Ring Motif Research Articles

Crystal structure of (μ2-7-{[bis(pyridin-2-ylmethyl)amino-1κ3 N,N′,N′′]methyl}-5-chloroquinolin-8-olato-2κN;1:2κ2 O)trichlorido-1κCl,2κ2 Cl-dizinc(II)

The title compound, [Zn2(C22H18ClN4O)Cl3], is a dinuclear zinc(II) complex with three chlorido ligands and one pentadentate ligand containing quinolin-8-olato and bis(pyridin-2-ylmethyl)amine groups. One of the two ZnII atom adopts a tetrahedral geometry and coordinates two chlorido ligands with chelate coordination of the N and O atoms of the quinolin-8-olato group in the ligand. The other ZnII atom adopts a distorted trigonal–bipyramidal geometry, and coordinates one chlorido-O atom of the quinolin-8-olato group and three N atoms of the bis(pyridin-2-ylmethyl)amine unit. In the crystal, two molecules are associated through a pair of intermolecular C—H...Cl hydrogen bonds, forming a dimer with an R 2 2(12) ring motif. Another intermolecular C—H...Cl hydrogen bond forms a spiral C(8) chain running parallel to the [010] direction. The dimers are linked by these two intermolecular C—H...Cl hydrogen bonds, generating a ribbon sheet structure in ac plane. Two other intermolecular C—H...Cl hydrogen bonds form a C(7) chain along the c-axis direction and another C(7) chain generated by a d-glide plane. The molecules are cross-linked through the four intermolecular C—H...Cl hydrogen bonds to form a three-dimensional network.

The crystal structures determination and Hirshfeld surface analysis of N-(4-bromo-3-methoxyphenyl)- and N-{[3-bromo-1-(phenylsulfonyl)-1H-indol-2-yl]methyl}- derivatives of N-{[3-bromo-1-(phenylsulfonyl)-1H-indol-2-yl]methyl}benzenesulfonamide

Two new phenylsulfonylindole derivatives, namely, N-{[3-bromo-1-(phenylsulfonyl)-1H-indol-2-yl]methyl}-N-(4-bromo-3-methoxyphenyl)benzenesulfonamide, C28H22Br2N2O5S2, (I), and N,N-bis{[3-bromo-1-(phenylsulfonyl)-1H-indol-2-yl]methyl}benzenesulfonamide, C36H27Br2N3O6S3, (II), reveal the impact of intramolecular π–π interactions of the indole moieties as a factor not only governing the conformation of N,N-bis(1H-indol-2-yl)methyl)amines, but also significantly influencing the crystal patterns. For I, the crystal packing is dominated by C—H...π and π–π bonding, with a particular significance of mutual indole–indole interactions. In the case of II, the molecules adopt short intramolecular π–π interactions between two nearly parallel indole ring systems [with the centroids of their pyrrole rings separated by 3.267 (2) Å] accompanied by a set of forced Br...O contacts. This provides suppression of similar interactions between the molecules, while the importance of weak C—H...O hydrogen bonding to the packing naturally increases. Short contacts of the latter type [C...O = 3.389 (6) Å] assemble pairs of molecules into centrosymmetric dimers with a cyclic R 2 2(13) ring motif. These findings are consistent with the results of a Hirshfeld surface analysis and together they suggest a tool for modulating the supramolecular behavior of phenylsulfonylated indoles.

Structural insights into supramolecular interactions in isostructural salts of 2,4,6-triaminopyrimidinium with various heterocyclic carboxylates.

