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 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 A 2:1 co-crystal ofp-nitrobenzoic acid andN,N′-bis(pyridin-3-ylmethyl)ethanediamide: crystal structure and Hirshfeld surface analysis

2016 ◽  
Vol 72 (1) ◽  
pp. 76-82 ◽  
Author(s):  
Sabrina Syed ◽  
Siti Nadiah Abdul Halim ◽  
Mukesh M. Jotani ◽  
Edward R. T. Tiekink
Keyword(s):  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Dihedral Angles ◽  
Inversion Symmetry ◽  
Stacking Interactions ◽  
Nitrobenzoic Acid ◽  
Hirshfeld Surfaces ◽  
Centroid Distance ◽  
Benzene Rings

The title 2:1 co-crystal, 2C7H5NO4·C14H14N4O2, in which the complete diamide molecule is generated by crystallographic inversion symmetry, features a three-molecule aggregate sustained by hydroxyl-O—H...N(pyridyl) hydrogen bonds. Thep-nitrobenzoic acid molecule is non-planar, exhibiting twists of both the carboxylic acid and nitro groups, which form dihedral angles of 10.16 (9) and 4.24 (4)°, respectively, with the benzene ring. The diamide molecule has a conformation approximating to a Z shape, with the pyridyl rings lying to either side of the central, almost planar diamide residue (r.m.s. deviation of the eight atoms being 0.025 Å), and forming dihedral angles of 77.22 (6)° with it. In the crystal, three-molecule aggregates are linked into a linear supramolecular ladder sustained by amide-N—H...O(nitro) hydrogen bonds and orientated along [10-4]. The ladders are connected into a double layerviapyridyl- and benzene-C—H...O(amide) interactions, which, in turn, are connected into a three-dimensional architectureviaπ–π stacking interactions between pyridyl and benzene rings [inter-centroid distance = 3.6947 (8) Å]. An evaluation of the Hirshfeld surfaces confirm the importance of intermolecular interactions involving oxygen atoms as well as the π–π interactions.

scholarly journals Bis[2-(4,5-diphenyl-1H-imidazol-2-yl)-4-nitrophenolato]copper(II) dihydrate: crystal structure and Hirshfeld surface analysis

2019 ◽  
Vol 75 (11) ◽  
pp. 1664-1671 ◽  
Author(s):  
Sailesh Chettri ◽  
Dhiraj Brahman ◽  
Biswajit Sinha ◽  
Mukesh M. Jotani ◽  
Edward R. T. Tiekink
Keyword(s):  
Chelate Ring ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Bidentate Ligands ◽  
Metal Centre ◽  
Hirshfeld Surfaces ◽  
Square Planar ◽  
Intermolecular Contacts

The crystal and molecular structures of the title CuII complex, isolated as a dihydrate, [Cu(C21H14N3O3)2]·2H2O, reveals a highly distorted coordination geometry intermediate between square-planar and tetrahedral defined by an N2O2 donor set derived from two mono-anionic bidentate ligands. Furthermore, each six-membered chelate ring adopts an envelope conformation with the Cu atom being the flap. In the crystal, imidazolyl-amine-N—H...O(water), water-O—H...O(coordinated, nitro and water), phenyl-C—H...O(nitro) and π(imidazolyl)–π(nitrobenzene) [inter-centroid distances = 3.7452 (14) and 3.6647 (13) Å] contacts link the components into a supramolecular layer lying parallel to (101). The connections between layers forming a three-dimensional architecture are of the types nitrobenzene-C—H...O(nitro) and phenyl-C—H...π(phenyl). The distorted coordination geometry for the CuII atom is highlighted in an analysis of the Hirshfeld surface calculated for the metal centre alone. The significance of the intermolecular contacts is also revealed in a study of the calculated Hirshfeld surfaces; the dominant contacts in the crystal are H...H (41.0%), O...H/H...O (27.1%) and C...H/H...C (19.6%).

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

2019 ◽  
Vol 75 (1) ◽  
pp. 1-7 ◽  
Author(s):  
Sang Loon Tan ◽  
Edward R. T. Tiekink
Keyword(s):  
Benzoic Acid ◽  
Dihedral Angle ◽  
Computational Study ◽  
Three Dimensional ◽  
Acid Group ◽  
Hirshfeld Surface ◽  
Carboxylic Acid Group ◽  
Title 1 ◽  
Axis Of Symmetry ◽  
Ring Centroid

The asymmetric unit of the title 1:2 co-crystal, C14H10O4S2·2C7H6O2, comprises half a molecule of dithiodibenzoic acid [systematic name: 2-[(2-carboxyphenyl)disulfanyl]benzoic acid, DTBA], as the molecule is located about a twofold axis of symmetry, and a molecule of benzoic acid (BA). The DTBA molecule is twisted about the disulfide 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 carboxylic 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 molecule [dihedral angle = 3.65 (15)°]. Three-molecule aggregates are formed in the crystal whereby two BA molecules are connected to a DTBA molecule via hydroxy-O—H...O(hydroxy) hydrogen bonds and eight-membered {...HOC=O}2 synthons. These are connected into a supramolecular layer in the ab plane through C—H...O interactions. The interactions between layers to consolidate the three-dimensional architecture are π–π stacking interactions between DTBA and BA rings [inter-centroid separation = 3.8093 (10) Å] and parallel DTBA-hydroxy-O...π(BA) contacts [O...ring centroid separation = 3.9049 (14) Å]. The importance of the specified interactions 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 interaction energies.

