coordinated in a cis-mode by two tridentate N,N',S-chelating Schiff base ligands, creating a distorted octa-hedron [the smallest angle being 77.57 (7)° and the widest being 168.97 (7)° for one mol-ecule, and 78.04 (7) and 167.55 (7)° for the second mol-ecule]. The dihedral angle between the mean coordination planes of the two ligands is 86.76 (7)° for one and 89.99 (7)° for the second mol-ecule. π-π inter-actions between neighbouring pyridine rings with plane-to-plane distances of 3.540 (1) and 3.704 (1) Å are observed.
The title compound, [Zn(C(15)H(14)N(3)S(2))(2)], contains two chemically equivalent Schiff base anions that are coordinated to the Zn(II) ion as tridentate N,N',S-chelating ligands, creating a distorted octa-hedral environment [the smallest angle being 75.40 (6)° and the widest angle being 162.87 (6)°], with the two S atoms in cis positions. The dihedral angle between the mean planes of the two coordinating ligands is 85.65 (5)°. Weak C-H⋯S hydrogen bonds are also observed.
In the title compound, [Zn(C(20)H(16)N(3)S(2))(2)]·CH(3)CN, two different Schiff base moieties coordinate to the central Zn(II) ion as tridentate N,N',S-chelating ligands, creating a distorted octa-hedral environment [the smallest angle being 73.24 (6)° and the widest angle being 155.73 (7)°], with the two S atoms in cis positions. The dihedral angle between the mean planes of the two coordinating ligands is 83.65 (5)°. The crystal packing is consolidated by weak C-H⋯N hydrogen-bonding inter-actions.
The structure of the title compound, [Ni(C(15)H(14)N(3)S(2))(2)]·H(2)O, has one mol-ecule in the asymmetric unit, along with a solvent water mol-ecule. The two different Schiff base moieties coordinate to the central Ni(II) ion as tridentate N,N',S-chelating ligands, creating a six-coordinate distorted octa-hedral environment [the smallest angle being 77.43 (7)° and the widest angle being 169.99 (7)°]. The mean planes of the two ligands are nearly orthogonal to each other with an angle of 89.53 (6)°. The packing of the complex is supported by O-H⋯N and O-H⋯S hydrogen bonding between the solvent water mol-ecule and the uncoordinated N and S atoms of neighbouring ligands.
In the title salt, C14H17N2(+)·Cl(-), the central N atom is pyramidal (sum of bond angles = 330.9°) and there is a near orthogonal relationship between the benzene rings [dihedral angle = 89.95 (10)°]. The crystal packing features N-H⋯Cl hydrogen bonds, which lead to a supra-molecular undulating ribbon along the a axis comprising edge-shared eight-membered {⋯HNH⋯Cl}2 synthons. The chains are connected into layers in the ab plane by C-H⋯π inter-actions.
The title compound, C(12)H(16)N(2)S(3), was obtained by the condensation reaction of S-benzyl dithio-carbazate and 3-mercaptobutan-2-one. The phenyl ring and thiol (SH) group are approximately perpendicular [S-C-C-C and N-C-C-S torsion angles = 67.8 (3) and 116.9 (2)°, respectively] to the rest of the mol-ecule. In the crystal, mol-ecules are linked by weak S-H⋯S and N-H⋯S hydrogen bonds, π-π inter-actions between the benzene rings [centroid-centroid distance = 3.823 (2) Å] and C-H⋯π inter-actions.
In the title compound, C(16)H(15)N(3)S(2), the central C(2)N(2)S(2) residue is planar (r.m.s. deviation = 0.045 Å) and the pyridyl and benzene rings are inclined and approximately coplanar to this plane, respectively [dihedral angles = 72.85 (9) and 10.73 (9)°], so that, overall, the mol-ecule adopts an L-shape. The conformation about each of the N=C [1.290 (3) Å] and C=C [1.340 (3) Å] bonds is E. Supra-molecular chains along [1-10] are stabilized by N-H⋯N(pyridine) hydrogen bonding and these are connected into a double layer that stacks along the c-axis direction by C-H⋯π(pyridine) inter-actions.
The title compound C(8)H(15)N(3)S has two mol-ecules in the asymmetric unit in which cis-trans isomerism is exhibited around the N(NH)C=S bonds. The cyclo-hexyl rings in both mol-ecules adopt a chair conformation. In the crystal, N-H⋯S hydrogen bonding produces dimers, which are inter-connected through further N-H⋯S hydrogen bonds, forming chains along the b-axis direction.