scholarly journals Crystal structure, Hirshfeld surface analysis and computational study of the 1:2 co-crystal formed between N,N′-bis(pyridin-4-ylmethyl)ethanediamide and 4-chlorobenzoic acid

2020 ◽  
Vol 76 (2) ◽  
pp. 245-253 ◽  
Author(s):  
Sang Loon Tan ◽  
Edward R. T. Tiekink
Keyword(s):  
Hydrogen Bonding ◽  
Computational Study ◽  
Three Dimensional ◽  
Dihedral Angles ◽  
Interaction Energies ◽  
Carbonyl Groups ◽  
Amide Hydrogen ◽  
Title 1 ◽  
Chlorobenzoic Acid ◽  
Hirshfeld Surfaces

The asymmetric unit of the title 1:2 co-crystal, C14H14N4O2·2C7H5ClO2, comprises two half molecules of oxalamide (4 LH2), as each is disposed about a centre of inversion, and two molecules of 4-chlorobenzoic acid (CBA), each in general positions. Each 4 LH2 molecule has a (+)antiperiplanar conformation with the pyridin-4-yl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angles between the respective central core and the pyridyl rings being 68.65 (3) and 86.25 (3)°, respectively, representing the major difference between the independent 4 LH2 molecules. The anti conformation of the carbonyl groups enables the formation of intramolecular amide-N—H...O(amide) hydrogen bonds, each completing an S(5) loop. The two independent CBA molecules are similar and exhibit C6/CO2 dihedral angles of 8.06 (10) and 17.24 (8)°, indicating twisted conformations. In the crystal, two independent, three-molecule aggregates are formed via carboxylic acid-O—H...N(pyridyl) hydrogen bonding. These are connected into a supramolecular tape propagating parallel to [100] through amide-N—H...O(amide) hydrogen bonding between the independent aggregates and ten-membered {...HNC2O}2 synthons. The tapes assemble into a three-dimensional architecture through pyridyl- and methylene-C—H...O(carbonyl) and CBA-C—H...O(amide) interactions. As revealed by a more detailed analysis of the molecular packing by calculating the Hirshfeld surfaces and computational chemistry, are the presence of attractive and dispersive Cl...C=O interactions which provide interaction energies approximately one-quarter of those provided by the amide-N—H...O(amide) hydrogen bonding sustaining the supramolecular tape.

scholarly journals The 1:2 co-crystal formed between N,N′-bis(pyridin-4-ylmethyl)ethanediamide and benzoic acid: crystal structure, Hirshfeld surface analysis and computational study

2020 ◽  
Vol 76 (1) ◽  
pp. 102-110 ◽  
Author(s):  
Sang Loon Tan ◽  
Edward R. T. Tiekink
Keyword(s):  
Hydrogen Bonds ◽  
Benzoic Acid ◽  
Computational Study ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Molecular Structures ◽  
Amide Hydrogen ◽  
Title 1 ◽  
Crystal And Molecular Structures ◽  
Hirshfeld Surfaces

The crystal and molecular structures of the title 1:2 co-crystal, C14H14N4O2·2C7H6O2, are described. The oxalamide molecule has a (+)-antiperiplanar conformation with the 4-pyridyl residues lying to either side of the central, almost planar C2N2O2 chromophore (r.m.s. deviation = 0.0555 Å). The benzoic acid molecules have equivalent, close to planar conformations [C6/CO2 dihedral angle = 6.33 (14) and 3.43 (10)°]. The formation of hydroxy-O—H...N(pyridyl) hydrogen bonds between the benzoic acid molecules and the pyridyl residues of the diamide leads to a three-molecule aggregate. Centrosymmetrically related aggregates assemble into a six-molecule aggregate via amide-N—H...O(amide) hydrogen bonds through a 10-membered {...HNC2O}2 synthon. These are linked into a supramolecular tape via amide-N—H...O(carbonyl) hydrogen bonds and 22-membered {...HOCO...NC4NH}2 synthons. The contacts between tapes to consolidate the three-dimensional architecture are of the type methylene-C—H...O(amide) and pyridyl-C—H...O(carbonyl). These interactions are largely electrostatic in nature. Additional non-covalent contacts are identified from an analysis of the calculated Hirshfeld surfaces.

