Conformational preferences in 2-nitrophenylthiolates: interplay between intra- and intermolecular forces; structures of (E)-1-(4-methyl-2-nitrobenzenethiolato)-2-phenylethene, S-(2-nitrophenyl)benzenecarbothiolate and 1-(2-nitrophenylthio)-2,5-pyrrolidinedione

2000 ◽  
Vol 56 (1) ◽  
pp. 58-67 ◽  
Author(s):  
John N. Low ◽  
Emily J. Storey ◽  
Mary McCarron ◽  
James L. Wardell ◽  
George Ferguson ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Nitro Group ◽  
Intermolecular Forces ◽  
Aryl Ring ◽  
Local Energy Minimum ◽  
Conformational Preferences ◽  
A Chain ◽  
Related Compounds ◽  
Scf Calculations ◽  
Intramolecular Forces

In (E)-1-(4-methyl-2-nitrobenzenethiolato)-2-phenylethene, C15H13NO2S (1) (orthorhombic Pbca), the nitro group is almost coplanar with the adjacent aryl ring, but the dihedral angles between the nitro-aryl and styryl fragments is ∼121°. The molecules are linked by paired C—H...O hydrogen bonds in a chain of rings. In S-(2-nitrophenyl)benzenecarbothiolate, C13H9NO3S (2) (monoclinic P21/a), the nitro group is rotated by 33.0 (2)° out of the plane of the adjacent aryl ring and the thiobenzoate group is strongly twisted away from the plane of the disubstituted aryl ring. The molecules of (2) are linked into chains by C—H...O hydrogen bonds, and each chain is linked to two neighbouring chains by means of aromatic π...π stacking interactions. In 1-(2-nitrophenylthio)-2,5-pyrrolidinedione, C10H8N2O4S (3) (monoclinic P21/a), the nitro group is again almost coplanar with the adjacent aryl ring, but the pyrrolidinedione unit is almost orthogonal to the O2NC6H4SN plane. There are three types of C—H...O hydrogen bond in the structure, and these link the molecules into a two-dimensional net. The conformations of these molecules have been investigated by SCF calculations and two energy minima have been identified for each: the molecules of (1) and (3) adopt conformations in their crystals which are close to those at the overall energy minima calculated for isolated molecules, while molecules of (2) adopt a conformation in the crystal close to that calculated for the local energy minimum. Comparisons are made with the structures of some related compounds and it is concluded that, while the nature of the two conformational minima is determined by intramolecular forces, the choice between them is determined primarily by intermolecular forces.

Conformational preferences and supramolecular aggregation in 2-nitrophenylthiolates: disulfides and thiosulfonates

2000 ◽  
Vol 56 (5) ◽  
pp. 893-905 ◽  
Author(s):  
Christopher Glidewell ◽  
John N. Low ◽  
James L. Wardell
Keyword(s):  
Hydrogen Bonds ◽  
Nitro Group ◽  
Molecular Conformation ◽  
Three Dimensional ◽  
Asymmetric Unit ◽  
Aryl Ring ◽  
Conformational Preferences ◽  
Independent Molecules ◽  
Centrosymmetric Dimers ◽  
Supramolecular Aggregation

In each of the asymmetrically substituted disulfides 2-nitro-4′-methyldiphenyl disulfide, C13H11NO2S2 (1), 2-nitro-4′-chlorodiphenyl disulfide, C12H8ClNO2S2 (2), 2,4-dinitro-4′-methyldiphenyl disulfide, C13H10N2O4S2 (3), and 2,4-dinitrophenyl-2′-methoxycarbonylmethyl disulfide, C9H8N2O6S2 (4), and in both of the symmetrically substituted disulfides bis(2-nitrophenyl) disulfide, C12H8N2O4S2 (5), and bis(2-nitro-4-trifluoromethylphenyl) disulfide, C14H6F6N2O4S2 (6), the 2-nitro groups are essentially coplanar with the adjacent aryl ring and the S atom remote from the nitrated aryl ring is also essentially coplanar and transoid to the nitro group. In S-(2-nitrophenyl) 2-nitrobenzene thiosulfonate, C12H8N2O6S2 (7), which contains three independent molecules in the asymmetric unit, all six of the independent nitro groups are twisted out of the plane of the adjacent aryl rings. The crystal structures of (1)–(3) contain isolated molecules, that of (4) contains centrosymmetric dimers held together by C—H...O hydrogen bonds, while in the structures of (5)—(7), respectively, the C—H...O hydrogen bonds generate one-, two- and three-dimensional arrays. The interplay between molecular conformation and supramolecular aggregation is discussed.