2,4,6-Triaminopyrimidine is an interesting and challenging molecule due to the presence of multiple hydrogen-bond donors and acceptors. Its noncovalent interactions with a variety of carboxylic acids provide several supramolecular aggregates with frequently occurring molecular synthons. The present work focuses on the supramolecular interactions of 2,4,6-triaminopyrimidinium 3-(indol-3-yl)propionate-3-(indol-3-yl)propionic acid (1/1), C4H8N5+·C11H10NO2-·C11H11NO2, (I), 2,4,6-triaminopyrimidinium 2-(indol-3-yl)acetate, C4H8N5+·C10H8NO2-, (II), 2,4,6-triaminopyrimidinium 5-bromothiophene-2-carboxylate, C4H8N5+·C5H2BrO2S-, (III), and 2,4,6-triaminopyrimidinium 5-chlorothiophene-2-carboxylate, C4H8N5+·C5H2ClO2S-, (IV). All four salts exhibit robust homomeric and heteromeric R22(8) ring motifs. Salts (I) and (II) develop sextuple [in (I)] and quadruple [in (I) and (II)] hydrogen-bonded arrays through fused-ring motifs. Salt (II) exhibits a rosette-like architecture. Salt (IV) is isostructural and isomorphous with salt (III), exhibiting an identical crystal structure with a different composition and an identical supramolecular architecture. In salts (III) and (IV), a linear hetero-tetrameric motif is formed and, in addition, both salts exhibit halogen-π interactions which enhance the crystal stability. All four salts develop a supramolecular hydrogen-bonded pattern facilitated by several N-H...O and N-H...N hydrogen bonds with multiple furcated donors and acceptors.

Direct Estimation of Aromatization Energy from 1H NMR and UV-Vis Absorption Data of Homodesmotic Molecules.

This study delves into the ring-opening reaction of two distinct diaryl-ring-pyran systems, referred to as drnp1 and drnp2, where the term 'ring' encompasses aromatic, nonaromatic, or antiaromatic motifs. These systems transform into the corresponding cis-ortho quinonoid systems, denoted as c-drnq1 and c-drnq2. Homodesmotic pairs (drnp1, drnp2) and (c-drnq1, c-drnq2) are categorized as (aromatic, nonaromatic), (aromatic, partially aromatic), (antiaromatic, nonaromatic), and (nonaromatic, nonaromatic), with their energy difference representing aromatization energy (Earoma). Using reliable density functional theory, Earoma is assessed for various aromatic and antiaromatic ring motifs, including borderline cases and nonaromatic structures. For example, benzene exhibits an Earoma of 23.4 kcal/mol, indicating 3.9 kcal/mol aromatic stabilization per CC bond, while cyclobutadiene shows -29.9 kcal/mol, indicating a 7.5 kcal/mol destabilization of the CC bond. This approach extends to evaluating global and local aromatic stabilization effects in polycyclic hydrocarbons, nonbenzenoid systems, and heterocyclic compounds. Additionally, variation in 1H NMR chemical shift (δavg) correlates with Earoma, suggesting that a -1.0 ppm shift corresponds to 24.2 kcal/mol aromatization energy. UV-vis absorption maxima difference (Δλavg) correlates linearly with Earoma, enabling direct assessment of aromatization energy from UV-vis spectra using suitable homodesmotic pairs. This comprehensive approach enhances our understanding of structural, energetic, and spectroscopic aspects of aromatic and antiaromatic systems.

New polymorph of N-benzoyl-morpholine-4-carbothioamide with ten crystallographically independent molecules in the asymmetric unit: Crystal structure, Hirshfeld surface analysis and Density functional theory calculations