scholarly journals Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate

2019 ◽  
Vol 75 (5) ◽  
pp. 565-570
Author(s):  
Abdullah M. Asiri ◽  
Khalid A. H. Alzahrani ◽  
Hassan M. Faidallah ◽  
Khalid A. Alamry ◽  
Mukesh M. Jotani ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Organic Molecules ◽  
Three Dimensional ◽  
Phenyl Group ◽  
Hirshfeld Surface ◽  
Neutral Molecule ◽  
Dihedral Angles ◽  
Central Ring ◽  
Hirshfeld Surfaces ◽  
Water Hydrogen

The title compound, 2C14H14N4O·H2O, comprises a neutral molecule 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 molecule of crystallization. Besides systematic variations in geometric parameters, the two independent organic molecules have broadly similar conformations, as seen in the dihedral angle between the five-membered rings [9.72 (9)° for the neutral molecule 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 molecule); 11.33 (9) and 11.81 (9)°]. In the crystal, pyrazolyl-N—H...O(carbonyl) and pyrazolium-N—H...N(pyrazolyl) hydrogen bonds between the independent organic molecules 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 supramolecular layer in the bc plane by water-O—H...N(pyrazolide), water-O—H...O(carbonyl) and pyrazolyl-N—H...O(water) hydrogen bonding. The layers are linked into a three-dimensional architecture by methyl-C—H...π(phenyl) interactions. The different interactions, in particular the weaker contacts, formed by the organic molecules are clearly evident in the calculated Hirshfeld surfaces, and the calculated electrostatic potentials differentiate the tautomers.

scholarly journals Bis{N′-[3-(4-nitrophenyl)-1-phenylprop-2-en-1-ylidene]-N-phenylcarbamimidothioato}zinc(II): crystal structure, Hirshfeld surface analysis and computational study

2021 ◽  
Vol 77 (8) ◽  
pp. 839-846
Author(s):  
Ming Yueh Tan ◽  
Huey Chong Kwong ◽  
Karen A. Crouse ◽  
Thahira B. S. A. Ravoof ◽  
Edward R. T. Tiekink
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Dihedral Angle ◽  
Chelate Ring ◽  
Computational Study ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Dihedral Angles ◽  
Screw Axis ◽  
Ethylene Bond

The title zinc bis(thiosemicarbazone) complex, [Zn(C22H17N4O2S)2], comprises two N,S-donor anions, leading to a distorted tetrahedral 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 ethylene bond is E. The major differences in the conformations of the ligands are seen in the dihedral angles between the chelate ring and nitrobenzene rings [40.48 (6) cf. 13.18 (4)°] and the N-bound phenyl and nitrobenzene ring [43.23 (8) and 22.64 (4)°]. In the crystal, a linear supramolecular 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(phenyl) contacts. The double chains are linked into a three-dimensional architecture through phenyl-C—H...O(nitro) and nitro-O...π(phenyl) interactions.

scholarly journals A 1:2 co-crystal of 2,2′-thiodibenzoic acid and triphenylphosphane oxide: crystal structure, Hirshfeld surface analysis and computational study

2018 ◽  
Vol 74 (12) ◽  
pp. 1764-1771 ◽  
Author(s):  
Sang Loon Tan ◽  
Edward R. T. Tiekink
Keyword(s):  
Hydrogen Bonds ◽  
Conformational Changes ◽  
Disulfide Bonds ◽  
Computational Study ◽  
Three Dimensional ◽  
Dihedral Angles ◽  
Asymmetric Unit ◽  
Hirshfeld Surfaces ◽  
Oxide Crystal ◽  
Phenyl Rings

