The asymmetric unit of the three-component title compound, 2,2'-di-thiodi-benzoic acid-2-chloro-benzoic acid-N,N-di-methyl-formamide (1/1/1), C14H10O4S2·C7H5ClO2·C3H7NO, contains a mol-ecule each of 2,2'-di-thiodi-benzoic acid (DTBA), 2-chloro-benzoic acid (2CBA) and di-methyl-formamide (DMF). The DTBA mol-ecule is twisted [the C-S-S-C torsion angle is 88.37 (17)°] and each carb-oxy-lic group is slightly twisted from the benzene ring to which it is connected [CO2/C6 dihedral angles = 7.6 (3) and 12.5 (3)°]. A small twist is evident in the mol-ecule of 2CBA [CO2/C6 dihedral angle = 4.4 (4)°]. In the crystal, the three mol-ecules are connected by hydrogen bonds with the two carb-oxy-lic acid residues derived from DTBA and 2CBA forming a non-symmetric eight-membered {⋯HOCO}2 synthon, and the second carb-oxy-lic acid of DTBA linked to the DMF mol-ecule via a seven-membered {⋯HOCO⋯HCO} heterosynthon. The three-mol-ecule aggregates are connected into a supra-molecular chain along the a axis via DTBA-C-H⋯O(hydroxyl-2CBA), 2CBA-C-H⋯O(hydroxyl-DTBA) and DTBA-C-H⋯S(DTBA) inter-actions. Supra-molecular layers in the ab plane are formed as the chains are linked via DMF-C-H⋯S(DTBA) contacts, and these inter-digitate along the c-axis direction without specific points of contact between them. A Hirshfeld surface analysis points to additional but, weak contacts to stabilize the three-dimensional architecture: DTBA-C=O⋯H(phenyl-DTBA), 2CBA-Cl⋯H(phenyl-DTBA), as well as a π-π contact between the delocalized eight-membered {⋯HOC=O}2 carb-oxy-lic dimer and the phenyl ring of 2CBA. The latter was confirmed by electrostatic potential (ESP) mapping.
The crystal and mol-ecular structures of C14H12Cl2, (I), and C14H12Br2, (II), are described. The asymmetric unit of (I) comprises two independent mol-ecules, A and B, each disposed about a centre of inversion. Each mol-ecule approximates mirror symmetry [the Cb-Cb-Ce-Ce torsion angles = -83.46 (19) and 95.17 (17)° for A, and -83.7 (2) and 94.75 (19)° for B; b = benzene and e = ethyl-ene]. By contrast, the mol-ecule in (II) is twisted, as seen in the dihedral angle of 59.29 (11)° between the benzene rings cf. 0° in (I). The mol-ecular packing of (I) features benzene-C-H⋯π(benzene) and Cl⋯Cl contacts that lead to an open three-dimensional (3D) architecture that enables twofold 3D-3D inter-penetration. The presence of benzene-C-H⋯π(benzene) and Br⋯Br contacts in the crystal of (II) consolidate the 3D architecture. The analysis of the calculated Hirshfeld surfaces confirm the influence of the benzene-C-H⋯π(benzene) and X⋯X contacts on the mol-ecular packing and show that, to a first approximation, H⋯H, C⋯H/H⋯C and C⋯X/X⋯C contacts dominate the packing, each contributing about 30% to the overall surface in each of (I) and (II). The analysis also clearly differentiates between the A and B mol-ecules of (I).
In the title compound, C18H12O3S2, synthesized by the Claisen-Schmidt condensation method, the essentially planar chalcone unit adopts an s-cis configuration with respect to the carbonyl group within the ethyl-enic bridge. In the crystal, weak C-H⋯π inter-actions connect the mol-ecules into zigzag chains along the b-axis direction. The mol-ecular structure was optimized geometrically using Density Functional Theory (DFT) calculations at the B3LYP/6-311 G++(d,p) basis set level and compared with the experimental values. Mol-ecular orbital calculations providing electron-density plots of HOMO and LUMO mol-ecular orbitals and mol-ecular electrostatic potentials (MEP) were also computed both with the DFT/B3LYP/6-311 G++(d,p) basis set. The experimental energy gap is 3.18 eV, whereas the theoretical HOMO-LUMO energy gap value is 2.73 eV. Hirshfeld surface analysis was used to further investigate the weak inter-actions present.