Herein, facile synthesis, single crystal X-ray diffraction (SC-XRD) structure, Hirshfeld surface (HS) analysis and Density functional theory (DFT) calculations of N-benzoyl-morpholine-4-carbothioamide 5(a) are presented. Hence, the synthesized compound, C12H14N2O2S 5(a), crystallizes in monoclinic crystal system having space group of P 21 with a = 22.2226 (9) Å, b = 11.7520 (3) Å, c = 24.9361 (8) Å, α = 90°, β = 111.054 (4)°, γ = 90°, Z = 20 and V = 6077.6 (4) Å3. The asymmetric unit of 5(a) contains ten crystallographically independent molecules, where the morpholine and benzene rings are in respective chair and planar conformations. In the crystal structure, some of the intermolecular, N—H···O, C—H···O and C—H···S, hydrogen bonds link the molecules into a 2D-network parallel to (010), enclosing R22(10) and R22(24) ring motifs, when viewed down the b-axis direction. Furthermore, contribution of the remaining hydrogen bonds consolidates a 3D-architecture. Similarly, HS analysis clarified the importance of hydrogen atom contacts with the major contributions of H…H (46.7 %), H…S/S…H (21.1 %), H…C/C…H (16.5 %), and H…O/O…H (12.5 %). Thus, hydrogen bond and van der Waals interactions play major role in the crystal packing. Finally, optimum molecular structure of compound 5(a) was related to the experimentally determined one employing DFT at B3LYP/6–311++G(d,p) level. Subsequently, the geometry of the optimized and most stable conformation turned out to be complementary with the crystal structure. The computational calculation of compound 5(a) revealed the molecule to be chemically hard in nature with high energy intrinsic reaction pathway. The associated band gap predicted compound 5(a) to be a wide band gap material. The intrinsic reaction pathway predicts hard-core behavior of the molecule.

Methyl 2-[(Z)-5-bromo-2-oxoindolin-3-yl-idene]-hydrazinecarbodi-thio-ate.

The title compound, C10H8BrN3OS2, a brominated di-thio-carbazate imine deriv-ative, was obtained from the condensation reaction of S-methyl-dithio-carbazate (SMDTC) and 5-bromo-isatin. The essentially planar mol-ecule exhibits a Z configuration, with the di-thio-carbazate and 5-bromo-isatin fragments located on the same sides of the C=N azomethine bond, which allows for the formation of an intra-molecular N-H⋯Ob (b = bromo-isatin) hydrogen bond generating an S(6) ring motif. In the crystal, adjacent mol-ecules are linked by pairs of N-H⋯O hydrogen bonds, forming dimers characterized by an R 2 2(8) loop motif. In the extended structure, mol-ecules are linked into a three-dimensional network by C-H⋯S and C-H⋯Br hydrogen bonds, C-Br⋯S halogen bonds and aromatic π-π stacking.

Visible-Light-Mediated [2+2] Photocycloadditions of Alkynes.

Visible-light-mediated [2+2] photocycloaddition reaction can be considered an ideal solution due to its green and sustainable properties, and is one of the most efficient methods to synthesize four-membered ring motifs. Although research on the [2+2] photocycloaddition of alkynes is challenging because of the diminished reactivity of alkynes, and the more significant ring strain of the products, remarkable achievements have been made in this field. In this article, we highlight the recent advances in visible-light-mediated [2+2] photocycloaddition reactions of alkynes, with focus on the reaction mechanism and the late-stage synthetic applications. Advances in obtaining cyclobutenes, azetines, and oxetene active intermediates continue to be breakthroughs in this fascinating field of research.

Synthesis and structural investigation of salts of 2-amino-3-methylpyridine with carboxylic acid derivatives: an experimental and theoretical study.

The salts bis(2-amino-3-methylpyridinium) fumarate dihydrate, 2C6H9N2+·C4H2O22-·2H2O (I), and 2-amino-3-methylpyridinium 5-chlorosalicylate, C6H9N2+·C7H4ClO3- (II), were synthesized from 2-amino-3-methylpyridine with fumaric acid and 5-chlorosalicylic acid, respectively. The crystal structures of these salts were characterized by single-crystal X-ray diffraction, revealing protonation in I and II by the transfer of a H atom from the acid to the pyridine base. In the crystals of both I and II, N-H...O interactions form an R22(8) ring motif. Hirshfeld surface analysis distinguishes the interactions present in the crystal structures of I and II, and the two-dimensional (2D) fingerprint plot analysis shows the percentage contribution of each type of interaction in the crystal packing. The volumes of the crystal voids of I (39.65 Å3) and II (118.10 Å3) have been calculated and reveal that the crystal of I is more mechanically stable than II. Frontier molecular orbital (FMO) analysis predicts that the band gap energy of II (2.6577 eV) is lower compared to I (4.0035 eV). The Quantum Theory of Atoms In Molecules (QTAIM) analysis shows that the pyridinium-carboxylate N-H...O interaction present in I is stronger than the other interactions, whereas in II, the hydroxy-carboxylate O-H...O interaction is stronger than the pyridinium-carboxylate N-H...O interaction; the bond dissociation energies also confirm these results. The positive Laplacian [∇2ρ(r) > 0] of these interactions shows that the interactions are of the closed shell type. An in-silico ADME (Absorption, Distribution, Metabolism and Excretion) study predicts that both salts will exhibit good pharmacokinetic properties and druglikeness.