The asymmetric unit of the title co-crystal, 2,2′-thiodibenzoic acid–triphenylphosphane oxide (1/2), C14H10O4S·2C18H15OP, comprises two molecules of 2,2′-thiodibenzoic acid [TDBA; systematic name: 2-[(2-carboxyphenyl)sulfanyl]benzoic acid] and four molecules of triphenylphosphane oxide [TPPO; systematic name: (diphenylphosphoryl)benzene]. The two TDBA molecules are twisted about their disulfide bonds and exhibit dihedral angles of 74.40 (5) and 72.58 (5)° between the planes through the two SC6H4 residues. The carboxylic acid groups are tilted out of the planes of the rings to which they are attached forming a range of CO2/C6 dihedral angles of 19.87 (6)–60.43 (8)°. Minor conformational changes are exhibited in the TPPO molecules with the range of dihedral angles between phenyl rings being −2.1 (1) to −62.8 (1)°. In the molecular packing, each TDBA acid molecule bridges two TPPO molecules via hydroxy-O—H...O(oxide) hydrogen bonds to form two three-molecule aggregates. These are connected into a three-dimensional architecture by TPPO-C—H...O(oxide, carbonyl) and TDBA-C—H...(oxide, carbonyl) interactions. The importance of H...H, O...H/H...O and C...H/H...C contacts to the calculated Hirshfeld surfaces has been demonstrated. In terms of individual molecules, O...H/H...O contacts are more important for the TDBA (ca 28%) than for the TPPO molecules (ca 13%), as expected from the chemical composition of these species. Computational chemistry indicates the four independent hydroxy-O—H...O(oxide) hydrogen bonds in the crystal impart about the same energy (ca 52 kJ mol−1), with DTBA-phenyl-C—H...O(oxide) interactions being next most stabilizing (ca 40 kJ mol−1).

scholarly journals 2,2′-(Disulfanediyl)dibenzoic acid N,N-dimethylformamide monosolvate: crystal structure, Hirshfeld surface analysis and computational study

2020 ◽  
Vol 76 (7) ◽  
pp. 1150-1157
Author(s):  
Sang Loon Tan ◽  
Edward R. T. Tiekink
Keyword(s):  
Benzene Ring ◽  
Computational Study ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Title 1 ◽  
Torsion Angles ◽  
Carboxylic Acid Groups ◽  
Hirshfeld Surfaces ◽  
Intermolecular Contacts ◽  
Benzene Rings

The title 1:1 solvate, C14H10O4S2·C3H7NO, features a twisted molecule of 2,2′-dithiodibenzoic acid (DTBA), with the central C—S—S—C torsion angle being −88.57 (6)°, and a molecule of dimethylformamide (DMF). The carboxylic acid groups are, respectively, close to co-planar and twisted with respect to the benzene rings to which they are connected as seen in the CO2/C6 torsion angles of 1.03 (19) and 7.4 (2)°. Intramolecular, hypervalent S←O interactions are noted [S...O = 2.6140 (9) and 2.6827 (9) Å]. In the crystal, four-molecule aggregates are formed via DTBA-O—H...O(DMF) and DTBA-O—H...O(DTBA) hydrogen bonding, the latter via an eight-membered {...OHCO}2 homosynthon. These are linked into supramolecular layers parallel to (011) via benzene-C—H...O(DTBA) and DTBA-C=O...π(benzene) interactions, with the connections between these, giving rise to a three-dimensional architecture, being of the type benzene-C—H...π(benzene). An analysis of the calculated Hirshfeld surfaces indicates, in addition to the aforementioned intermolecular contacts, the presence of stabilizing interactions between a benzene ring and a quasi-π-system defined by O—H...O hydrogen bonds between a DTBA dimer, i.e. the eight-membered {...OCOH}2 ring system, and between a benzene ring and a quasi-π(OCOH...OCH) system arising from the DTBA-O—H...O(DMF) hydrogen bond. The inter-centroid separations are 3.65 and 3.49 Å, respectively.

scholarly journals Crystal structure, Hirshfeld surface analysis and computational study of the 1:2 co-crystal formed between N,N′-bis[(pyridin-4-yl)methyl]ethanediamide and 3-chlorobenzoic acid

2020 ◽  
Vol 76 (6) ◽  
pp. 870-876
Author(s):  
Sang Loon Tan ◽  
Edward R. T. Tiekink
Keyword(s):  
Hydrogen Bonding ◽  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Dihedral Angle ◽  
Computational Study ◽  
Three Dimensional ◽  
Molecular Packing ◽  
Hirshfeld Surface ◽  
Pyridyl Ring ◽  
Chlorobenzoic Acid

