The mol-ecule of the title Schiff base compound, C14H14N2O2, displays an E conformation with respect the imine C=N double bond. The mol-ecule is approximately planar, with the dihedral angle formed by the planes of the pyridine and benzene rings being 5.72 (6)°. There is an intra-molecular hydrogen bond involving the phenolic H and imine N atoms.
The compounds 2-(1-benzo-furan-2-yl)-2-oxoethyl 2-nitro-benzoate, C17H11NO6 (I), and 2-(1-benzo-furan-2-yl)-2-oxoethyl 2-amino-benzoate, C17H13NO4 (II), were synthesized under mild conditions. Their mol-ecular structures were characterized by both spectroscopic and single-crystal X-ray diffraction analysis. The mol-ecular conformations of both title compounds are generally similar. However, different ortho-substituted moieties at the phenyl ring of the two compounds cause deviations in the torsion angles between the carbonyl group and the attached phenyl ring. In compound (I), the ortho-nitro-phenyl ring is twisted away from the adjacent carbonyl group whereas in compound (II), the ortho-amino-phenyl ring is almost co-planar with the carbonyl group. In the crystal of compound (I), two C-H⋯O hydrogen bonds link the mol-ecules into chains propagating along the c-axis direction and the chains are inter-digitated, forming sheets parallel to [20-1]. Conversely, pairs of N-H⋯O hydrogen bonds in compound (II) link inversion-related mol-ecules into dimers, which are further extended by C-H⋯O hydrogen bonds into dimer chains. These chains are inter-connected by π-π inter-actions involving the furan rings, forming sheets parallel to the ac plane.
In the title compounds, (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(2-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (I), (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (II) and (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3,4-di-meth-oxy-phen-yl)prop-2-en-1-one], C28H26O6 (III), the asymmetric unit consists of a half-mol-ecule, completed by crystallographic inversion symmetry. The dihedral angles between the central and terminal benzene rings are 56.98 (8), 7.74 (7) and 7.73 (7)° for (I), (II) and (III), respectively. In the crystal of (I), mol-ecules are linked by pairs of C-H⋯π inter-actions into chains running parallel to [101]. The packing for (II) and (III), features inversion dimers linked by pairs of C-H⋯O hydrogen bonds, forming R2(2)(16) and R2(2)(14) ring motifs, respectively, as parts of [201] and [101] chains, respectively.
In the title isonicotinohydrazide hydrate, C14H12BrN3O2·H2O {systematic name: N'-[(1E)-1-(5-bromo-2-hy-droxy-phen-yl)ethyl-idene]pyridine-4-carbohydrazide monohydrate}, the central CN2O region of the organic mol-ecule is planar and the conformation about the imine-C=N bond is E. While an intra-molecular hy-droxy-O-H⋯N(imine) hydrogen bond is evident, the dihedral angle between the central residue and the benzene rings is 48.99 (9)°. Overall, the mol-ecule is twisted, as seen in the dihedral angle of 71.79 (6)° between the outer rings. In the crystal, hydrogen-bonding inter-actions, i.e. hydrazide-N-H⋯O(water), water-O-H⋯O(carbon-yl) and water-O-H⋯N(pyrid-yl), lead to supra-molecular ribbons along the a-axis direction. Connections between these, leading to a three-dimensional architecture, are mediated by Br⋯Br halogen bonding [3.5366 (3) Å], pyridyl-C-H⋯O(carbon-yl) as well as weak π-π inter-actions [inter-centroid separation between benzene rings = 3.9315 (12) Å]. The Hirshfeld surface analysis reveals the importance of hydrogen atoms in the supra-molecular connectivity as well as the influence of the Br⋯Br halogen bonding.
In the anion of the title salt hydrate, H5N2(+)·C7H5N2O4(-)·2H2O, the carboxyl-ate and nitro groups lie out of the plane of the benzene ring to which they are bound [dihedral angles = 18.80 (10) and 8.04 (9)°, respectively], and as these groups are conrotatory, the dihedral angle between them is 26.73 (15)°. An intra-molecular amino-N-H⋯O(carboxyl-ate) hydrogen bond is noted. The main feature of the crystal packing is the formation of a supra-molecular chain along the b axis, with a zigzag topology, sustained by charge-assisted water-O-H⋯O(carboxyl-ate) hydrogen bonds and comprising alternating twelve-membered {⋯OCO⋯HOH}2 and eight-membered {⋯O⋯HOH}2 synthons. Each ammonium-N-H atom forms a charge-assisted hydrogen bond to a water mol-ecule and, in addition, one of these forms a hydrogen bond with a nitro-O atom. The amine-N-H atoms form hydrogen bonds to carboxyl-ate-O and water-O atoms, and the amine N atom accepts a hydrogen bond from an amino-H atom. The hydrogen bonds lead to a three-dimensional architecture. An analysis of the Hirshfeld surface highlights the major contribution of O⋯H/H⋯O hydrogen bonding to the overall surface, i.e. 46.8%, compared with H⋯H contacts (32.4%).