Crystal structure and Hirshfeld surface analysis of 6,6'-dimethyl-2,2'-bi-pyridine-1,1'-diium tetra-chlorido-cobaltate(II).

In the title mol-ecular salt, (C12H14N2)[CoCl4], the dihedral angle between the pyridine rings of the cation is 52.46 (9)° and the N-C-C-N torsion angle is -128.78 (14)°, indicating that the ring nitro-gen atoms are in anti-clinal conformation. The Cl-Co-Cl bond angles in the anion span the range 105.46 (3)-117.91 (2)°. In the extended structure, the cations and anions are linked by cation-to-anion N-H⋯Cl and C-H⋯Cl inter-actions, facilitating the formation of R 4 4(18) and R 4 4(20) ring motifs. Furthermore, the crystal structure features weak anion-to-cation Cl⋯π inter-actions [Cl⋯π = 3.4891 (12) and 3.5465 (12) Å]. Hirshfeld two-dimensional fingerprint plots revealed that the most significant inter-actions are Cl⋯H/H⋯Cl (45.5%), H⋯H (29.0%), Cl⋯C/C⋯Cl (7.8%), Cl⋯N/N⋯Cl (3.5%), Cl⋯Cl (1.4) and Co⋯H (1%) contacts.

Chlorido(2-{(2-hydroxyethyl)[tris(hydroxymethyl)methyl]amino}ethanolato-κ5 N,O,O′,O′′,O′′′)copper(II)

The title complex, [Cu(C8H18NO5)Cl] or [Cu(H4bis-tris)Cl], was obtained starting from the previously reported [Cu(H5bis-tris)Cl]Cl compound. The deprotonation of the aminopolyol ligand H5bis-tris {[bis(2-hydroxyethyl)amino]tris(hydroxymethyl)methane, C8H19NO5} promotes the formation of a very strong O—H...O intermolecular hydrogen bond, characterized by an H...O separation of 1.553 (19) Å and an O—H...O angle of 178 (4)°. The remaining hydroxy groups are also engaged in hydrogen bonds, forming R 2 2(8), R 4 4(16), R 4 4(20) and R 4 4(22) ring motifs, which stabilize the triperiodic supramolecular network.

Extension and Fusion of Cyclic Polyantimony Units.

The synthesis and characterization of a series of polyantimony anionic clusters are reported. The products [(NbCp)2Sb10]2-, [MSb13]3- (M = Ru/Fe), and [MSb15]3- (M = Ru/Fe) were isolated as either K(18-crown-6) or K([2.2.2]-crypt) salts. The Sb10 ring contained in the [(NbCp)2Sb10]2- cluster can be viewed as an extension of two envelope-like cyclo-Sb5 units and represents by far the largest monocyclic all-antimony species. The clusters [MSb13]3- and [MSb15]3- (M = Ru/Fe) illustrate the variability of crown-like Sb8 ring motifs and reveal the fusion of different antimony fragments featuring unique Sb-Sb chain-like units. The reported synthetic approaches involve the fabrication of a variety of distinctive polyantimony anionic clusters, enhancing our understanding of the coordination chemistry of heavier group 15 elements.