The title compound, C23H15NO3, adopts an s-cis conformation with respect to the ethyl-ene C=C and carbonyl C=O double bonds in the enone unit. The mol-ecule is significantly twisted with a dihedral angle of 48.63 (14)° between the anthracene ring system and the benzene ring. In the crystal, mol-ecules are linked into inversion dimers with an R 2 2(10) graph-set motif via pairs of C-H⋯O hydrogen bonds. The inter-molecular inter-actions were analysed and qu-anti-fied by Hirshfeld surface analysis. The mol-ecular structure was optimized and a small HOMO-LUMO energy gap of 2.55 eV was obtained using the DFT method at the B3LYP/6-311 G++(d,p) level of theory. This value is in close agreement with the experimental value of 2.52 eV obtained from the UV-vis analysis. The crystal used was a two-component merohedral twin with a refined ratio of 0.1996 (16):0.8004 (16).
In the title compound, C10H13N3OS, the azomethine C=N double bond has an E configuration. The phenyl ring and methyl-hydrazine carbo-thio-amide moiety [maximum deviation = 0.008 (2) Å] are twisted slightly with a dihedral angle of 14.88 (10)°. In the crystal, mol-ecules are linked into sheets parallel to the ab plane via N-H⋯S hydrogen bonds and C-H⋯π inter-actions.
In the redetermination of the title compound, C3H5N2OS+·CI-, the asymmetric unit consists of one independent 2-oxo-1,3-thia-zolidin-4-iminium cation and one independent chloride anion. The cation inter-acts with a chloride anion via N-H⋯Cl hydrogen bonds forming a supra-molecular chain along [010]. These supra-molecular chains are further extended by weak C-H⋯Cl and C-H⋯O inter-actions, forming a two-dimensional network parallel to (001). The crystal structure is further stabilized by weak C-O⋯π inter-actions, supporting a three-dimensional architecture. The structure was previously determined by Ananthamurthy & Murthy [Z. Kristallogr. (1975). 8, 356-367] but has been redetermined with higher precision to allow the hydrogen-bonding patterns and supra-molecular inter-actions to be investigated.
The title compound, C15H13BrO2S, comprises three different substituents bound to a central (and chiral) methine-C atom, i.e. (4-bromo-phen-yl)sulfanyl, benzaldehyde and meth-oxy residues: crystal symmetry generates a racemic mixture. A twist in the mol-ecule is evident about the methine-C-C(carbon-yl) bond as evidenced by the O-C-C-O torsion angle of -20.8 (7)°. The dihedral angle between the bromo-benzene and phenyl rings is 43.2 (2)°, with the former disposed to lie over the oxygen atoms. The most prominent feature of the packing is the formation of helical supra-molecular chains as a result of methyl- and methine-C-H⋯O(carbon-yl) inter-actions. The chains assemble into a three-dimensional architecture without directional inter-actions between them. The nature of the weak points of contacts has been probed by a combination of Hirshfeld surface analysis, non-covalent inter-action plots and inter-action energy calculations. These point to the importance of weaker H⋯H and C-H⋯C inter-actions in the consolidation of the structure.
In the title quinoline derivative, C14H14ClNO3, there is an intra-molecular C-H⋯O hydrogen bond forming an S(6) graph-set motif. The mol-ecule is essentially planar with the mean plane of the ethyl acetate group making a dihedral angle of 5.02 (3)° with the ethyl 6-chloro-2-eth-oxy-quinoline mean plane. In the crystal, offset π-π inter-actions with a centroid-to-centroid distance of 3.4731 (14) Å link inversion-related mol-ecules into columns along the c-axis direction. Hirshfeld surface analysis indicates that H⋯H contacts make the largest contribution (50.8%) to the Hirshfeld surface.