The title di-thio-carbazate ester (I), C18H18N2S2 [systematic name: (E)-4-methyl-benzyl 2-[(E)-3-phenyl-allyl-idene]hydrazinecarbodi-thio-ate, comprises an almost planar central CN2S2 residue [r.m.s. deviation = 0.0131 Å]. The methyl-ene(tolyl-4) group forms a dihedral angle of 72.25 (4)° with the best plane through the remaining non-hydrogen atoms [r.m.s. deviation = 0.0586 Å] so the mol-ecule approximates mirror symmetry with the 4-tolyl group bis-ected by the plane. The configuration about both double bonds in the N-N=C-C=C chain is E; the chain has an all trans conformation. In the crystal, eight-membered centrosymmetric thio-amide synthons, {⋯HNCS}2, are formed via N-H⋯S(thione) hydrogen bonds. Connections between the dimers via C-H⋯π inter-actions lead to a three-dimensional architecture. A Hirshfeld surface analysis shows that (I) possesses an inter-action profile similar to that of a closely related analogue with an S-bound benzyl substituent, (II). Computational chemistry indicates the dimeric species of (II) connected via N-H⋯S hydrogen bonds is about 0.94 kcal mol(-1) more stable than that in (I).
The asymmetric unit of the title compound, C24H14F4O2, comprises of one and a half mol-ecules; the half-mol-ecule is completed by crystallographic inversion symmetry. In the crystal, mol-ecules are linked into a three-dimensional network by C-H⋯F and C-H⋯O hydrogen bonds. Some of the C-H⋯F links are unusually short (< 2.20 Å). Hirshfeld surface analyses (dnorm surfaces and two-dimensional fingerprint plots) for the title compound are presented and discussed.
In the title mol-ecular salt, 2C6H10N3O+·C8H4O42-, the N atom of each of the two 2-amino-4-meth-oxy-6-methyl-pyrimidine mol-ecules lying between the amine and methyl groups has been protonated. The dihedral angles between the pyrimidine rings of the cations and the benzene ring of the succinate dianion are 5.04 (8) and 7.95 (8)°. Each of the cations is linked to the anion through a pair of N-H⋯O(carboxyl-ate) hydrogen bonds, forming cyclic R22(8) ring motifs which are then linked through inversion-related N-H⋯O hydrogen bonds, giving a central R24(8) motif. Peripheral amine N-H⋯O hydrogen-bonding inter-actions on either side of the succinate anion, also through centrosymmetric R22(8) extensions, form one-dimensional ribbons extending along [211]. The crystal structure also features π-π stacking inter-actions between the aromatic rings of the pyrimidine cations [minimum ring centroid separation = 3.6337 (9) Å]. The inter-molecular inter-actions were also investigated using Hirshfeld surface studies and two-dimensional fingerprint images.
In the title mol-ecular salt, C6H10N3O(+)·C7H5O3(-), the cation is protonated at the N atom lying between the amine and methyl substituents and the dihedral angle between the carboxyl group and its attached ring in the anion is 4.0 (2)°. The anion features an intra-molecular O-H⋯O hydrogen bond, which closes an S(6) ring. The cation and anion are linked by two N-H⋯O hydrogen bonds [R2(2)(8) motif] to generate an ion pair in which the dihedral angle between the aromatic rings is 8.34 (9)°. Crystal symmetry relates two ion pairs bridged by further N-H⋯O hydrogen bonds into a tetra-meric DDAA array. The tetra-mers are linked by pairs of C-H⋯O hydrogen bonds to generate [100] chains. Hirshfeld surface and fingerprint plot analyses are presented.