Crystal structure and Hirshfeld surface analysis of 3,3′-[ethane-1,2-diylbis(oxy)]bis(5,5-dimethylcyclohex-2-en-1-one) including an unknown solvate

The title molecule, C18H26O4, consists of two symmetrical halves related by the inversion centre at the mid-point of the central –C—C– bond. The hexene ring adopts an envelope conformation. In the crystal, the molecules are connected into dimers by C—H...O hydrogen bonds with R 2 2(8) ring motifs, forming zigzag ribbons along the b-axis direction. According to a Hirshfeld surface analysis, H...H (68.2%) and O...H/H...O (25.9%) interactions are the most significant contributors to the crystal packing. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9–18] in PLATON. The solvent contribution was not included in the reported molecular weight and density.

Crystal structure and Hirshfeld surface analysis of (Z)-4-oxo-4-{phenyl[(thiophen-2-yl)methyl]amino}but-2-enoic acid

In the title compound, C15H13NO3S, the molecular conformation is stable with the intramolecular O—H...O hydrogen bond forming a S(7) ring motif. In the crystal, molecules are connected by C—H...O hydrogen bonds, forming C(8) chains running along the a-axis direction. Cohesion of the packing is provided by weak van der Waals interactions between the chains. A Hirshfeld surface analysis was undertaken to investigate and quantify the intermolecular interactions. The thiophene ring is disordered in a 0.9466 (17):0.0534 (17) ratio over two positions rotated by 180°.

Trans-Dichloridobis(secnidazole-κN 3)copper(II)

The use of acetic acid (HOAc) in a reaction between CuCl2·2H2O and secnidazole, an active pharmaceutical ingredient useful in the treatment against a variety of anaerobic Gram-positive and Gram-negative bacteria, affords the title complex, [CuCl2(C7H11N3O3)2]. This compound was previously synthesized using ethanol as solvent, although its crystal structure was not reported [Betanzos-Lara et al. (2013). Inorg. Chim. Acta, 397, 94–100]. In the molecular complex, the Cu2+ cation is situated at an inversion centre and displays a square-planar coordination environment. There is a hydrogen-bonded framework based on intermolecular O—H...Cl interactions, characterized by H...Cl separations of 2.28 (4) Å and O—H...Cl angles of 175 (3)°. The resulting supramolecular network is based on R2 2 (18) ring motifs, forming chains in the [010] direction.

Synthesis, crystal structure and Hirshfeld surface analysis of 4-{(1E)-1-[(car-bamo-thioyl-amino)-imino]-eth-yl}phenyl propano-ate.

The title compound, C12H15N3O2S, adopts an E configuration with respect to the C=N bond. The propionate group adopts an anti-periplanar (ap) conformation. There are short intra-molecular N-H⋯N and C-H⋯O contacts, forming S(5) and S(6) ring motifs, respectively. In the crystal, mol-ecules are connected into ribbons extending parallel to [010] by pairs of N-H⋯S inter-actions, forming rings with R 2 2(8) graph-set motifs, and by pairs of C-H⋯S inter-actions, where rings with the graph-set motif R 2 1(7) are observed. The O atom of the carbonyl group is disordered over two positions, with a refined occupancy ratio of 0.27 (2):0.73 (2). The studied crystal consisted of two domains.

Crystal structure and Hirshfeld surface analysis of dimethyl 4'-bromo-3-oxo-5-(thio-phen-2-yl)-3,4,5,6-tetra-hydro-[1,1'-biphen-yl]-2,4-di-carboxyl-ate.

In the title compound, C20H17BrO5S, mol-ecules are connected by inter-molecular C-H⋯S hydrogen bonds with R 2 2(10) ring motifs, forming ribbons along the b-axis direction. C-H⋯π inter-actions consolidate the ribbon structure while van der Waals forces between the ribbons ensure the cohesion of the crystal structure. According to a Hirshfeld surface analysis, H⋯H (40.5%), O⋯H/H⋯O (27.0%), C⋯H/H⋯C (13.9%) and Br⋯H/H⋯Br (11.7%) inter-actions are the most significant contributors to the crystal packing. The thio-phene ring and its adjacent di-carboxyl-ate group and the three adjacent carbon atoms of the central hexene ring to which they are attached were refined as disordered over two sets of sites having occupancies of 0.8378 (15) and 0.1622 (15). The thio-phene group is disordered by a rotation of 180° around one bond.