scholarly journals Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products

2021 ◽  
Vol 77 (4) ◽  
pp. 335-340
Author(s):  
Chayanna Harish Chinthal ◽  
Hemmige S. Yathirajan ◽  
Nagaraja Manju ◽  
Balakrishna Kalluraya ◽  
Sabine Foro ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Intermolecular Interactions ◽  
Cycloaddition Reactions ◽  
Independent Components ◽  
Analogous Compound ◽  
A Chain ◽  
Related Compounds ◽  
Centrosymmetric Dimers

Cycloaddition reactions between 3-(5-aryloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-(thiophen-2-yl)prop-2-en-1-ones and thiosemicarbazide leads to the formation of reduced 3,4′-bipyrazole-2-carbothioamides. Further cycloaddition of these intermediates with either diethyl acetylenedicarboxylate or 4-bromophenacyl bromide leads to reduced 3,4′-bipyrazoles carrying oxothiazole or thiazole substituents, respectively. The structures of two representative intermediates and two representative products established unambiguously the regiochemistry of the cycloaddition reactions. The molecules of 3′-methyl-5′-(2-methylphenoxy)-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-carbothioamide, C25H23N5OS2 (Ia), are linked by N—H...N hydrogen bonds to form simple C(8) chains. The analogous compound 5′-(2,4-dichlorophenoxy)-3′-methyl-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-carbothioamide hemihydrate crystallizes as a hemihydrate, C24H19Cl2N5OS2·0.5H2O (Ib), and the independent components are linked into a chain of spiro-fused R 4 4(20) rings by a combination of O—H...N and N—H...O hydrogen bonds. In the structure of ethyl (Z)-2-{2-[3′-methyl-1′-phenyl-5-(thiophen-2-yl)-5′-(2-methylphenoxy)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-yl]-4-oxo-4,5-dihydrothiazol-5-ylidene}acetate, C31H27N5O4S2 (II), inversion-related pairs of molecules are linked by paired C—H...π(arene) hydrogen bonds to form cyclic centrosymmetric dimers, but there are no direction-specific intermolecular interactions in 4-(4-bromophenyl)-2-[5′-(2,4-dichlorophenoxy)-3′-methyl-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-yl]-4-thiazole, C32H22BrCl2N5OS2 (III). Comparisons are made with the structures of some related compounds.

Interplay of hydrogen bonds, iodo...nitro interactions and aromatic π...π stacking interactions in iodo-nitroanilines

2002 ◽  
Vol 58 (4) ◽  
pp. 701-709 ◽  
Author(s):  
Simon J. Garden ◽  
Silvia P. Fontes ◽  
James L. Wardell ◽  
Janet M. S. Skakle ◽  
John N. Low ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Nitro Group ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Single Type ◽  
Stacking Interactions ◽  
Π Stacking ◽  
Independent Molecules ◽  
Related Compounds ◽  
Centrosymmetric Dimers

Molecules of 2-iodo-5-nitroaniline (I) are linked by N—H...O hydrogen bonds into centrosymmetric dimers and by asymmetric three-centre iodo...nitro interactions into chains, so forming chains of fused centrosymmetric rings: these chains are linked by aromatic π...π stacking interactions to form a three-dimensional structure. In the isomeric 4-iodo-2-nitroaniline (II), each of the two independent molecules forms hydrogen-bonded chains that are linked by two-centre iodo...nitro interactions into sheets of two types, each containing only a single type of molecule: π...π stacking interactions are absent. In 2,4-diiodo-3-nitroaniline (III), where the nitro group is almost orthogonal to the aryl ring, a combination of N—H...O hydrogen bonds and two distinct two-centre iodo...nitro interactions links the molecules into a three-dimensional framework that is reinforced by aromatic π...π stacking interactions. Bond lengths and conformations are discussed and comparisons are drawn with related compounds.