The asymmetric unit of the title compound, C15H21N3OS, comprises of two crystallographically independent mol-ecules (A and B). Each mol-ecule consists of a cyclo-hexane ring and a 2-hy-droxy-3-methyl-benzyl-idene ring bridged by a hydrazinecarbo-thio-amine unit. Both mol-ecules exhibit an E configuration with respect to the azomethine C=N bond. There is an intra-molecular O-H⋯N hydrogen bond in each mol-ecule forming an S(6) ring motif. The cyclo-hexane ring in each mol-ecule has a chair conformation. The benzene ring is inclined to the mean plane of the cyclo-hexane ring by 47.75 (9)° in mol-ecule A and 66.99 (9)° in mol-ecule B. The mean plane of the cyclo-hexane ring is inclined to the mean plane of the thio-urea moiety [N-C(=S)-N] by 55.69 (9) and 58.50 (8)° in mol-ecules A and B, respectively. In the crystal, the A and B mol-ecules are linked by N-H⋯S hydrogen bonds, forming 'dimers'. The A mol-ecules are further linked by a C-H⋯π inter-action, hence linking the A-B units to form ribbons propagating along the b-axis direction. The conformation of a number of related cyclo-hexa-nehydrazinecarbo-thio-amides are compared to that of the title compound.
In the title bis-chalcone, C17H12Br2O, the olefinic double bonds are almost coplanar with their attached 4-bromo-phenyl rings [torsion angles = -10.2 (4) and -6.2 (4)°], while the carbonyl double bond is in an s-trans conformation with with respect to one of the C=C bonds and an s-cis conformation with respect to the other [C=C-C=O = 160.7 (3) and -15.2 (4)°, respectively]. The dihedral angle between the 4-bromo-phenyl rings is 51.56 (2)°. In the crystal, mol-ecules are linked into a zigzag chain propagating along [001] by weak C-H⋯π inter-actions. The conformations of related bis-chalcones are surveyed and a Hirshfeld surface analysis is used to investigate and qu-antify the inter-molecular contacts.
The title CuII complex, [Cu(C13H11N2OS2)2], features a trans-N2S2 donor set as a result of the CuII atom being located on a crystallographic centre of inversion and being coordinated by thiol-ate-S and imine-N atoms derived from two di-thio-carbazate anions. The resulting geometry is distorted square-planar. In the crystal, π(chelate ring)-π(fur-yl) [inter-centroid separation = 3.6950 (14) Å and angle of inclination = 5.33 (13)°] and phenyl-C-H⋯π(phen-yl) inter-actions sustain supra-molecular layers lying parallel to (02). The most prominent inter-actions between layers, as confirmed by an analysis of the calculated Hirshfeld surface, are phenyl-H⋯H(phen-yl) contacts. Indications for Cu⋯Cg(fur-yl) contacts (Cu⋯Cg = 3.74 Å) were also found. Inter-action energy calculations suggest the contacts between mol-ecules are largely dispersive in nature.
In the title benzohydrazide derivative, C14H12N2O4, the azomethine C=N double bond has an E configuration. The hydrazide connecting bridge, (C=O)-(NH)-N=(CH), is nearly planar with C-C-N-N and C-N-N=C torsion angles of -177.33 (10) and -174.98 (12)°, respectively. The 4-hy-droxy-phenyl and 3,4-di-hydroxy-phenyl rings are slightly twisted, making a dihedral angle of 9.18 (6)°. In the crystal, mol-ecules are connected by N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network, while further consolidated via π-π inter-actions [centroid-centroid distances = 3.6480 (8) and 3.7607 (8) Å]. The conformation is compared to those of related benzyl-idene-4-hy-droxy-benzohydrazide derivatives.
The asymmetric unit of the title compound, 2C17H12N2O3·H2O comprises two mol-ecules of (E)-3-(1H-indol-2-yl)-1-(4-nitro-phen-yl)prop-2-en-1-one and a water mol-ecule. The main mol-ecule adopts an s-cis configuration with respect to the C=O and C=C bonds. The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64 (16)°. In the crystal, mol-ecules are linked by O--H⋯O and N-H⋯O hydrogen bonds, forming chains along [010]. In addition, weak C-H⋯O, C-H⋯π and π-π inter-actions further link the structure into a three-dimensional network. The optimized structure was generated theoretically via a density functional theory (DFT) approach at the B3LYP/6-311 G++(d,p) basis level and the HOMO-LUMO behaviour was elucidated to determine the energy gap. The obtained values of 2.70 eV (experimental) and 2.80 eV (DFT) are desirable for optoelectronic applications. The inter-molecular inter-actions were qu-anti-fied and analysed using Hirshfeld surface analysis.