Structure directing interactions in the crystals of o-hydroxyaryl/naphthyl derived aldimines: X-ray structure, Hirshfeld surface analysis, DFT and Molecular docking studies

We have synthesized and thoroughly analyzed many intermolecular interactions present in (E)-1-(((3-nitrophenyl)amino)methylene)naphthalen-2(1H)-one (a), (E)-5-(diethylamino)-2-(((3-nitrophenyl)imino)methyl)phenol(b) and (E)-2-(((3-nitrophenyl)imino)methyl)phenol (c). Compounds a (keto-amine tautomeric form) and b, which have one molecule in the asymmetric unit, crystallize in the monoclinic crystal system with space groups P21/n and C2/c, respectively. Compound C, on the other hand, crystallizes in an orthorhombic crystal structure with the space group Pca21. The structural analysis showed that the construction of ring motifs to stabilize the crystal packing involves several interactions, including pi stacking interactions, NH…O, and CH…O interactions. Hirshfeld surface analysis has been used to examine their solid-state structures, including the evaluation of several energy frameworks. The results show that hydrogen bonds play a major role in the formation of the molecular sheets, and that electrostatic energy contribution dominates stability. Using fingerprint plots, it was possible to examine the variations and commonalities in the target compounds' relative contributions from noncovalent interactions. In addition, B3LYP hybrid functional with 6- 311 G (d, p) level basis set was used in the density functional theory computations to optimize the structural coordinates. Through the examination of the molecular electrostatic potential surface, the chemically active areas of the target imine molecules were located. Additionally, using the internal ribosome entry site of the Hepatitis C virus ED42 (PDB-ID 3T4B), molecular docking of the title compounds was performed based on PASS analysis and literature findings.

Crystal structure, intermolecular interactions, charge-density distribution and ADME properties of the acridinium 4-nitrobenzoate and 2-amino-3-methylpyridinium 4-nitrobenzoate salts: a combined experimental and theoretical study.

Acridines are a class of bioactive agents which exhibit high biological stability and the ability to intercalate with DNA; they have a wide range of applications. Pyridine derivatives have a wide range of biological activities. To enhance the properties of acridine and 2-amino-3-methylpyridine as the active pharmaceutical ingredient (API), 4-nitrobenzoic acid was chosen as a coformer. In the present study, a mixture of acridine and 4-nitrobenzoic acid forms the salt acridinium 4-nitrobenzoate, C13H10N+·C7H4NO4- (I), whereas a mixture of 2-amino-3-methylpyridine and 4-nitrobenzoic acid forms the salt 2-amino-3-methylpyridinium 4-nitrobenzoate, C6H9N2+·C7H4NO4- (II). In both salts, protonation takes place at the ring N atom. The crystal structure of both salts is predominantly governed by hydrogen-bond interactions. In salt I, C-H...O and N-H...O interactions form an infinite chain in the crystal, whereas in salt II, intermolecular N-H...O interactions form an eight-membered R22(8) ring motif. A theoretical charge-density analysis reveals the charge-density distribution of the inter- and intramolecular interactions of both salts. An in-silico ADME analysis predicts the druglikeness properties of both salts and the results confirm that both salts are potential drug candidates with good bioavailability scores and there is no violation of the Lipinski rules, which supports the druglikeness properties of both salts. However, although both salts exhibit drug-like properties, salt I has higher gastrointestinal absorption than salt II and hence it may be considered a potential drug candidate.