scholarly journals 2-(2-Amino-4-nitrophenyl)-7-nitro-4H-3,1-benzoxazin-4-one

2014 ◽  
Vol 70 (2) ◽  
pp. o158-o159
Author(s):  
Edward R. T. Tiekink ◽  
James L. Wardell
Keyword(s):  
Benzene Ring ◽  
Three Dimensional ◽  
Ring System ◽  
Torsion Angles ◽  
Compound C ◽  
Centroid Distance ◽  
Benzene Rings ◽  
Fused Ring ◽  
Fused Ring System ◽  
Dimeric Aggregates

In the title compound, C14H8N4O6, the benzoxazin-4-one fused-ring system (r.m.s. deviation = 0.018 Å) is coplanar with the attached benzene ring [dihedral angle = 0.81 (4)°], there being an intramolecular N—H...N hydrogen bond between them. Each nitro group is twisted out of the plane of the attached benzene ring [O—N—C—C torsion angles = 167.94 (11) and 170.38 (11)°]. In the crystal, amine–nitro N—H...O hydrogen bonds lead to centrosymmetric dimeric aggregates that are connected into a three-dimensional architecture by oxazinyl–nitro C—H...O and π–π interactions [inter-centroid distance between the oxazinyl and terminal benzene rings = 3.5069 (7) Å].

scholarly journals (E)-{[(Butylsulfanyl)methanethioyl]amino}(4-methoxybenzylidene)amine: crystal structure and Hirshfeld surface analysis

2020 ◽  
Vol 76 (2) ◽  
pp. 208-213 ◽  
Author(s):  
Aqilah Fasihah Rusli ◽  
Huey Chong Kwong ◽  
Karen A. Crouse ◽  
Mukesh M. Jotani ◽  
Edward R. T. Tiekink
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Two Dimensional ◽  
Prominent Feature ◽  
Torsion Angles ◽  
Hirshfeld Surfaces ◽  
Butyl Group ◽  
Close Contacts

The title hydrazine carbodithioate, C13H18N2OS2, is constructed about a central and almost planar C2N2S2 chromophore (r.m.s. deviation = 0.0263 Å); the terminal methoxybenzene 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 = methylene and me = methyl]. The most prominent feature of the molecular packing is the formation of centrosymmetric eight-membered {...HNCS}2 synthons, as a result of thioamide-N—H...S(thioamide) hydrogen bonds; these are linked via methoxy-C–H...π(methoxybenzene) interactions to form a linear supramolecular 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 interactions, i.e. the N—H...S and C—H...π interactions 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 methoxybenzene–hydrogen contact (occurring within the chains along the a axis) and between methylene-H atoms (occurring between chains to consolidate the three-dimensional architecture), are largely dispersive in nature.

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 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 [(Z)-N-(3-Fluorophenyl)-O-methylthiocarbamato-κS](triphenylphosphane-κP)gold(I): crystal structure, Hirshfeld surface analysis and computational study

2020 ◽  
Vol 76 (8) ◽  
pp. 1284-1290
Author(s):  
Chien Ing Yeo ◽  
Sang Loon Tan ◽  
Huey Chong Kwong ◽  
Edward R. T. Tiekink
Keyword(s):  
Computational Study ◽  
Close Contact ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Thiolate Ligand ◽  
Intermolecular Contacts ◽  
Stabilization Energies ◽  
Type C ◽  
Dimeric Aggregates ◽  
Linear Geometry

The title phosphanegold(I) thiolate, C26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494 (8) Å] and thiolate-S [2.3007 (8) Å] atoms to define a close to linear geometry [P—Au—S = 176.10 (3)°]. The thiolate ligand is orientated so that the methoxy-O atom is directed towards the Au atom, forming an Au...O close contact of 2.986 (2) Å. In the crystal, a variety of intermolecular contacts are discerned with fluorobenzene-C—H...O(methoxy) and phenyl-C—H...F interactions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C—H...S(thiolate) and phenyl-C—H...π(fluorobenzene, phenyl) interactions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C...H/H...C but this is less than the H...H contacts, at 44.9%. Other significant contributions to the surface come from H...F/F...H [8.1%], H...S/S...H [6.9%] and H...O/O...H [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C—H...π(fluorobenzene) and fluorobenzene-C—H...C(imine) interactions (−37.2 kcal mol−1), and from the fluorobenzene-C—H...F and phenyl-C—H...O interactions (−34.9 kcal mol−1), the latter leading to the dimeric aggregate.

scholarly journals 1-Chloro-4-[2-(4-chlorophenyl)ethyl]benzene and its bromo analogue: crystal structure, Hirshfeld surface analysis and computational chemistry

2019 ◽  
Vol 75 (5) ◽  
pp. 624-631 ◽  
Author(s):  
Mukesh M. Jotani ◽  
See Mun Lee ◽  
Kong Mun Lo ◽  
Edward R. T. Tiekink
Keyword(s):  
Mirror Symmetry ◽  
Three Dimensional ◽  
Molecular Packing ◽  
Molecular Structures ◽  
Ethyl Benzene ◽  
Torsion Angles ◽  
Hirshfeld Surfaces ◽  
First Approximation ◽  
Benzene Rings ◽  
3D Architecture

The crystal and molecular structures of C14H12Cl2, (I), and C14H12Br2, (II), are described. The asymmetric unit of (I) comprises two independent molecules, A and B, each disposed about a centre of inversion. Each molecule 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 = ethylene]. By contrast, the molecule in (II) is twisted, as seen in the dihedral angle of 59.29 (11)° between the benzene rings cf. 0° in (I). The molecular 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 interpenetration. 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 molecular 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 molecules of (I).

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