Nine closely related tetrahydro-1,4-epoxy-1-benzazepines carrying pendant heterocyclic substituents: hydrogen-bonded supramolecular assembly in zero, one and two dimensions

2012 ◽  
Vol 68 (3) ◽  
pp. o131-o140 ◽  
Author(s):  
Maria C. Blanco ◽  
Alirio Palma ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Supramolecular Assembly ◽  
Two Dimensions ◽  
Specific Interactions ◽  
Space Groups ◽  
Racemic Mixtures ◽  
Sheet Structure ◽  
A Chain ◽  
Related Compounds

The structures are reported of nine closely related tetrahydro-1,4-epoxy-1-benzazepines carrying pendant heterocyclic substituents, namely: 2-exo-(5-nitrofuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C14H12N2O4, (I), 7-fluoro-2-exo-(1-methyl-1H-pyrrol-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H15FN2O, (II), 7-fluoro-2-exo-(5-methylfuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14FNO2, (III), 7-fluoro-2-exo-(3-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14FNOS, (IV), 7-fluoro-2-exo-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14FNOS, (V), 7-chloro-2-exo-(5-methylfuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H14ClNO2, (VI), 2-exo-(5-methylfuran-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C16H14F3NO3, (VII), 2-exo-(3-methylthiophen-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C16H14F3NO2S, (VIII), and 2-exo-(5-nitrofuran-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro-1,4-epoxy-1H-1-benzazepine, C15H11F3N2O5, (IX). All nine compounds crystallize in centrosymmetric space groups as racemic mixtures with configuration (2RS,4SR). There are no direction-specific interactions between the molecules in (V). The molecules in (III), (IV), (VI) and (VII) are linked into simple chains, by means of a single C—H...O hydrogen bond in each of (III), (VI) and (VII), and by means of a single C—H...π(arene) hydrogen bond in (IV), while the molecules in (VIII) are linked into a chain of rings. In each of (I) and (II), a combination of one C—H...O hydrogen bond and one C—H...π(arene) hydrogen bond links the molecules into sheets, albeit of completely different construction in the two compounds. In (IX), the sheet structure is built from a combination of four independent C—H...O hydrogen bonds and one C—H...π(arene) hydrogen bond. Comparisons are made with some related compounds.

A chain of π-stacked molecules in 4-(2-chlorophenyl)pyrrolo[1,2-a]quinoxaline and a hydrogen-bonded sheet in (4RS)-4-(1,3-1,3-benzodioxol-6-yl)-4,5-dihydropyrrolo[1,2-a]quinoxaline

2013 ◽  
Vol 69 (5) ◽  
pp. 544-548 ◽  
Author(s):  
Juan C. Castillo ◽  
Rodrigo Abonía ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Double Bond ◽  
Hydrogen Bonds ◽  
Electron Delocalization ◽  
Central Ring ◽  
Stacking Interaction ◽  
Bond Lengths ◽  
Π Stacking Interaction ◽  
Conformation Intermediate ◽  
A Chain ◽  
Related Compounds

In the molecule of 4-(2-chlorophenyl)pyrrolo[1,2-a]quinoxaline, C17H11ClN2, (I), the bond lengths are consistent with electron delocalization in the two outer rings of the fused tricyclic system, with a localized double bond in the central ring. The molecules of (I) are linked into chains by a π–π stacking interaction. In (4RS)-4-(1,3-benzodioxol-6-yl)-4,5-dihydropyrrolo[1,2-a]quinoxaline, C18H14N2O2, (II), the central ring of the fused tricyclic system adopts a conformation intermediate between screw-boat and half-chair forms. A combination of N—H...O and C—H...π(arene) hydrogen bonds links the molecules of (II) into a sheet. Comparisons are made with related compounds.

A concise, efficient and versatile synthesis of amino-substituted benzo[b]pyrimido[5,4-f]azepines: synthesis and spectroscopic characterization, together with the molecular and supramolecular structures of three products and one intermediate

2018 ◽  
Vol 74 (3) ◽  
pp. 312-320 ◽  
Author(s):  
Lina M. Acosta Quintero ◽  
Isidro Burgos ◽  
Alirio Palma ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Mass Spectrometry ◽  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Spectroscopic Characterization ◽  
Supramolecular Structures ◽  
Boat Conformation ◽  
Reaction Intermediates ◽  
A Chain ◽  
Related Compounds ◽  
C Nmr