The asymmetric unit of the title 1:2 co-crystal, C14H14N4O2·2C7H5ClO2, comprises a half-molecule of oxalamide (4 LH2), being located about a centre of inversion, and a molecule of3-chlorobenzoic acid (3-ClBA) in a general position. From symmetry, the 4 LH2 molecule has a (+)antiperiplanar conformation with the 4-pyridyl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angle between the core and pyridyl ring being 74.69 (11)°; intramolecular amide-N—H...O(amide) hydrogen bonds are noted. The 3-ClBA molecule exhibits a small twist as seen in the C6/CO2 dihedral angle of 8.731 (12)°. In the molecular packing, three-molecule aggregates are formed via carboxylic acid-O—H...N(pyridyl) hydrogen bonding. These are connected into a supramolecular tape along [111] through amide-N—H...O(carbonyl) hydrogen bonding. Additional points of contact between molecules include pyridyl and benzoic acid-C—H...O(amide), methylene-C—H...O(carbonyl) and C—Cl...π(pyridyl) interactions so a three-dimensional architecture results. The contributions to the calculated Hirshfeld surface are dominated by H...H (28.5%), H...O/O...H (23.2%), H...C/C...H (23.3%), H...Cl/Cl...H (10.0%) and C...Cl/C...Cl (6.2%) contacts. Computational chemistry confirms the C—Cl...π interaction is weak, and the importance of both electrostatic and dispersion terms in sustaining the molecular packing despite the strong electrostatic term provided by the carboxylic acid-O—H...N(pyridyl) hydrogen bonds.

scholarly journals N,N′-Bis(pyridin-4-ylmethyl)oxalamide benzene monosolvate: crystal structure, Hirshfeld surface analysis and computational study

2019 ◽  
Vol 75 (8) ◽  
pp. 1133-1139 ◽  
Author(s):  
Sang Loon Tan ◽  
Nathan R. Halcovitch ◽  
Edward R. T. Tiekink
Keyword(s):  
Computational Study ◽  
Hirshfeld Surface ◽  
Pyridyl Ring ◽  
Central Plane ◽  
Dispersion Forces ◽  
Amide Hydrogen ◽  
Asymmetric Unit ◽  
Title 1 ◽  
Orthogonal Relationship ◽  
Hirshfeld Surfaces

The asymmetric unit of the title 1:1 solvate, C14H14N4O2·C6H6 [systematic name of the oxalamide molecule: N,N′-bis(pyridin-4-ylmethyl)ethanediamide], comprises a half molecule of each constituent as each is disposed about a centre of inversion. In the oxalamide molecule, the central C2N2O2 atoms are planar (r.m.s. deviation = 0.0006 Å). An intramolecular amide-N—H...O(amide) hydrogen bond is evident, which gives rise to an S(5) loop. Overall, the molecule adopts an antiperiplanar disposition of the pyridyl rings, and an orthogonal relationship is evident between the central plane and each terminal pyridyl ring [dihedral angle = 86.89 (3)°]. In the crystal, supramolecular layers parallel to (10\overline{2}) are generated owing the formation of amide-N—H...N(pyridyl) hydrogen bonds. The layers stack encompassing benzene molecules which provide the links between layers via methylene-C—H...π(benzene) and benzene-C—H...π(pyridyl) interactions. The specified contacts are indicated in an analysis of the calculated Hirshfeld surfaces. The energy of stabilization provided by the conventional hydrogen bonding (approximately 40 kJ mol−1; electrostatic forces) is just over double that by the C—H...π contacts (dispersion forces).

scholarly journals 3-{(E)-[4-(4-Hydroxy-3-methoxyphenyl)butan-2-ylidene]amino}-1-phenylurea: crystal structure and Hirshfeld surface analysis

2018 ◽  
Vol 74 (1) ◽  
pp. 21-27 ◽  
Author(s):  
Ming Yueh Tan ◽  
Karen A. Crouse ◽  
Thahira B. S. A. Ravoof ◽  
Mukesh M. Jotani ◽  
Edward R. T. Tiekink
Keyword(s):  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Dihedral Angles ◽  
Amide Hydrogen ◽  
Asymmetric Unit ◽  
Compound C ◽  
Hirshfeld Surfaces ◽  
Disubstituted Benzene ◽  
Independent Molecules