2-(Benzo-furan-2-yl)-2-oxoethyl 2-chloro-benzoate, C17H11ClO4 (I), and 2-(benzo-furan-2-yl)-2-oxoethyl 2-meth-oxy-benzoate, C18H14O5 (II), were synthesized under mild conditions. Their chemical and mol-ecular structures were analyzed by spectroscopic and single-crystal X-ray diffraction studies, respectively. These compounds possess different ortho-substituted functional groups on their phenyl rings, thus experiencing extra steric repulsion force within their mol-ecules as the substituent changes from 2-chloro (I) to 2-meth-oxy (II). The crystal packing of compound (I) depends on weak inter-molecular hydrogen bonds and π-π inter-actions. Mol-ecules are related by inversion into centrosymmetric dimers via C-H⋯O hydrogen bonds, and further strengthened by π-π inter-actions between furan rings. Conversely, mol-ecules in compound (II) are linked into alternating dimeric chains propagating along the [101] direction, which develop into a two-dimensional plate through extensive inter-molecular hydrogen bonds. These plates are further stabilized by π-π and C-H⋯π inter-actions.
The asymmetric unit of the title compound, C15H15N3O3·0.5H2O, comprises two 2-{[(4-iminiumyl-3-methyl-1,4-di-hydro-pyridin-1-yl)meth-yl]carbamo-yl}benzoate zwitterions (A and B) and a water mol-ecule. The dihedral angles between the pyridine and phenyl rings in the zwitterions are 53.69 (10) and 73.56 (11)° in A and B, respectively. In the crystal, mol-ecules are linked by N-H⋯O, O-H⋯O, C-H⋯O and C-H⋯π(ring) hydrogen bonds into a three-dimensional network. The crystal structure also features π-π inter-actions involving the centroids of the pyridine and phenyl rings [centroid-centroid distances = 3.5618 (12) Å in A and 3.8182 (14) Å in B].
The full mol-ecule of the binuclear title compound, [Cd2Cl2(C6H8O4)(C6H8N2)2(H2O)2], is generated by the application of a centre of inversion located at the middle of the central CH2-CH2 bond of the adipate dianion; the latter chelates a CdII atom at each end. Along with two carboxyl-ate-O atoms, the CdII ion is coordinated by the two N atoms of the chelating benzene-1,2-di-amine ligand, a Cl- anion and an aqua ligand to define a distorted octa-hedral CdClN2O3 coordination geometry with the monodentate ligands being mutually cis. The disparity in the Cd-N bond lengths is related to the relative trans effect exerted by the Cd-O bonds formed by the carboxyl-ate-O and aqua-O atoms. The packing features water-O-H⋯O(carboxyl-ate) and benzene-1,2-di-amine-N-H⋯Cl hydrogen bonds, leading to layers that stack along the a-axis direction. The lack of directional inter-actions between the layers is confirmed by a Hirshfeld surface analysis.
In the title tri-substituted thio-urea derivative, C13H18N2O3S, the thione-S and carbonyl-O atoms lie, to a first approximation, to the same side of the mol-ecule [the S-C-N-C torsion angle is -49.3 (2)°]. The CN2S plane is almost planar (r.m.s. deviation = 0.018 Å) with the hy-droxy-ethyl groups lying to either side of this plane. One hy-droxy-ethyl group is orientated towards the thio-amide functionality enabling the formation of an intra-molecular N-H⋯O hydrogen bond leading to an S(7) loop. The dihedral angle [72.12 (9)°] between the planes through the CN2S atoms and the 4-tolyl ring indicates the mol-ecule is twisted. The experimental mol-ecular structure is close to the gas-phase, geometry-optimized structure calculated by DFT methods. In the mol-ecular packing, hydroxyl-O-H⋯O(hydrox-yl) and hydroxyl-O-H⋯S(thione) hydrogen bonds lead to the formation of a supra-molecular layer in the ab plane; no directional inter-actions are found between layers. The influence of the specified supra-molecular inter-actions is apparent in the calculated Hirshfeld surfaces and these are shown to be attractive in non-covalent inter-action plots; the inter-action energies point to the important stabilization provided by directional O-H⋯O hydrogen bonds.
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.
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.
A new polymorphic form of the title compound, C8H8O3, is described in the centrosymmetric monoclinic space group P21/c with Z' = 1 as compared to the first polymorph, which crystallizes with two conformers (Z' = 2) in the asymmetric unit in the same space group. In the crystal of the second polymorph, inversion dimers linked by O-H⋯O hydrogen bonds occur and these are linked into zigzag chains, propagating along the b-axis direction by C-H⋯O links. The crystal structure also features a weak π-π inter-action, with a centroid-to-centroid distance of 3.8018 (6) Å. The second polymorph of the title compound is less stable than the reported first polymorph, as indicated by its smaller calculated lattice energy.