The asymmetric unit of the title halogenated chalcone derivative, C15H10BrFO, contains two independent mol-ecules, both adopting an s-cis configuration with respect to the C=O and C=C bonds. In the crystal, centrosymmetrically related mol-ecules are linked into dimers via inter-molecular hydrogen bonds, forming rings with R 1 2(6), R 2 2(10) and R 2 2(14) graph-set motifs. The dimers are further connected by C-H⋯O inter-actions into chains parallel to [001]. A Hirshfeld surface analysis suggests that the most significant contribution to the crystal packing is by H⋯H contacts (26.3%). Calculations performed on the optimized structure obtained using density functional theory (DFT) at B3LYP with the 6-311 G++(d,p) basis set reveal that the HOMO-LUMO energy gap is 4.12 eV, indicating the suitability of this crystal for optoelectronic and biological applications. The nucleophilic and electrophilic binding site regions are elucidated using the mol-ecular electrostatic potential (MEP).
In this study, a new monoclinic polymorph (space group C2/c) of 2,2'-methyl-enebis(isoindoline-1,3-dione), C17H10N2O4, is reported and compared to the previously reported triclinic polymorph (space group P ). Similarly, both polymorphs consist of a unique mol-ecule in the asymmetric unit (Z' = 1). The mol-ecular conformations of the two polymorphs are very similar, as shown by the r.m.s. deviation of 0.368 Å (excluding all H atoms). The inter-molecular inter-actions of both polymorphs are described along with the Hirshfeld surface analysis, and the lattice energies are calculated.
The X-ray crystal structure of the title phthalazin-1-one derivative, C17H16N2O3S {systematic name: 2-[(2,4,6-tri-methyl-benzene)-sulfon-yl]-1,2-di-hydro-phthalazin-1-one}, features a tetra-hedral sulfoxide-S atom, connected to phthalazin-1-one and mesityl residues. The dihedral angle [83.26 (4)°] between the organic substituents is consistent with the mol-ecule having the shape of the letter V. In the crystal, phthalazinone-C6-C-H⋯O(sulfoxide) and π(phthalazinone-N2C4)-π(phthalazinone-C6) stacking [inter-centroid distance = 3.5474 (9) Å] contacts lead to a linear supra-molecular tape along the a-axis direction; tapes assemble without directional inter-actions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of the C-H⋯O and π-stacking inter-actions but, also H⋯H and C-H⋯C contacts. The calculation of the inter-action energies indicate the importance of dispersion terms with the greatest energies calculated for the C-H⋯O and π-stacking inter-actions.
The title compound, [Cu(C5H5NO2S2)(C18H15P)2]·CHCl3, features a tetra-hedrally coordinated CuI atom within a P2S2 donor set defined by two phosphane P atoms and by two S atoms derived from a symmetrically coordinating di-thio-carbamate ligand. Both intra- and inter-molecular hy-droxy-O-H⋯O(hydroxy) hydrogen bonding is observed: the former closes an eight-membered {⋯HOC2NC2O} ring, whereas the latter connects centrosymmetrically related mol-ecules into dimeric aggregates via eight-membered {⋯H-O⋯H-O}2 synthons. The complex mol-ecules are arranged to form channels along the c axis in which reside the chloro-form mol-ecules, being connected by Cl⋯π(arene) and short S⋯Cl [3.3488 (9) Å] inter-actions. The inter-molecular inter-actions have been investigated further by Hirshfeld surface analysis, which shows the conventional hydrogen bonding to be very localized with the main contributors to the surface, at nearly 60%, being H⋯H contacts. Solution NMR studies indicate that whilst the same basic mol-ecular structure is retained in solution, the tri-phenyl-phosphane ligands are highly labile, exchanging rapidly with free Ph3P at room temperature.