A concise, efficient and versatile synthesis of amino-substituted benzo[b]pyrimido[5,4-f]azepines is described: starting from a 5-allyl-4,6-dichloropyrimidine, the synthesis involves base-catalysed aminolysis followed by intramolecular Friedel–Crafts cyclization. Four new amino-substituted benzo[b]pyrimido[5,4-f]azepines are reported, and all the products and reaction intermediates have been fully characterized by IR,1H and13C NMR spectroscopy and mass spectrometry, and the molecular and supramolecular structures of three products and one intermediate have been determined. In each ofN,2,6,11-tetramethyl-N-phenyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepin-4-amine, C22H24N5, (III), 4-(1H-benzo[d]imidazol-1-yl)-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, which crystallizes as a 0.374-hydrate, C21H19N5·0.374H2O, (VIIIa), and 6,7,9,11-tetramethyl-4-(5-methyl-1H-benzo[d]imidazol-1-yl)-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, C24H25N5, (VIIIc), the azepine ring adopts a boat conformation, but with a different configuration at the stereogenic centre in (VIIIc), as compared with (III) and (VIIIa). In the intermediate 5-allyl-6-(1H-benzo[d]imidazol-1-yl)-N-methyl-N-(4-methylphenyl)pyrimidin-4-amine, C22N21N5, (VIIb), the immediate precursor of 4-(1H-benzo[d]imidazol-1-yl)-6,8,11-trimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine, (VIIIb), the allyl group is disordered over two sets of atomic sites having occupancies of 0.688 (5) and 0.312 (5). The molecules of (III) are linked into chains by a C—H...π(pyrimidine) hydrogen bond, and those of (VIIb) are linked into complex sheets by three hydrogen bonds, one of the C—H...N type and two of C—H...π(arene) type. The molecules of the organic component in (VIIIa) are linked into a chain of rings by two C—H...π(arene) hydrogen bonds, and these chains are linked into sheets by the water components; a single weak C—H...N hydrogen bond links molecules of (VIIIc) into centrosymmetricR22(10) dimers. Comparisons are made with some related compounds.

scholarly journals Twelve 4-(4-methoxyphenyl)piperazin-1-ium salts containing organic anions: supramolecular assembly in one, two and three dimensions

2019 ◽  
Vol 75 (10) ◽  
pp. 1494-1506 ◽  
Author(s):  
Haruvegowda Kiran Kumar ◽  
Hemmige S. Yathirajan ◽  
Sabine Foro ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Supramolecular Assembly ◽  
Organic Anions ◽  
Three Dimensions ◽  
Space Group ◽  
Dimensional Array ◽  
A Chain ◽  
Related Compounds

Twelve 4-(4-methoxyphenyl)piperazin-1-ium salts containing organic anions have been prepared and structurally characterized. The monohydrated benzoate, 4-fluorobenzoate, 4-chlorobenzoate and 4-bromobenzoate salts, C11H17N2O+·C7H5O2 −·H2O (I), C11H17N2O+·C7H4FO2 −·H2O (II), C11H17N2O+·C7H4ClO2 −·H2O (III), and C11H17N2O+·C7H4BrO2 −·H2O (IV), respectively, are isomorphous and all exhibit disorder in the 4-methoxyphenyl unit: the components are linked by N—H...O and O—H...O hydrogen bond to form chains of rings. The unsolvated 2-hydroxybenzoate, pyridine-3-carboxylate and 2-hydroxy-3,5-dinitrobenzoate salts, C11H17N2O+·C7H5O3 − (V), C11H17N2O+·C6H4NO2 − (VI) and C11H17N2O+·C7H3N2O7 − (VII), respectively, are all fully ordered: the components of (V) are linked by multiple N—H...O hydrogen bonds to form a chain of rings; those of (VI) are linked into a three-dimensional framework by a combination of N—H...O, C—H...O and C—H...N hydrogen bonds and those of (VII), where the anion has a structure reminiscent of the picrate anion, are linked into a three-dimensional array by N—H...O and C—H...O hydrogen bonds. The hydrogensuccinate and hydrogenfumarate salts, C11H17N2O+·C4H5O4 − (VIII) and C11H17N2O+·C4H3O3 − (IX), respectively, are isomorphous, and both exhibit disorder in the anionic component: N—H...O and O—H...O hydrogen bonds link the ions into sheets, which are further linked by C—H...π(arene) interactions. The anion of the hydrogenmaleate salt, C11H17N2O+·C4H3O3 − (X), contains a very short and nearly symmetrical O...H...O hydrogen bond, and N—H...O hydrogen bonds link the anions into chains of rings. The ions in the trichloroacetate salt, C11H17N2O+·C2Cl3O2 − (XI), are linked into simple chains by N—H...O hydrogen bonds. In the hydrated chloranilate salt, 2C11H17N2O+·C6Cl2O4 2−·2H2O (XII), which crystallizes as a non-merohedral twin, the anion lies across a centre of inversion in space group P21/n, and a combination of N—H...O and O—H...O hydrogen bonds generates complex sheets. Comparisons are made with the structures of some related compounds.