The asymmetric unit of the title 1:2 co-crystal, C14H10O4S2·2C7H6O2, comprises half a mol-ecule of di-thiodi-benzoic acid [systematic name: 2-[(2-carb-oxy-phen-yl)disulfan-yl]benzoic acid, DTBA], as the mol-ecule is located about a twofold axis of symmetry, and a mol-ecule of benzoic acid (BA). The DTBA mol-ecule is twisted about the di-sulfide bond [the C-S-S-C torsion angle is -83.19 (8)°] resulting in a near perpendicular relationship between the benzene rings [dihedral angle = 71.19 (4)°]. The carb-oxy-lic acid group is almost co-planar with the benzene ring to which it is bonded [dihedral angle = 4.82 (12)°]. A similar near co-planar relationship pertains for the BA mol-ecule [dihedral angle = 3.65 (15)°]. Three-mol-ecule aggregates are formed in the crystal whereby two BA mol-ecules are connected to a DTBA mol-ecule via hy-droxy-O-H⋯O(hydroxy) hydrogen bonds and eight-membered {⋯HOC=O}2 synthons. These are connected into a supra-molecular layer in the ab plane through C-H⋯O inter-actions. The inter-actions between layers to consolidate the three-dimensional architecture are π-π stacking inter-actions between DTBA and BA rings [inter-centroid separation = 3.8093 (10) Å] and parallel DTBA-hy-droxy-O⋯π(BA) contacts [O⋯ring centroid separation = 3.9049 (14) Å]. The importance of the specified inter-actions as well as other weaker contacts, e.g. π-π and C-H⋯S, are indicated in the analysis of the calculated Hirshfeld surface and inter-action energies.
The mol-ecular structure of the title chalcone derivative, C15H10FNO3, is nearly planar and the mol-ecule adopts a trans configuration with respect to the C=C double bond. The nitro group is nearly coplanar with the attached benzene ring, which is nearly parallel to the second benzene ring. In the crystal, mol-ecules are connected by pairs of weak inter-molecular C-H⋯O hydrogen bonds into inversion dimers. The dimers are further linked by another C-H⋯O hydrogen bond and a C-H⋯F hydrogen bond into sheets parallel to (104). π-π inter-actions occur between the sheets, with a centroid-centroid distance of 3.8860 (11) Å. Hirshfeld surface analysis was used to investigate and qu-antify the inter-molecular inter-actions.
The title compound, 2C14H14N4O·H2O, comprises a neutral mol-ecule containing a central pyrazol-3-one ring flanked by an N-bound phenyl group and a C-bound 5-methyl-1H-pyrazol-3-yl group (at positions adjacent to the carbonyl substituent), its zwitterionic tautomer, whereby the N-bound proton of the central ring is now resident on the pendant ring, and a water mol-ecule of crystallization. Besides systematic variations in geometric parameters, the two independent organic mol-ecules have broadly similar conformations, as seen in the dihedral angle between the five-membered rings [9.72 (9)° for the neutral mol-ecule and 3.32 (9)° for the zwitterionic tautomer] and in the dihedral angles between the central and pendant five-membered rings [28.19 (8) and 20.96 (8)° (neutral mol-ecule); 11.33 (9) and 11.81 (9)°]. In the crystal, pyrazolyl-N-H⋯O(carbon-yl) and pyrazolium-N-H⋯N(pyrazol-yl) hydrogen bonds between the independent organic mol-ecules give rise to non-symmetric nine-membered {⋯HNNH⋯NC3O} and {⋯HNN⋯HNC3O} synthons, which differ in the positions of the N-bound H atoms. These aggregates are connected into a supra-molecular layer in the bc plane by water-O-H⋯N(pyrazolide), water-O-H⋯O(carbon-yl) and pyrazolyl-N-H⋯O(water) hydrogen bonding. The layers are linked into a three-dimensional architecture by methyl-C-H⋯π(phen-yl) inter-actions. The different inter-actions, in particular the weaker contacts, formed by the organic mol-ecules are clearly evident in the calculated Hirshfeld surfaces, and the calculated electrostatic potentials differentiate the tautomers.
In the mol-ecule of the title compound, C21H17N3O2, the 5,6-di-hydro-benzimidazo[1,2-c]quinazoline moiety is disordered over two orientations about a pseudo-mirror plane, with a refined occupancy ratio of 0.863 (2):0.137 (2). The dihedral angles formed by the benzimidazole ring system and the benzene ring of the quinazoline group are 14.28 (5) and 4.7 (3)° for the major and minor disorder components, respectively. An intra-molecular O-H⋯O hydrogen bond is present. In the crystal, mol-ecules are linked by O-H⋯N hydrogen bonds, forming chains running parallel to [10-1].