The title compound, C15H14N2O3, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit that differ in the orientation of the 3-meth-oxy-phenyl group with respect to the methyl-idenebenzohydrazide unit. The dihedral angles between the two benzene rings are 24.02 (10) and 29.30 (9)° in mol-ecules A and B, respectively. In mol-ecule A, the meth-oxy group is twisted slightly relative to its bound benzene ring, with a Cmeth-yl-O-C-C torsion angle of 14.2 (3)°, whereas it is almost co-planar in mol-ecule B, where the corresponding angle is -2.4 (3)°. In the crystal, the mol-ecules are linked by N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds, as well as by weak C-H⋯O inter-actions, forming sheets parallel to the bc plane. The N-H⋯O hydrogen bond and weak C-H⋯O inter-action link different mol-ecules (A⋯B) whereas both O-H⋯N and O-H⋯O hydrogen bonds link like mol-ecules (A⋯A) and (B⋯B). Pairs of inversion-related B mol-ecules are stacked approximately along the a axis by π-π inter-actions in which the distance between the centroids of the 3-meth-oxy-phenyl rings is 3.5388 (12) Å. The B mol-ecules also participate in weak C-H⋯π inter-actions between the 4-hy-droxy-phenyl and the 3-meth-oxy-phenyl rings.
The complete mol-ecule of the binuclear title complex, bis-[μ-1H-1,2,4-triazole-5(4H)-thione-κ2 S:S]bis-{(thio-cyanato-κS)[1H-1,2,4-triazole-5(4H)-thione-κS]silver(I)}, [Ag2(SCN)2(C2H3N3S)4], is generated by crystallographic inversion symmetry. The independent triazole-3-thione ligands employ the exocyclic-S atoms exclusively in coordination. One acts as a terminal S-ligand and the other in a bidentate (μ2) bridging mode to provide a link between two AgI centres. Each AgI atom is also coordinated by a terminal S-bound thio-cyanate ligand, resulting in a distorted AgS4 tetra-hedral coordination geometry. An intra-molecular N-H⋯S(thio-cyanate) hydrogen bond is noted. In the crystal, amine-N-H⋯S(thione), N-H⋯N(triazol-yl) and N-H⋯N(thio-cyanate) hydrogen bonds give rise to a three-dimensional architecture. The packing is consolidated by triazolyl-C-H⋯S(thio-cyanate), triazolyl-C-H⋯N(thiocyanate) and S⋯S [3.2463 (9) Å] inter-actions as well as face-to-face π-π stacking between the independent triazolyl rings [inter-centroid separation = 3.4444 (15) Å]. An analysis of the calculated Hirshfeld surfaces shows the three major contributors are due to N⋯H/H⋯N, S⋯H/H⋯S and C⋯H/H⋯C contacts, at 35.8, 19.4 and 12.7%, respectively; H⋯H contacts contribute only 7.6% to the overall surface.
The title homoleptic Schiff base complexes, [M(C14H9Cl2N2O)2], for M = CoII, (I), and CuII, (II), present distinct coordination geometries despite the Schiff base dianion coordinating via the phenolato-O and imine-N atoms in each case. For (I), the coordination geometry is based on a trigonal bipyramid whereas for (II), a square-planar geometry is found (Cu site symmetry ). In the crystal of (I), discernible supra-molecular layers in the ac plane are sustained by chloro-benzene-C-H⋯O(coordinated), chloro-benzene-C-H⋯π(fused-benzene ring) as well as π(fused-benzene, chloro-benzene)-π(chloro-benzene) inter-actions [inter-centroid separations = 3.6460 (17) and 3.6580 (16) Å, respectively]. The layers inter-digitate along the b-axis direction and are linked by di-chloro-benzene-C-H⋯π(fused-benzene ring) and π-π inter-actions between fused-benzene rings and between chloro-benzene rings [inter-centroid separations = 3.6916 (16) and 3.7968 (19) Å, respectively] . Flat, supra-molecular layers are also found in the crystal of (II), being stabilized by π-π inter-actions formed between fused-benzene rings and between chloro-benzene rings [inter-centroid separations = 3.8889 (15) and 3.8889 (15) Å, respectively]; these stack parallel to [10] without directional inter-actions between them. The analysis of the respective calculated Hirshfeld surfaces indicate diminished roles for H⋯H contacts [26.2% (I) and 30.5% (II)] owing to significant contributions by Cl⋯H/H⋯Cl contacts [25.8% (I) and 24.9% (II)]. Minor contributions by Cl⋯Cl [2.2%] and Cu⋯Cl [1.9%] contacts are indicated in the crystals of (I) and (II), respectively. The inter-action energies largely arise from dispersion terms; the aforementioned Cu⋯Cl contact in (II) gives rise to the most stabilizing inter-action in the crystal of (II).