scholarly journals Conversion of diarylchalcones into 4,5-dihydropyrazole-1-carbothioamides: molecular and supramolecular structures of two precursors and three products

2020 ◽  
Vol 76 (3) ◽  
pp. 360-365 ◽  
Author(s):  
Mohammed A. E. Shaibah ◽  
Hemmige S. Yathirajan ◽  
Asma ◽  
Nagaraja Manju ◽  
Balakrishna Kalluraya ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Pyrazole Ring ◽  
Supramolecular Structures ◽  
Phenyl Substituent ◽  
Aryl Ring ◽  
Envelope Conformation ◽  
Cyclocondensation Reaction ◽  
Related Compounds ◽  
Axial Site

Chalcones of type 4-XC6H4C(O)CH=CHC6H4(OCH2CCH)-4, where X = Cl, Br or MeO, have been converted to the corresponding 4,5-dihydropyrazole-1-carbothioamides using a cyclocondensation reaction with thiosemicarbazide. The chalcones 1-(4-chlorophenyl)-3-[4-(prop-2-ynyloxy)phenyl]prop-2-en-1-one, C18H13ClO2, (I), and 1-(4-bromophenyl)-3-[4-(prop-2-ynyloxy)phenyl]prop-2-en-1-one, C18H13BrO2, (II), are isomorphous, and their molecules are linked into sheets by two independent C—H...π(arene) interactions, both involving the same aryl ring with one C—H donor approaching each face. In each of the products (RS)-3-(4-chlorophenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide, C19H16ClN3OS, (IV), (RS)-3-(4-bromophenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide, C19H16BrN3OS, (V), and (RS)-3-(4-methoxyphenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide, C20H19N3O2S, (VI), the reduced pyrazole ring adopts an envelope conformation with the C atom bearing the 4-prop-2-ynyloxy)phenyl substituent, which occupies the axial site, displaced from the plane of the four ring atoms. Compounds (IV) and (V) are isomorphous and their molecules are linked into chains of edge-fused rings by a combination of N—H...S and C—H...S hydrogen bonds. The molecules of (VI) are linked into sheets by a combination of N—H...S, N—H...N and C—H...π(arene) hydrogen bonds. Comparisons are made with the structures of some related compounds.

The preparation of sodium 4-Amino-3-nitro-benzenesulfonate and some related compounds

1982 ◽  
Vol 35 (8) ◽  
pp. 1727 ◽  
Author(s):  
J Rosevear ◽  
JFK Wilshire
Keyword(s):  
Sodium Hydroxide ◽  
Nitro Group ◽  
Sodium Salt ◽  
Sulfonic Acid ◽  
Sodium Hydroxide Solution ◽  
Hydroxide Solution ◽  
Dilute Sodium Hydroxide ◽  
Related Compounds

The sodium salt of 4-amino-3-nitrobenzenesulfonic acid (O-nitroaniline-p-sulfonic acid) has been prepared by the action of dilute sodium hydroxide solution on ethyl [(4-chlorosulfonyl-2-nitro)- phenyllcarbamate. Central to this synthesis is the finding that the N-ethoxycarbonyl group, when located ortho to a nitro group (but not to a bromo group), is readily removed by dilute sodium hydroxide solution.

scholarly journals Cyclooctanaminium hydrogen succinate monohydrate

2012 ◽  
Vol 68 (4) ◽  
pp. o1204-o1204 ◽  
Author(s):  
Sanaz Khorasani ◽  
Manuel A. Fernandes
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Ammonium Cation ◽  
Water Molecules ◽  
Hydrated Salt ◽  
A Chain ◽  
Hydrogen Bonded

In the title hydrated salt, C8H18N+·C4H5O4−·H2O, the cyclooctyl ring of the cation is disordered over two positions in a 0.833 (3):0.167 (3) ratio. The structure contains various O—H.·O and N—H...O interactions, forming a hydrogen-bonded layer of molecules perpendicular to thecaxis. In each layer, the ammonium cation hydrogen bonds to two hydrogen succinate anions and one water molecule. Each hydrogen succinate anion hydrogen bonds to neighbouring anions, forming a chain of molecules along thebaxis. In addition, each hydrogen succinate anion hydrogen bonds to two water molecules and the ammonium cation.

Sign in / Sign up

Export Citation Format

Share Document