Two independent molecules (AandB) 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 (Econformation), which is linked in turn to an ethane bridge that links a disubstituted benzene ring. Intramolecular amine-N—H...N(imine) and hydroxyl-O—H...O(methoxy) hydrogen bonds closeS(5) loops in each case. The molecules 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 moleculesAandB viaan eight-membered {...HNCO}2synthon. Further associations between molecules, leading to supramolecular layers in theacplane, are hydrogen bonds of the type hydroxyl-O—H...N(imine) and phenylamine-N—H...O(methoxy). Connections between layers, leading to a three-dimensional architecture, comprise benzene-C—H...O(hydroxy) interactions. A detailed analysis of the calculated Hirshfeld surfaces shows moleculesAandBparticipate in very similar intermolecular interactions and that any variations relate to conformational differences between the molecules.

scholarly journals 4-Amino-N-(2,3-dihydro-1,3-thiazol-2-ylidene)benzenesulfonamide–2,4,6-tris(pyridin-2-yl)-1,3,5-triazine (1/1)

2014 ◽  
Vol 70 (4) ◽  
pp. o402-o403
Author(s):  
Hadi D. Arman ◽  
Trupta Kaulgud ◽  
Edward R. T. Tiekink
Keyword(s):  
Hydrogen Bonding ◽  
Dihedral Angle ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Dihedral Angles ◽  
Central Ring ◽  
Title 1 ◽  
The Third ◽  
Supramolecular Chain

The sulfathiazole molecule in the title 1:1 co-crystal, C9H9N3O2S2·C18H12N6, adopts an approximate L-shape [dihedral angle between the five- and six-membered rings = 86.20 (9)°] and features an intramolecular hypervalent S...O interaction [2.8666 (15) Å]. Overall, the triazine molecule has the shape of a disk as the pendant pyridine rings are relatively close to coplanar with the central ring [dihedral angles = 18.35 (9), 6.12 (9) and 4.67 (9)°]. In the crystal packing, a linear supramolecular chain aligned along [01-1] is formed as a result of amino–pyridyl N—H...N hydrogen bonding withsyn-disposed pyridyl molecules of one triazine, and amine–pyridyl N—H...N hydrogen bonding with the third pydridyl ring of a second triazine molecule. A three-dimensional architecture arises as the chains are connected by C—H...O interactions.

scholarly journals A 1:1:1 co-crystal solvate comprising 2,2′-dithiodibenzoic acid, 2-chlorobenzoic acid and N,N-dimethylformamide: crystal structure, Hirshfeld surface analysis and computational study

2019 ◽  
Vol 75 (4) ◽  
pp. 475-481
Author(s):  
Sang Loon Tan ◽  
Edward R. T. Tiekink
Keyword(s):  
Carboxylic Acid ◽  
Surface Analysis ◽  
Phenyl Ring ◽  
Computational Study ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Hirshfeld Surface Analysis ◽  
Dihedral Angles ◽  
Asymmetric Unit ◽  
Chlorobenzoic Acid

The asymmetric unit of the three-component title compound, 2,2′-dithiodibenzoic acid–2-chlorobenzoic acid–N,N-dimethylformamide (1/1/1), C14H10O4S2·C7H5ClO2·C3H7NO, contains a molecule each of 2,2′-dithiodibenzoic acid (DTBA), 2-chlorobenzoic acid (2CBA) and dimethylformamide (DMF). The DTBA molecule is twisted [the C—S—S—C torsion angle is 88.37 (17)°] and each carboxylic 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 molecule of 2CBA [CO2/C6 dihedral angle = 4.4 (4)°]. In the crystal, the three molecules are connected by hydrogen bonds with the two carboxylic acid residues derived from DTBA and 2CBA forming a non-symmetric eight-membered {...HOCO}2 synthon, and the second carboxylic acid of DTBA linked to the DMF molecule via a seven-membered {...HOCO...HCO} heterosynthon. The three-molecule aggregates are connected into a supramolecular chain along the a axis via DTBA-C—H...O(hydroxyl-2CBA), 2CBA-C—H...O(hydroxyl-DTBA) and DTBA-C—H...S(DTBA) interactions. Supramolecular 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 carboxylic dimer and the phenyl ring of 2CBA. The latter was confirmed by electrostatic potential (ESP) mapping.

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