Crystal structure, hydrogen bonding interactions, Hirshfeld surfaces, energy frameworks, and DFT calculation of Diethyl 3-(4-substitutedbenzoyl)indolizine-1,2-dicarboxylates

The diethyl 3-(4-substitutedbenzoyl)indolizine-1,2-dicarboxylates have been synthesized by reacting the electron-deficient diethyl but-2-ynedioate with 1-(2-(4-substitutedphenyl)-2-oxoethyl)pyridin-1-ium bromide, the intermediates obtained from the reaction of pyridine and 4-substituted phenacyl bromides. The synthesized compounds were investigated by FT-IR, NMR (1H and 13C), LC-MS, and elemental analysis spectroscopic methods along with PXRD. The molecular structures were determined using the single crystal X-ray diffraction technique which revealed that 5a and 5c crystallize in triclinic space group P1¯. The crystal structures of 5a and 5c preferred the C-H···O hydrogen-bonded dimeric ring motifs, resembling those observed in the earlier reported 5b. Furthermore, various computational analyzes such as Hirshfeld surface, Energy framework, and MEP analysis predicted the interaction site and inter-molecular interactions in these molecules. The FMOs analysis was carried out to obtain global reactivity parameters for the synthesized compounds (5a-c). The NCI and QTAIM studies revealed the nature as well as qualitative and quantitative description of intra and inter-molecular hydrogen bonding interactions present in these molecules and their crystal packing.

N-Benzoyl-morpholine-4-carbothioamides: Crystal structures, Hirshfeld surface analysis, and Density functional theory calculations

The current research work describes facile synthesis, single crystal X-ray structures, Hirshfeld surface (HS) analysis, and density functional theory (DFT) calculations of two N-benzoyl-morpholine-4-carbothioamides (NDMC and NMMC). Consequently, the synthesized compounds, C12H12Cl2N2O2S (NDMC) and C13H16N2O2S (NMMC) crystallized in triclinic and monoclinic crystal systems each having respective space groups of P -1 and P 21, with corresponding a = 7.8045 (3) Å, b = 12.8458 (6) Å, c = 13.4946 (7) Å, α = 97.313 (4)°, β = 94.358 (4)°, γ = 93.348 (3)°, Z = 4 and V = 1334.84 (11) Å3 for compound (NDMC). Similarly, for compound (NMMC),a = 7.3322 (2) Å, b = 5.3045 (1) Å, c = 16.3367 (5) Å, α = 90°, β = 94.285 (3)°, γ = 90°, Z = 2 and V = 633.62 (3) Å3. Subsequently, the asymmetric unit of compound (NDMC) contains two molecules, while compound (NMMC) has single molecule. Strong intermolecular NH⋯O, and weaker CH⋯Cl and CH⋯S hydrogen bonds link the molecules of (NDMC) into dimers, enclosing R22(7) and R22(9) ring motifs. Intermolecular CH⋯S, bifurcated NH⋯O and CH⋯O hydrogen bonds, as well as CH⋯π interactions in (NMMC), attach molecules, enclosing R22(7) and R22(14) ring motifs. Furthermore, HS analysis explored, visualized, and quantified the significance of hydrogen bond contacts, and revealed active contributions for the packed crystals encompasses H…H 33.6 % for (NDMC), and 46.6 % for (NMMC), H…S/S…H 17.9 % for (NDMC), and 17.0 % for (NMMC), H…C/C…H 9.0 % for (NDMC), and 19.7 % for (NMMC), H…O/O…H 14.8 % for (NDMC), and 14.3 % for (NMMC), and H…Cl/Cl…H 17.8 % for (NMMC). Hydrogen bonding and van der Waals contacts strongly influence crystal packings of the crystallized compounds. Similarly, evaluation of energy frameworks (electrostatic, dispersion and total energies) indicated stabilization is strongly dominated by dispersion energy contribution in compound (NMMC). Finally, optimum molecular structures of both the compounds (NDMC and NMMC), were related with the experimental ones employing DFT at B3LYP/6–311G**(d,p) level. The most stable optimized conformation was geometrically complementary with the crystal structure. DFT computed frontier molecular energies and isodensities predicted these compounds to exhibit better electron pair acceptance nature than electron pair donor.